JP2022110943A - Resin composition, method for manufacturing laminate and cured film - Google Patents

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 The present disclosure relates to a resin composition, a method for producing a laminate, and a cured film.

In recent years, there has been an increasing demand for electronic devices to be smaller, lighter, and more functional. In response to these demands, miniaturization, thinning, and high-density mounting are also required for semiconductor devices that constitute electronic equipment (see, for example, Non-Patent Document 1).

Fan-out wafer level packages and multi-die wafer level packages have been proposed as semiconductor packages that can be made smaller and thinner. etc.

A process called RDL (Redistribution layer) first has been proposed as one of the manufacturing processes of a semiconductor device having a thin and high-density wiring structure such as a fan-out wafer level package. In this step, a thin-film wiring layer is formed on a temporary fixing layer formed on a support, then a semiconductor element is connected to the wiring layer, and then the semiconductor element is sealed with a sealing material to fabricate a semiconductor device. . After that, the semiconductor device is separated from the support.

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, sputtering, CVD (chemical vapor deposition), PVD (physical vapor deposition), lithography, plating, wet etching, cleaning, hardening of interlayer insulating films, CMP (chemical mechanical polishing: Chemical mechanical polishing), die bonding, mounting, annealing, packaging, and other processes are required to prevent peeling between the support and the wiring layer.

As a technique for such a temporary fixing layer, for example, the technique described in Patent Document 1 is known. That is, in Patent Document 1, a separation layer and an adhesive layer, which are temporary fixing layers, are formed on the support side, and a semiconductor device is formed thereon. Then, a laser beam is irradiated from the support side to change the properties of the separation layer, thereby changing the adhesive strength. It is disclosed to release a semiconductor device by lowering the .

Further, in Patent Document 2, a temporary fixing sheet containing a resin composition containing an acrylic material is laminated on a light-transmitting support, and after temporarily fixing a semiconductor chip on the temporary fixing sheet, the semiconductor chip is sealed. Covering with a stopper, grinding the encapsulant, and forming wiring on the surface of the semiconductor chip are performed in this order, and then irradiating the temporary fixing sheet with radiant energy from the light-transmitting support side. discloses decomposing a resin composition to separate a temporary fixing sheet from a semiconductor device.

JP 2018-93021 JP 2017-98481

“Semiconductor Technology Yearbook 2013 Packaging/Mounting”, Nikkei Business Publications, pp.41-50.

When manufacturing a plurality of semiconductor electronic components on a support substrate such as a fan-out wafer level package, fine wiring layers, etc. with warpage suppressed are formed on the support by using the above-mentioned RDL first process. Therefore, it is possible to further reduce the size and thickness of the semiconductor device.

However, in the method described in Patent Literature 1, the temporary fixing layer consists of two layers, the adhesive layer and the release layer, and therefore the process for producing the temporary fixing layer is complicated.

In the method described in Patent Document 2, a resin composition containing an acrylic material is used to produce the temporary fixing sheet, so the temporary fixing sheet has a heat resistance of about 150°C. Therefore, when a target object is heat-treated at 200° C. or more in manufacturing a semiconductor device, voids or the like are generated in the temporary fixing sheet due to decomposition of the acrylic material, and the temporary fixing sheet and the semiconductor chip or the light-transmitting support are separated from each other. Delamination may occur during

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, from the viewpoint of suppressing damage to the laminate, the peelability of the laminate is improved. Excellent is desirable.

The present disclosure has been made in view of the above, a resin composition capable of forming a cured film having excellent heat resistance and peelability when separating the laminate from the support, and a laminate using the resin composition An object of the present invention is to provide a method for producing a body and a cured film obtained by curing the resin composition.

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

In general formula (1), X represents a tetravalent organic group and Y represents a divalent organic group. ^R6 and ^R7 each independently represent a hydrogen atom or a monovalent organic group.
<6> The resin composition according to <5>, wherein the monovalent organic group includes a group represented by the following general formula (2).

In general formula (2), R ⁸ to R ¹⁰ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R ^x represents a divalent linking group.
<7> The resin composition according to any one of <1> to <6>, further comprising a polymerizable monomer and a thermal polymerization initiator.
<8> The resin composition according to any one of <1> to <7>, which is used for the treatment (d) below.
(d) removing the residue of the cured film remaining on the laminate after being separated from the support;
<9> The resin composition according to <8>, wherein in (d), the residue of the cured film remaining on the laminate can be removed by solvent treatment.

<10> A step of preparing the resin composition according to any one of <1> to <9>;
forming a cured film of the resin composition on a support;
A step of producing a laminate on the cured film;
separating the laminate from the support;
A method of manufacturing a laminate comprising:
<11> The method for producing a laminate according to <10>, wherein the support has a thermal expansion coefficient of 3 ppm/K to 15 ppm/K at 25°C to 300°C.
<12> The method for producing a laminate according to <10> or <11>, wherein the support has a thickness of 100 μm to 10000 μm, and has a transmittance of 90% or more for light having a wavelength of 355 nm.
<13> The laminate according to any one of <10> to <12>, wherein the laminate is separated from the support after irradiating the cured film with an active energy ray to modify the cured film. Production method.
<14> The method for producing a laminate according to any one of <10> to <13>, further comprising removing a residue of the cured film remaining on the laminate after being separated from the support. .
<15> The method for producing a laminate according to any one of <10> to <14>, wherein the heating temperature for forming the cured film is 100°C to 450°C.
<16> The method for producing a laminate according to any one of <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 comprising a wiring layer, an insulating layer and a semiconductor chip,
The step of fabricating the laminate comprises: forming the wiring layer on the cured film; forming the insulating layer that insulates at least 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 producing a laminate according to <17>, wherein the step of producing the laminate further includes 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 <1> to <9>.

According to the present disclosure, a resin composition capable of forming a cured film having excellent heat resistance and peelability when separating a laminate from a support, a method for producing a laminate using the resin composition, and the resin composition A cured film obtained by curing an object can be provided.

4A to 4D are drawings showing steps of a method for manufacturing a semiconductor device according to an embodiment of the present disclosure; 4A to 4D are drawings showing steps of a method for manufacturing a semiconductor device according to an embodiment of the present disclosure; 4A to 4D are drawings showing steps of a method for manufacturing a semiconductor device according to an embodiment of the present disclosure;

Hereinafter, embodiments for implementing the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and their ranges, which do not limit the present disclosure.

In the present disclosure, “A or B” may include either A or B, or may include both.
In the present disclosure, the term "process" includes a process that is independent of other processes, and even if the purpose of the process is achieved even if it cannot be clearly distinguished from other processes. .
In the present disclosure, the numerical range indicated using "-" includes the numerical values before and after "-" as the minimum and maximum values, respectively.
In the numerical ranges described step by step in the present disclosure, the upper limit or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described step by step. . Moreover, in the numerical ranges described in the present disclosure, the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.
In the present disclosure, each component may contain multiple types of applicable substances. When there are multiple types of substances corresponding to each component in the composition, the content rate or content of each component is the total content rate or content of the multiple types of substances present in the composition unless otherwise specified. means quantity.
In the present disclosure, the term “layer” or “film” refers to the case where the layer or film is formed in the entire region when observing the region where the layer or film is present, and only a part of the region. It also includes the case where it is formed.
In the present disclosure, the average thickness of a layer or film is a value obtained by measuring the thickness of the target layer or film at five points and giving the arithmetic mean value.
The thickness of a layer or film can be measured using a micrometer or the like. In this disclosure, where the thickness of a layer or film can be measured directly, it is measured using a micrometer. On the other hand, when measuring the thickness of one layer or the total thickness of a plurality of layers, the thickness may be measured by observing the cross section of the object to be measured using an electron microscope.
In the present disclosure, "(meth)acrylic group" means "acrylic group" and "methacrylic group".
When embodiments are described in the present disclosure with reference to drawings, the configurations of the embodiments are not limited to the configurations shown in the drawings. In addition, the sizes of the members in each drawing are conceptual, and the relative relationship between the sizes of the members is not limited to this.

<Resin composition>
The resin composition of the present disclosure contains a polyimide precursor and is used for the following treatments (a) to (c).
(a) forming a cured film of the resin composition on a support;
(b) producing a laminate on the cured film;
(c) separating the laminate from the support;

The resin composition of the present disclosure can form a cured film that is excellent in heat resistance and peelability when the laminate is separated from the support. The reason for this is that since the resin composition contains a polyimide precursor, the cured film of the resin composition produced on the support has excellent heat resistance, and the cured film is exposed to active energy rays such as laser light. It is presumed that this is because when the cured film is irradiated, when the cured film is subjected to heat treatment, or the like, the properties of the cured film are altered, resulting in excellent releasability when the laminate is separated from the support. Furthermore, the cured film obtained by curing the resin composition of the present disclosure functions both as an adhesive layer that bonds the laminate and the support, and as a release layer that allows the laminate to be separated from the support by altering the properties. do. Therefore, when using the resin composition of the present disclosure in a method for manufacturing a laminate, it is not necessary to form both an adhesive layer and a peeling layer, and the manufacturing process for the laminate can be simplified.

The polyimide precursor may contain a polyimide precursor having a polymerizable unsaturated bond. As a result, when the resin composition contains at least one of the polymerizable monomer and the thermal polymerization initiator described later, preferably both the polymerizable monomer and the thermal polymerization initiator, the properties of the cured film (e.g., thermal properties) are improved. tend to be able to
Examples of polymerizable unsaturated bonds include carbon-carbon double bonds.

It is preferable that the cured film obtained by curing the resin composition of the present disclosure is not degraded after being heat-treated at 100° C. to 400° C. for 4 hours or less. More specifically, the deterioration of the cured film includes thermal decomposition, peeling, change in removability, and the like.

The resin composition of the present disclosure is preferably used for the treatment (d) below.
(d) removing the residue of the cured film remaining on the laminate after being separated from the support;
For example, when the cured film is irradiated with an active energy ray such as a laser beam, or when the cured film is subjected to a heat treatment, the cured film deteriorates and the laminate is separated from the support. Residues of the cured film may adhere to the laminated body after the coating. Therefore, it is preferable to remove the residue of the cured film remaining on the laminate by the treatment (d) described above.

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

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

In general formula (1), X represents a tetravalent organic group and Y represents a divalent organic group. ^R6 and ^R7 each independently represent 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, R ⁶ and R ⁷ in the plurality of structural units may be the same or different. may be

In the 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 benzene ring, naphthalene ring, and phenanthrene ring. Among these, a benzene ring is preferable 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 substituents on the aromatic ring include alkyl groups, fluorine atoms, halogenated alkyl groups, hydroxyl groups, amino groups and the like.
When the tetravalent organic group represented by X contains a benzene ring, the tetravalent organic group represented by X preferably contains 1 to 4 benzene rings, and contains 1 to 3 benzene rings. is more preferred, and it is even more preferred to contain one or two benzene rings.
When the tetravalent organic group represented by X contains two or more benzene rings, each benzene ring may be connected by 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 —; each R ^A independently represents a hydrogen atom, an alkyl group or a phenyl group), Siloxane bond (-O-(Si(R ^B ) ₂ -O-) _n ; each R ^B 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 in which at least two of these linking groups are combined. In addition, two benzene rings may be bonded at two locations 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.

In general formula (1), the -COOR ⁶ group and the -CONH- group are preferably positioned ortho to each other, and the -COOR ⁷ and -CO- groups are preferably positioned ortho to each other.

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

In formula (D), A and B are each independently a single bond, a methylene group, a methylene halide group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-) or a silylene bond (—Si(R ^A ) ₂ —; each R ^A independently represents a hydrogen atom, an alkyl group or a phenyl group), and both A and B are not single bonds.

In formula (E), C is a single bond, or 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 —; each R ^A independently represents a hydrogen atom, an alkyl group or a phenyl group), a siloxane bond (—O—(Si( ^{R B} ) ₂ —O—) _n ; 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 in which at least two of these are combined. Moreover, C may have a structure represented by the following formula (C1).

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 1 carbon atom. or 2 alkylene groups are more preferred.
Specific examples of the alkylene group represented by C in formula (E) include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene; methylmethylene; methylethylene group, ethylmethylene group, dimethylmethylene group, 1,1-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, ethylethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1-ethyltrimethylene group, 2-ethyltrimethylene group, 1,1-dimethyltrimethylene 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- branched chain alkylene groups such as a dimethyltetramethylene group, a 1,3-dimethyltetramethylene group, a 2,3-dimethyltetramethylene group and a 1,4-dimethyltetramethylene group; Among these, a methylene group is preferred.

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. More preferably, it is a halogenated alkylene group having 1 to 3 carbon atoms.
Specific examples of the halogenated alkylene group represented by C in formula (E) include at least one hydrogen atom contained in the alkylene group represented by C in the above formula (E) being a fluorine atom, a chlorine atom, or the like. An alkylene group substituted with a halogen atom is mentioned. Among these, a fluoromethylene group, a difluoromethylene group, a hexafluorodimethylmethylene group and the like are preferable.

The alkyl group represented by R ^A or R ^B contained in the silylene bond or siloxane bond is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. is more preferred, and an alkyl group having 1 or 2 carbon atoms is even more preferred. Specific examples of the alkyl group represented by R ^A or R ^B include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group and the like. mentioned.

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 preferable.
C in Formula (E) is preferably a single bond, an ether bond, a carbonyl group, or the like.

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.

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

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, or 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 —; each R ^A independently represents a hydrogen atom, an alkyl group or a phenyl group.), a siloxane bond (—O—(Si( ^{R B} ) ₂ —O—) _n ; , 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 in which at least two of these are combined. D may also have a structure represented by the above formula (C1). Specific examples of D in formula (G) are the same as the specific examples of C in formula (E).
D in the general formula (G) is preferably a single bond.

The alkyl group represented by R in general formula (F) or general formula (G) is preferably an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms. More preferably, it is 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 methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, and the like.

The alkoxy group represented by R in the general formula (F) or general formula (G) is preferably an alkoxy group having 1 to 10 carbon atoms, preferably an alkoxy group having 1 to 5 carbon atoms. More preferably, it is 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 methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s- butoxy group, t-butoxy group and the like.

The halogenated alkyl group represented by R in the general formula (F) or general formula (G) is preferably a halogenated alkyl group having 1 to 5 carbon atoms, and a halogenated alkyl group having 1 to 3 carbon atoms. An alkyl group is more preferred, and a halogenated alkyl group having 1 or 2 carbon atoms is even more preferred.
Specific examples of the halogenated alkyl group represented by R in general formula (F) or general formula (G) include at least Examples thereof include alkyl groups in which one hydrogen atom 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 and the like are preferable.

n in general formula (F) or general formula (G) is each independently preferably 0 to 2, more preferably 0 or 1, and still more preferably 0.

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. and the like.

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. More preferably, it is an alkylene group with a number of 1-10.
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, and a 2-methylpentamethylene group. , 2-methylhexamethylene group, 2-methylheptamethylene group, 2-methyloctamethylene group, 2-methylnonamethylene group, 2-methyldecamethylene group and the like.

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

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. 1 to 4 alkylene oxide structures are more preferred. 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 number of unit structures in the polyalkylene oxide structure may be one, or two or more.

As the divalent group having a polysiloxane structure represented by Y, 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. A divalent group having a polysiloxane structure is included.
Specific examples of the alkyl group having 1 to 20 carbon atoms bonded to the silicon atom in the polysiloxane structure include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n- octyl group, 2-ethylhexyl group, n-dodecyl group and the like. Among these, a methyl group is preferred.
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. When the aryl group has a substituent, specific examples of the 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 phenyl group, naphthyl group, benzyl group and the like. 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 two or more types.
A silicon atom constituting a divalent group having a polysiloxane structure represented by Y is an NH group in the general formula (1) via an alkylene group such as a methylene group, an ethylene group, an arylene group such as a phenylene group, or the like. may be combined with

The combination of the tetravalent organic group represented by X and the divalent organic group represented by Y in the general formula (1) is not particularly limited. As a combination of a tetravalent organic group represented by X and a divalent organic group represented by Y, X is a combined use of a group represented by formula (A) and a group represented by formula (E) and Y is a combination of groups represented by formula (G); X is a combination of a group represented by formula (D) and a group represented by formula (E); A combination of represented groups and the like can be mentioned.
By using a group represented by the formula (A) and a group represented by the formula (E) as X in combination, and using a group represented by the general formula (G) as Y, a relatively low temperature of 300 ° C. or less Even if the heat treatment is performed at , the elastic modulus of the obtained polyimide resin tends to be further improved.
When X is a combination of a group represented by formula (A) and a group represented by formula (E), a group XA represented by formula (A) and a group XE represented by formula (E) The number-based ratio (XA/XE) is preferably in the range of 1/99 to 99/1, more preferably in the range of 50/50 to 90/10, 70/30 to 90/10 is more preferably in the range of

R ⁶ and R ⁷ each independently represent a hydrogen atom or a monovalent organic group, and from the viewpoint of removability of the cured film residue adhering to the laminate after peeling from the support, R ⁶ and R ⁷ 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, an aliphatic hydrocarbon group having 1 or 2 carbon atoms or the following general formula It more preferably contains a group represented by (2), and more 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-line transmittance is high, and even when cured at a low temperature of 300 ° C. or less. It tends to form a good cured film.
Specific examples of aliphatic hydrocarbon groups having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and the like.

In general formula (2), R ⁸ to R ¹⁰ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R ^x represents a divalent linking group.

The number of carbon atoms in the aliphatic hydrocarbon group represented by R ⁸ to R ¹⁰ in general formula (2) is 1 to 3, preferably 1 or 2. Specific examples of the aliphatic hydrocarbon group represented by R ⁸ to R ¹⁰ include methyl group, ethyl group, n-propyl group, isopropyl group and the like, with methyl group being preferred.

As for the combination of R ⁸ to R ¹⁰ in general formula (2), a combination in which R ⁸ and R ⁹ are hydrogen atoms and R ¹⁰ is a hydrogen atom or a methyl group is preferred.

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

In general formula (1), at least one of R ⁶ and R ⁷ is preferably a group represented by general formula (2) above, and both R ⁶ and R ⁷ are represented by general formula (2) above. more preferably a group represented by

When the polyimide precursor contains a compound having a structural unit represented by the above general formula (1), the total of R ⁶ and R ⁷ of all structural units contained in the compound is represented by general formula (2) is preferably 50 ^mol % or more, more preferably 80 ^mol % or more, even more preferably 90 mol % or more. The upper limit is not particularly limited, and may be 100 mol %.
In addition, the aforementioned ratio may be 0 mol % or more and less than 50 mol %.

The group represented by general formula (2) is preferably a group represented by general formula (3) below.

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

q in the general formula (3) is preferably an integer of 1 to 10, more preferably an integer of 2 to 5, and even more preferably 2 or 3.

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 the residue derived from the tetracarboxylic dianhydride, and Y corresponds to the residue derived from the diamine compound. The polyimide precursor may be synthesized using tetracarboxylic acid instead of tetracarboxylic dianhydride.

Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, anhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride anhydride, 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-di Carboxyphenoxy)phenyl}propane dianhydride, 2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3,3,3-hexafluoro- 2,2-bis{4′-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 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, 9,9-bis(3,4-di carboxyphenyl)fluorene dianhydride and the like.
Tetracarboxylic dianhydrides may be used alone or in combination of two or more.

Specific examples of diamine compounds 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 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-tolysine, o-tolysine 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-aminophenyl)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, di Aminopolysiloxane and the like can be mentioned.
A diamine compound may be used individually by 1 type, or may use 2 or more types together.

A compound having a structural unit represented by the general formula (1) and in which at least one of R ⁶ and R ⁷ in the general formula (1) is a monovalent organic group is represented by the following general formula (8) A tetracarboxylic dianhydride represented by and a compound represented by R—OH are reacted in a solvent such as N-methyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide to form a diester. After conversion into a derivative, either the diester derivative and a diamine compound represented by H ₂ N--Y--NH ₂ are condensed, or a tetracarboxylic dianhydride and H ₂ N--Y--NH ₂ are subjected to a condensation reaction. It can be obtained by reacting a diamine compound in a solvent to obtain a polyamic acid, adding a compound represented by R—OH, and reacting it in a solvent to introduce an ester group.
Here, the solvent used in the above reaction may be a solvent that can be contained in the resin composition of the present disclosure, which will be described later.
Y in the diamine compound represented by H ₂ N--Y--NH ₂ is the same as Y in general formula (1), and specific examples and preferred examples are also the same. Further, R in the compound represented by R--OH represents a monovalent organic group, and specific examples and preferable examples are the same as those of R ⁶ and R ⁷ in general formula (1).
Each of the tetracarboxylic dianhydride represented by the general formula (8), the diamine compound represented by H ₂ N--Y--NH ₂ and the compound represented by R--OH may be used alone. Well, you may combine two or more types.
Further, the above-mentioned compound contained in the polyimide precursor is a diester derivative obtained by reacting a compound represented by R-OH on a tetracarboxylic dianhydride represented by the following general formula (8), and then thionyl chloride. It can be obtained by reacting a diamine compound represented by H ₂ N--Y--NH ₂ with the acid chloride by reacting with a chlorinating agent such as chlorinating agent to convert it into an acid chloride.
Furthermore, the above-mentioned compound contained in the polyimide precursor is a diester derivative obtained by reacting a compound represented by R-OH on a tetracarboxylic dianhydride represented by the following general formula (8), and then a carbodiimide compound. can be obtained by reacting a diamine compound represented by H ₂ N--Y--NH ₂ with a diester derivative in the presence of .
Furthermore, the aforementioned compound contained in the polyimide precursor is obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a diamine compound represented by H ₂ N--Y--NH ₂ to obtain a polyamic. After converting to an acid, the polyamic acid is isoimidated in the presence of trifluoroacetic anhydride, and then reacted with a compound represented by R--OH. Alternatively, a part of the tetracarboxylic dianhydride is reacted in advance with a compound represented by R—OH to form a partially esterified tetracarboxylic dianhydride and H ₂ N—Y—NH ₂ . may be reacted with the diamine compound to be used.

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

Compounds represented by R—OH used for synthesizing the aforementioned compounds contained in the polyimide precursor include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, Hydroxyethyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxy methacrylate Butyl and the like are preferred, and 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate are more preferred.

The molecular weight of the polyimide precursor is not particularly limited, and for example, it is preferably 10,000 to 200,000 in weight average molecular weight.
The weight average molecular weight can be measured, for example, by gel permeation chromatography, and can be obtained by conversion using a standard polystyrene calibration curve.

The resin composition of the present disclosure may contain resin components other than the polyimide precursor. For example, from the viewpoint of heat resistance, the resin composition of the present disclosure includes polyimide resin, novolak resin, acrylic resin, polyethernitrile resin, polyethersulfone resin, epoxy resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polyvinyl chloride. Other resins such as resins may be contained. Other resins may be used singly or in combination of two or more.

In the resin composition of the present disclosure, the content of the polyimide precursor relative to the total amount of the resin component is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and 90% by mass. More preferably, it is up to 100% by mass.

(solvent)
The resin composition of the present disclosure preferably further contains a solvent. The solvent is not particularly limited, and examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylacetamide, cyclopentanone, dimethylsulfoxide, 3-methoxy-N ,N-dimethylpropanamide, N,N,2-trimethylpropionamide, dimethylimidazolidinone, N-formylpiperidine, N-dimethylmorpholine and propylene glycol 1-monomethyl ether-2-acetate. Among them, as solvents, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, γ-butyrolactone, cyclopentanone, dimethylsulfoxide, dimethylimidazolidinone and N-formylpiperidine is preferred. A solvent may be used individually by 1 type, and may combine 2 or more types.

When the resin composition of the present disclosure contains a solvent, the content of the solvent is preferably 50 parts by mass to 10000 parts by mass with respect to 100 parts by mass of the resin component, and is 100 parts by mass to 10000 parts by mass. is more preferred.

(Polymerizable monomer)
From the viewpoint of improving the physical properties of the cured film, the resin composition of the present disclosure preferably further contains a polymerizable monomer. 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 with a coupling agent or the like. preferable. From the viewpoint of improving the crosslink density and improving the photosensitivity, it is preferable to have 2 to 4 groups containing a polymerizable unsaturated double bond, and the cured film adhered to the laminate after peeling from the support. From the viewpoint of removability of the residue, it is more preferable to have two.
A polymerizable monomer may be used individually by 1 type, and may combine 2 or more types.

The (meth)polymerizable monomer having an 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, methacrylates, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, Trimethylolpropane 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, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate are preferable as the polymerizable monomer.

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

When the resin composition of the present disclosure contains a polymerizable monomer, the content of the polymerizable monomer is not particularly limited, with respect to 100 parts by weight of the polyimide precursor, preferably 1 part by weight to 50 parts by weight, From the viewpoint of the thermal properties of the cured film, it 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.

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

(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. Moreover, the resin composition of the present disclosure more preferably contains both the polymerizable monomer and the thermal polymerization initiator described above.

The thermal polymerization initiator is not particularly limited, and ketone peroxides such as methyl ethyl ketone peroxide, 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy) oxy)cyclohexane, peroxyketals such as 1,1-di(t-butylperoxy)cyclohexane, hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide , dicumyl peroxide, dialkyl peroxide such as di-t-butyl peroxide, dilauroyl peroxide, diacyl peroxide such as dibenzoyl peroxide, di(4-t-butylcyclohexyl)peroxydicarbonate, di(2-ethylhexyl)peroxy Peroxydicarbonates such as dicarbonates, t-butyl peroxy-2-ethylhexanoate, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxybenzoate, 1,1,3,3-tetramethylbutyl per Peroxy esters such as oxy-2-ethylhexanoate, bis(1-phenyl-1-methylethyl) peroxide, and the like. The thermal polymerization initiator may be used singly or in combination of two or more.

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 with respect to 100 parts by mass of the polyimide precursor, It may be 1 part by mass to 15 parts by mass, or may be 5 parts by mass to 10 parts by mass.

(light absorber)
The resin composition of the present disclosure may further contain a light absorbent from the viewpoint of suppressing the transmittance of light of a specific wavelength, for example, the transmittance of light of 355 nm.
A light absorber may be used individually by 1 type, and may combine 2 or more types.

Specific examples of light absorbers include:
benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenylketone, dibenzylketone, fluorenone;
Acetophenone derivatives such as 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone;
thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone;
benzyl derivatives such as benzyl, benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal;
Benzoin derivatives such as benzoin and benzoin methyl ether;
1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propane dione-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), oxime esters, and the like.

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

When the resin composition of the present disclosure contains a light absorber, the content of the light absorber may be 0.1 parts by mass to 1.0 parts by mass with respect to 100 parts by mass of the polyimide precursor, It may be 0.2 parts by mass to 0.8 parts by mass.

(coupling agent)
The resin composition of the present disclosure may further contain a coupling agent. In the heat treatment, the coupling agent reacts with the polyimide precursor to be crosslinked, or the coupling agent itself is polymerized. This tends to further improve the adhesiveness between the resulting cured film and the support.

Specific examples of the coupling agent are not particularly limited. Coupling agents 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]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1 , 4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, silane cups such as N-phenylaminopropyltrimethoxysilane ring agents; aluminum-based adhesion promoters such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetoacetate aluminum diisopropylate; and the like.

A coupling agent may be used individually by 1 type, and may combine 2 or more types.

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 with respect to 100 parts by mass of the polyimide precursor, and 0.3 parts by mass. ~10 parts by mass is more preferable, and 1 part by mass to 10 parts by mass is even more preferable.

(Surfactant and leveling agent)
The resin composition of the present disclosure may contain at least one of a surfactant and a leveling agent. By containing at least one of a surfactant and a leveling agent in the resin composition, coatability (for example, suppression of striation (unevenness in film thickness)) can be improved.

Surfactants or leveling agents include polyoxyethylene uralyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether and the like.

Surfactants and leveling agents may be used singly or in combination of two or more.

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 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the polyimide precursor. It is preferably 0.05 to 5 parts by mass, even more preferably 0.05 to 3 parts by mass.

(Polymerization inhibitor)
The resin composition of the present disclosure may contain a polymerization inhibitor from the viewpoint of ensuring good storage stability. Examples of polymerization inhibitors include radical polymerization inhibitors and radical polymerization inhibitors.

Specific examples of polymerization inhibitors include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, and N-phenyl-2. -naphthylamine, cupferron, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines and the like. A polymerization inhibitor may be used individually by 1 type, and may combine 2 or more types.

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

The resin composition of the present disclosure contains a polyimide precursor, and further includes a solvent, a polymerizable monomer, a thermal polymerization initiator, a light absorber, a coupling agent, a surfactant, a leveling agent, a polymerization inhibitor, etc. as optional components. It may 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,
polyimide precursors and solvents,
a polyimide precursor, a solvent, and at least one of a polymerizable monomer and a thermal polymerization initiator;
A polyimide precursor and a solvent, and at least one 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 as an optional component. ,
A polyimide precursor, a solvent, a polymerizable monomer, a thermal polymerization initiator and a light absorber or a polyimide precursor, a solvent, a polymerizable monomer, a thermal polymerization initiator and a light absorber, and optional components such as a coupling agent, a surfactant, at least one selected from the group consisting of leveling agents and polymerization inhibitors;
may consist of

<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 produced on a support using the resin composition of the present disclosure, and is used in a method of obtaining a laminate by separating the laminate from the support after producing a laminate on the cured film. be done.

Next, a method for producing a cured film will be described. Examples of the above-described method for producing a cured film include the steps of (α) coating a resin composition on a support and drying it to form a resin film, and heat-treating the resin film; (β) a step of forming a film with a certain thickness using a resin composition on a film that has been subjected to release treatment, and then transferring the resin film to a support by a lamination method; and a step of heat-treating the resin film. From the point of flatness, the method (α) is preferable. By this method, a flat cured film can be easily obtained, and reliability is excellent when a laminate is formed on the cured film.

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

The material of the support is preferably a material that maintains the laminate in a flat state and does not break during the process of producing the laminate and the transportation operation, and suppresses the warping of the laminate during the process of producing the laminate. From the point of view, it is preferable that the material has sufficient rigidity. Examples of the support include acrylic plates, glass substrates, semiconductor substrates such as silicon wafers, metal oxide insulator substrates such as _TiO2 substrates and _SiO2 substrates, silicon nitride substrates, copper substrates, copper alloy substrates, and the like.

When separating the laminate from the support by irradiating the cured film with an active energy ray such as a laser beam from the support side to alter the cured film, the support is preferably permeable to the active energy ray. For example, an acrylic plate or a glass substrate is preferable, and a glass substrate is preferable from the viewpoint of heat resistance.

In addition, from the viewpoint of suppressing peeling between the cured film and the support in the process of producing the laminate and from the viewpoint of suppressing warping during sealing in the subsequent process, the thermal expansion coefficient of the support at 25 ° C. to 300 ° C. is preferably 3 ppm/K to 15 ppm/K, more preferably 5 ppm/K to 15 ppm/K.

The shape, size, etc. of the support are not limited, and may be appropriately selected according to the shape, size, etc. of the laminate to be produced. good.

The thickness of the support is preferably 100 μm to 10000 μm, more preferably 100 μm to 2000 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. preferable.
In addition, from the viewpoint of suitably separating the laminate from the support by irradiating the cured film with a laser beam from the support side to modify the cured film, the support should have a transmittance of 90% or more for light having a wavelength of 355 nm. is preferred.

In the spin coating method, for example, the rotation speed is 300 rpm (rotation per minute) to 3,500 rpm, preferably 500 rpm to 1,500 rpm, the acceleration is 500 rpm / sec to 15,000 rpm / sec, and the rotation time is 30 seconds to 300 seconds. Under certain conditions, the resin composition may be spin-coated.

A drying step may be included after applying the resin composition 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., 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.
Drying may be performed twice or more. As a result, a resin film can be obtained by forming the above-described resin composition into a film.

In addition, in the slit coating method, for example, the chemical liquid discharge speed is 10 μL/sec to 400 μL/sec, the chemical liquid discharge portion height is 0.1 μm to 1.0 μm, and the stage speed (or the chemical liquid discharge portion speed) is 1.0 mm/sec to 50 mm/sec. 0 mm/sec, stage acceleration 10 mm/sec to 1000 mm/sec, final vacuum degree during reduced pressure drying 10 Pa to 100 Pa, reduced pressure drying time 30 seconds to 600 seconds, drying temperature 60°C to 150°C, and drying time 30 to 300 seconds. Under these conditions, the resin composition may be slit-coated.

The formed resin film may be heat-treated. The heating temperature is preferably 100°C to 450°C, preferably 150°C to 400°C, more preferably 250°C to 380°C. When the heating temperature is within the above range, a cured film can be favorably produced while suppressing damage to the support and realizing energy saving in the process.

The heating time is preferably 5 hours or less, more preferably 30 minutes to 3 hours. When the heat treatment time is within the above range, the cross-linking reaction or the dehydration ring-closing reaction can be sufficiently advanced.
The atmosphere of the heat treatment may be the air or an inert atmosphere such as nitrogen, but the nitrogen atmosphere is preferable from the viewpoint of preventing oxidation of the resin film.

Devices used for the heat treatment include quartz tube furnaces, hot plates, rapid thermal annealing, vertical diffusion furnaces, infrared curing furnaces, electron beam curing furnaces, microwave curing furnaces, and the like.

The average thickness of the cured film produced on the support is preferably 0.1 μm or more, more preferably 0.5 μm to 10 μm, even more preferably 0.5 μm to 5 μm.

<Method for manufacturing laminate>
A method for manufacturing the laminate of the present disclosure using the resin composition of the present disclosure will be described below. A method for producing a laminate of the present disclosure includes steps of preparing a resin composition of the present disclosure, forming a cured film of the resin composition on a support, and producing a laminate on the cured film. and separating the laminate from the support.

A method for manufacturing a laminate of the present disclosure includes a step of preparing a resin composition of the present disclosure. For example, a polyimide precursor is synthesized as described above, and the synthesized polyimide precursor is mixed with optional components such as a solvent, a polymerizable monomer, a thermal polymerization initiator, a light absorber, a coupling agent, a surfactant, and a leveling agent. , a polymerization inhibitor, etc., as necessary to prepare the resin composition of the present disclosure.

A method for producing a laminate of the present disclosure includes a step of forming a cured film of a resin composition on a support. The step of forming a cured film is the same as the above-described method of forming a cured film.

A method for producing a laminate of the present disclosure includes a step of producing a laminate on a cured film. Examples of laminates include semiconductor devices, more specifically, semiconductor devices including wiring layers, insulating layers, and semiconductor chips. In addition, semiconductor devices include semiconductor wafers, semiconductor chips, glass substrates, resin substrates, metal substrates, metal films such as metal foil, polishing pads, resin coatings such as insulating layers, wiring layers, sealing materials, etc., as required. may be prepared. At least one selected from bumps, wiring, through holes, through hole vias, insulating films and various elements may be formed on the semiconductor wafer and semiconductor chip, and various elements may be formed or mounted thereon. good too. The resin coating film includes, for example, a layer 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, A photosensitive insulating resin layer formed from a photosensitive insulating resin material may be used.

A method of manufacturing a semiconductor device including a wiring layer, an insulating layer, and a semiconductor chip as a laminate will be described below. At this time, the steps of fabricating the laminate include a step of forming a wiring layer on the cured film, a step of forming an insulating layer that insulates at least between the wiring layers, a step of placing a semiconductor chip on the insulating layer, and placing the semiconductor chip on the insulating layer. and a step of connecting with the wiring layer.

First, a metal film may be formed on the cured film. Sputtering is mentioned as a method of forming a metal film. 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 of two or more of these, and Nitride etc. are mentioned. As metals, alloys, and nitrides that can be contained in the metal film, each may be one kind, or two or more kinds may be used.

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

Next, after forming a patterned resist layer on the metal film, a wiring layer may be formed on the metal film. A liquid containing resist may be applied onto the metal film. A film-like resist material may be used, and a resist layer may be formed on the metal film by lamination or the like. The resist may be either positive type or negative type, and can be appropriately set according to the process.

The method of applying the liquid material containing the resist is not particularly limited, and examples thereof include coating methods such as spin coating, dipping, roller blade, doctor blade, spray, slit nozzle, and ink jet. Heating or the like may be performed after the liquid containing the resist is applied.

After the resist layer is formed, a resist patterning step is performed. In the resist patterning process, the resist layer is exposed with an arbitrary pattern and then developed by being immersed in a developer. These treatments preferably include a step of heating the resist layer before or after exposing the resist layer.

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 so as to be connected to the metal film by a technique such as sputtering. Materials used for forming the wiring layer include metals such as gold, silver, copper, and aluminum, and conductive resins. After forming the wiring layer, the patterned resist layer is removed.

Also, the plating process may be performed after the wiring layer forming process. In the plating step, a plating layer is formed on the wiring layer by electroless plating or electrolytic plating. In the plating process, a plating layer is formed on the wiring layer by immersing the object in a predetermined plating bath. Materials used for forming the plating layer include chemicals used for solder plating, copper plating, gold plating, nickel plating, silver-tin plating, and the like. Note that the plating process may be omitted when a wiring layer having a sufficient thickness can be formed by a technique such as sputtering.

Next, an insulating layer for insulating at least between 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, phenol resin, and acrylic resin. . An insulating material may be used individually by 1 type, or may use 2 or more types together. In the insulating layer forming step, for example, a liquid containing an insulating material may be applied between the wiring layers and on the wiring layers. The method for applying the liquid containing the insulating material is not particularly limited, and examples thereof include coating methods such as spin coating, dipping, roller blade, doctor blade, spray, slit nozzle, and inkjet. . As an example, while the support is held on the stage and the stage and the slit nozzle are relatively moved, a liquid containing an insulating material is ejected from the slit nozzle to form an insulating film between the wiring layers and on the wiring layer. A liquid containing the material may be applied. Alternatively, the liquid containing the insulating material may be applied and then dried by heating or the like.

Subsequently, vias are formed in the above-described insulating layers for connection between the layers. Methods of forming vias include a method of forming by patterning using a photosensitive resin, a method of processing a non-photosensitive resin, and the like. When a photosensitive resin is used, the photosensitive resin layer may be exposed in an arbitrary pattern and then developed by being immersed in a developer. These treatments preferably include a step of heating the photosensitive resin layer before or after the photosensitive resin layer is exposed.

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, more preferably in the range of 180°C to 380°C. In addition, in the present disclosure, the cured film has a high heat resistance temperature, for example, the deterioration of the cured film is suppressed even when heated at 280 ° C. to 350 ° C., and it is possible to improve the reliability of the manufactured semiconductor device. .

When patterning the photosensitive resin layer, the active energy rays to be irradiated include broadband light (wavelength 350 nm to 450 nm), ultraviolet rays such as i-line, visible light, radiation, etc. Among them, i-line is preferable. . As an exposure device, a parallel exposure device, a projection exposure device, a stepper, a scanner exposure device, a proximity exposure device, or the like may be used.

When a non-photosensitive resin is used, the method of forming vias is not particularly limited, and may be processed by forming a resist layer on the non-photosensitive resin layer, or may be processed by laser via, dry etching, or the like. good.

Also, if an insulating layer having a sufficient thickness can be formed by vapor deposition, CVD, sputtering, or the like, the insulating layer may be used to form the vias.

Next, a semiconductor chip is placed 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 through the connection terminals.

A connection terminal for connecting the semiconductor chip and the wiring layer may be formed by a method similar to the method for forming the wiring layer described above. Metals used for connection terminals 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 metals of these metals. Nitride etc. are mentioned. 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 through connection terminals using a flip-chip bonder. From the viewpoint of improving the reliability between the semiconductor chip and the connection terminal, an underfill material may be supplied between them.

The step of producing 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 examples thereof include compression molding and transfer molding. Alternatively, the sealing material may be heat-treated after sealing the semiconductor chip with the sealing material.

From the viewpoint of suppressing warpage of the semiconductor device after encapsulation, when the thermal expansion coefficient of the support is 3 ppm/K to 15 ppm/K at 25° C. to 300° C., the heat of the encapsulant at 25° C. to 300° C. The expansion coefficient is preferably between 4 ppm/K and 8 ppm/K (CTE1: CTE below the glass transition temperature (Tg)). By adjusting the thermal expansion coefficients of the support and the encapsulating material, warping of the semiconductor device after encapsulation is suppressed, so that it is possible to suppress breakage of the semiconductor chip and decrease in yield.

A method of manufacturing a 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 denatured by heating, and the laminate is removed from the support after the cured film is denatured by irradiating the cured film with active energy rays. may be separated. As the latter method, the cured film may be denatured by irradiating the cured film with an active energy ray such as a laser beam from the support side.

By irradiating the cured film with an active energy ray such as a laser beam, the cured film deteriorates and the adhesive strength of the cured film decreases. This makes it possible to easily separate the laminate from the support after irradiation with active energy rays.

The active energy ray is preferably light having a wavelength in the ultraviolet region, for example, ultraviolet rays with a wavelength of 10 nm to 400 nm are preferred, and ultraviolet rays with a wavelength of 300 nm to 400 nm are more preferred. Examples of light sources for active energy rays include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, LED lamps, and lasers.

Examples of lasers include YAG lasers, ruby lasers, glass lasers, _YVO4 lasers, LD lasers, solid lasers such as fiber lasers, liquid lasers such as dye lasers, _CO2 lasers, excimer lasers, Ar lasers, and He-Ne lasers. and other gas lasers, semiconductor lasers, free electron lasers, and the like.

The type of active energy ray, the type of light source, the type of laser, etc. may be appropriately selected according to the composition of the cured film.

It is preferable to separate the laminate from the support after modifying the cured film by irradiating it with an active energy ray or the like. At this time, by lifting the support in a vertically upward direction with the laminate placed vertically below and the support vertically above the object, the cured film is physically destroyed and the laminate is separated from the support. can do. The work of lifting the support may be performed by using a device for lifting the support by suction, or by lifting the support by an operator. At this time, it is preferable that the laminate is adsorbed, for example, on a stage or the like.

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

Examples of the method for removing the residue of the cured film include polishing and cleaning with a solvent or the like, and cleaning with a solvent or the like is preferable from the viewpoint of convenience.

The solvent used for removing the residue of the cured film is a solvent that can remove the residue of the cured film without dissolving the materials contained in each structure that may be included in the laminate such as the wiring layer and the sealing resin. is not particularly limited. The supply of the solvent to the residue of the cured film may be performed, for example, by scanning a supply device such as a dispenser over the laminate, or by immersing the laminate in a tank containing the solvent.

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

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

Residues of the cured film may be removed using a general resist remover or the like.

The method for manufacturing the laminate of the present disclosure may include a step of etching the laminate, a step of dicing the laminate, etc. after the step of removing the residue of the cured film. In the case where the laminate is a semiconductor device including a semiconductor chip, individualized semiconductor devices can be obtained by performing dicing in a range including the semiconductor chip.

A method for manufacturing a semiconductor device according to an embodiment of the present disclosure will be described below with reference to FIGS. In addition, the same code|symbol is attached|subjected to the same element in description of drawing.

As shown in FIG. 1(a), 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. By heat-treating the formed resin film, a cured film 2 is formed on the support 1 as shown in FIG. 1(b).
As shown in (c) of FIG. 1, a metal film 3 is formed on the cured film 2 . The metal film 3 may be formed by sputtering or the like.

Next, a resist layer is formed by applying a liquid containing a resist onto the metal film 3 . After the resist layer is formed, the resist layer is exposed in an arbitrary pattern and then developed by being immersed in a developer. Also, the resist layer may be heated before or after the resist layer is exposed. As a result, a patterned resist layer 4 is formed on the metal film 3, as shown in FIG. 1(d).

After the patterned resist layer 4 is formed, a wiring layer 5 such as a copper wiring is formed between the patterns. The wiring layer 5 may be formed by sputtering or the like. From the viewpoint of forming the wiring layer 5 with a sufficient thickness, the plating process may be performed after the wiring layer forming process. Thus, the wiring layer 5 is formed on the metal film 3 as shown in FIG. 1(e).

Next, the liquid containing the insulating material is applied between the wiring layers 5 and on the wiring layers 5 by discharging the liquid containing the insulating material from the 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 layers 5 as shown in FIG. 2(a).

As shown in FIG. 2B, vias 7 are formed in the insulating layer 6 . For example, the vias 7 may be formed by processing the insulating layer 6 by laser vias, dry etching, or the like. Thereafter, as shown in FIG. 2C, connection terminals 8 are formed in the vias 7 by sputtering or the like.

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 . As a result, as shown in FIG. 2D, a semiconductor device is obtained in which the semiconductor chip 10 and the wiring layer 5 are connected to each other through the connection terminals 8. Next, as shown in FIG.

As shown in (a) of FIG. 3, the semiconductor chip 10 connected to the wiring layer 5 may be sealed using a sealing material 20 . Alternatively, the sealing material 20 may be heat-treated after the semiconductor chip 10 is sealed.

Next, as shown in FIG. 3B, the cured film 2 may be denatured by irradiating the cured film 2 with an active energy ray X from the support 1 side. After denaturing the cured film 2 by irradiating the active energy ray X, the semiconductor device is separated from the support 1 . As a result, as shown in FIG. 3C, a semiconductor device 100 is obtained in which the residue 30 of the cured film 2 adheres to the metal film 3 .

Residues 30 remaining on the semiconductor device are removed by cleaning with a solvent. As a result, the semiconductor device 100 from which the residue 30 has been removed is obtained as shown in FIG. 3(d). Further, by removing the metal film 3 by etching or the like, the semiconductor device 100 is obtained as shown in FIG. 3(e).

Hereinafter, the present disclosure will be described more specifically based on examples and comparative examples. It should be noted that the present disclosure is not limited to the following examples.

<Synthesis Example 1: Synthesis of pyromellitic acid-hydroxyethyl methacrylate diester>
43.5 g of pyromellitic dianhydride (hereinafter also referred to as PMDA), 54.9 g of 2-hydroxyethyl methacrylate and 0.220 g of hydroquinone was dissolved in 394 g of N-methyl-2-pyrrolidone, and a catalytic amount of 1,8-diazabicycloundecene was added to prepare a mixed solution. The mixture was stirred at room temperature (25° C.) for 24 hours for esterification to obtain a pyromellitic acid-hydroxyethyl methacrylate diester solution. Let this solution be the PMDA (HEMA) solution.

<Synthesis Example 2: Synthesis of 4,4′-oxydiphthalic acid diester>
15.5 g of 4,4′-oxydiphthalic anhydride (hereinafter also referred to as ODPA) and 14 g of 2-hydroxyethyl methacrylate dried in a 160° C. dryer for 24 hours in a 0.5 liter plastic bottle. .1 g 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 mixture was stirred at room temperature (25° C.) for 48 hours for esterification to obtain a 4,4′-oxydiphthalic acid-hydroxyethyl methacrylate diester solution. Let this solution be the ODPA (HEMA) solution.

<Synthesis Example 3: Synthesis of Polyimide Precursor (Synthesis of A1)>
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 put into a 0.5 liter flask equipped with a stirrer and a thermometer, After that, under ice-cooling, 124.9 g of thionyl chloride was added dropwise using a dropping funnel so as to keep the temperature of the reaction liquid below 10°C. At this time, the molar ratio of PMDA (HEMA) and ODPA (HEMA) was 4:1. After the dropwise addition of thionyl chloride was completed, reaction was carried out for 2 hours under ice-cooling to obtain a solution of acid chlorides of PMDA (HEMA) and ODPA (HEMA). Then, using a dropping funnel, dissolve 80 g of 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (TFMB), 83 g of pyridine and 0.2 g of hydroquinone in 227 g of N-methyl-2-pyrrolidone. The resulting solution was ice-cooled and added dropwise while taking care that the temperature of the reaction solution did not exceed 10°C. This reaction liquid was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyamic acid ester as a polyimide precursor. Let this be A1. A1 had a weight average molecular weight of 40,000 determined by standard polystyrene conversion using a gel permeation chromatography (GPC) method. 1 g of A1 is dissolved in 1.5 g of N-methyl-2-pyrrolidone, applied onto a glass substrate by spin coating, and heated on a hot plate at 100° C. for 180 seconds to volatilize N-methyl-2-pyrrolidone. to form a coating film having a thickness of 20 μm. At this time, the i-line transmittance of the obtained coating film was 30%.

<Synthesis Example 4: Synthesis of Polyimide Precursor (Synthesis of A2)>
A polyimide precursor was obtained in the same manner as in Synthesis Examples 1 to 3 described above, except that N-methyl-2-pyrrolidone was changed to 3-methoxy-N,N-dimethylpropionamide. Let this be A2. The weight-average molecular weight of A2 was 42,000 determined by standard polystyrene conversion using a gel permeation chromatography (GPC) method. Moreover, the esterification rate was 100 mol%.

<Synthesis Example 5: Synthesis of Polyimide Precursor (Synthesis of A3)>
2,2′-Bis(trifluoromethyl)-4,4 was added to a solution of 30.20 g of PMDA and 7.51 g of ODPA dried in a dryer at 160° C. for 24 hours dissolved in 400 g of N-methyl-2-pyrrolidone. A solution of 49.5 g of '-diaminobiphenyl (TFMB) dissolved in 100 g of N-methyl-2-pyrrolidone was added dropwise to prepare a mixed solution. A reaction liquid was obtained by stirring the mixed liquid at 30° C. for 4 hours. This reaction liquid was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyimide precursor which is a polyamic acid. Let this be A3. A3 had a weight average molecular weight of 36,000 as determined by standard polystyrene conversion using a gel permeation chromatography (GPC) method.

<Synthesis Example 6: Synthesis of Polyimide Precursor (Synthesis of A4)>
A mixed solution was prepared by dissolving 7.07 g of ODPA and 4.12 g of DMAP in 30 g of N-methyl-2-pyrrolidone (NMP). The mixed solution was stirred at 30° C. for 4 hours and then at room temperature overnight to obtain a reaction solution containing polyamic acid. After adding 9.45 g of trifluoroacetic anhydride to the reaction solution, the mixture was stirred at 45° C. for 2 to 3 hours. Then, 7.08 g of 2-hydroxyethyl methacrylate (HEMA) was added to the stirred reaction solution, and the mixture was stirred at 45° C. for about 15 hours. This reaction liquid was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyimide precursor. Let this be A4. The weight average molecular weight of A4 was 20,000 as determined by standard polystyrene conversion using gel permeation chromatography (GPC).

<Reference Example 1: Preparation of A5>
As a polymer other than the polyimide precursor, a 4-hydroxystyrene polymer (weight average molecular weight = 10000, Maruzen Petrochemical Co., Ltd., trade name "Marukalinker M") was prepared.

<Measurement of weight average molecular weight>
The weight average molecular weights of A1 to A5 were measured as follows. Specifically, a solution of 0.5 mg of A1 to A4 dissolved in 1 mL of a solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1/1 (volume ratio)], and 0.5 mg of A5 dissolved in 1 mL of THF Measurement was performed under the following conditions using the solution obtained by
(Measurement condition)
Measuring device: Detector Hitachi, Ltd. L4000UV
Pump: Hitachi Ltd. L6000
Shimadzu Corporation C-R4A Chromatopac
Measurement conditions: Column Gelpack GL-S300MDT-5 × 2 Eluent: THF/DMF = 1/1 (volume ratio) for A1 to A4
THF in A5
LiBr (0.03 mol/L), _{H3PO4 (} 0.06 mol/L)
Flow rate: 1.0 mL/min, detector: UV270 nm
Standard polystyrene: TSKgel standard Polystyrene Type F-1, F-4, F-20, F-80, A-2500 manufactured by Tosoh Co., Ltd. A calibration curve was prepared and used.

<Esterification rate>
By performing NMR measurement under the following conditions, the esterification rate of A1 and A4 (for A1 and A4, the ester group reacted with HEMA to the total of the ester group reacted with HEMA and the carboxyl group unreacted with HEMA base ratio) was calculated. The esterification rate was 100 mol % for A1 and 80 mol % for A4 (the remaining 20 mol % being carboxy groups).
(Measurement condition)
Measuring instrument: Bruker Biospin AV400M
Magnetic field strength: 400MHz
Reference substance: Tetramethylsilane (TMS)
Solvent: dimethyl sulfoxide (DMSO)

<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 blending amounts shown in Table 1. The blending amounts in Table 1 are parts by mass of each component with respect to 100 parts by mass of each polymer component. A blank in Table 1 means that the corresponding component is not blended.

Components used in Examples 1 to 10 and Comparative Example 1 are as follows.
(High molecular)
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 (adhesion aid)
E1: 3-glycidoxypropyltrimethoxysilane E2: 3-methacryloxypropyltrimethoxysilane E3: triethoxysilylpropylethylcarbamate E4: 50% methanol solution of 3-ureidopropyltriethoxysilane E5: Formula (Y) below A compound represented by

<Peelability evaluation>
(Preparation of sample for peelability evaluation)
The resin compositions of Examples 1 to 10 and Comparative Example 1 were spin-coated on a glass wafer (TEMPAX) as a support using an 8-inch spin coater, and dried to form a resin film.
The obtained resin film was heated at a predetermined 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 titanium layer of 50 nm and a copper layer of 200 nm were vapor-deposited on the resulting cured film using a sputtering apparatus. The film thickness was measured from the cross section by SEM (scanning electron microscope).
Next, electrolytic copper plating was performed on the deposited metal layer to form a copper layer of 20 μm, thereby preparing a sample for evaluation of peelability.

(Evaluation method and evaluation criteria)
Using a laser irradiation device 5331 (ESI Co.), the above sample for peelability evaluation was irradiated with a laser from the glass wafer side under the conditions of a wavelength of 355 nm, a laser output of 0.4 W, a repetition frequency of 40 kHz, and a feed rate of 500 mm / s. Light was applied to an area of 10 mm width and 100 mm length.
After the laser light irradiation, a cutter knife was used to cut into the peelability evaluation sample along the outer periphery of the laser light irradiated range from the copper layer side. Then, a cutter knife was inserted between the cured film of the resin composition having a width of 10 mm and a length of 100 mm and the glass wafer to peel off the copper layer.

The peeled portion of the cured film was held with tweezers and pulled at an angle of 90 degrees with respect 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. Evaluation criteria are as follows. Table 1 shows the results.
-Evaluation criteria-
A: The cured film and the metal layer on the cured film could be 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 occurred during the separation.
C The cured film and the metal layer on the cured film could not be separated from the glass wafer.

<Evaluation of residue removability>
The resin compositions of Examples 1 to 10 and Comparative Example 1 were spin-coated on a silicon wafer as a support using an 8-inch spin coater, followed by drying to form a resin film.
The obtained resin film was heated at a predetermined 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 (Dynastrip 7700, Dynaloy Co.) heated to a predetermined temperature. After cooling the silicon wafer, it was washed with acetone and dried.
After drying, the film thickness of the cured film adhering to the silicon wafer was measured, and the film thickness change rate was calculated based on the following formula.
Film thickness change rate (%) = 100 × [(film thickness before immersion in chemical solution) - (film thickness of pattern cured film after drying)] / film thickness before immersion in chemical solution

Using the value of the film thickness change rate calculated as described above, the residue removability was evaluated according to the following criteria. Table 1 shows the results.
-Evaluation criteria-
A The film thickness change rate is 100% to 90%.
B The film thickness change rate exceeds 90% and is 50%.
C Film thickness change rate is less than 50%.

<Evaluation of adhesion with metal layer>
The resin compositions of Examples 1 to 10 and Comparative Example 1 were spin-coated on silicon wafers using an 8-inch spin coater, and dried to form resin films.
The obtained resin film was heated at a predetermined 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 titanium layer of 50 nm and a copper layer of 200 nm were vapor-deposited on the resulting cured film using a sputtering apparatus. After that, it was heated at the temperature shown in Table 1 for 2 hours in a nitrogen atmosphere using a vertical diffusion furnace. The object was visually observed to check for the presence or absence of peeling between the cured film and the metal layer. Evaluation criteria are as follows. Here, the absence of peeling means that a laminated body, particularly a semiconductor device, can be manufactured without lowering the yield. Table 1 shows the results.
-Evaluation criteria-
A: No peeling such as air bubbles was observed between the cured film and the metal layer.
B Detachment such as air bubbles was confirmed between the cured film and the metal layer.

<Adaptability evaluation at the time of laminate production>
Using a 12-inch spin coater, the resin compositions of Examples 1 to 10 and Comparative Example 1 were spin-coated onto a 12-inch glass wafer as a support (thickness: 800 μm), followed by a drying process to form a resin film. .
The obtained resin film was heated at a predetermined 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 titanium layer of 50 nm and a copper layer of 200 nm were vapor-deposited on the obtained cured film-coated substrate using a sputtering apparatus to obtain a metal thin film layer-coated substrate. The film thickness was measured from the cross section by SEM (Scanning Electron Microscope).

Dry film resist RY5110 (Showa Denko Materials Co., Ltd.) was applied to the substrate with the metal thin film layer using a vacuum laminator, the temperature of the upper crimping part was 110 ° C., the temperature of the lower crimping part was 40 ° C., the pressure was 0.5 MPa, and the crimping time was 90. Lamination was carried out under the condition of seconds to obtain a substrate with a dry film resist-metal thin film layer.
The substrate with the dry film resist-metal thin film layer was exposed using a stepper type exposure machine at an exposure amount of 210 mJ/cm ² to pattern the circuit diagram on the dry film resist.
The patterned substrate was developed using a developing machine within 1 to 3 hours after exposure to obtain a patterned substrate. The development was carried out using a 1% aqueous solution of sodium hydrogen carbonate as a developer under conditions of a developer temperature of 30° C. and a development time of 30 seconds.

The resulting patterned substrate was subjected to electrolytic copper plating treatment to form copper wiring between the patterns to obtain a copper wiring-patterned substrate. In the electrolytic copper plating treatment, a solution containing predetermined amounts of an aqueous copper sulfate solution from Okuno Pharmaceutical Co., Ltd. and an additive NSV series was used as a plating solution. Electrolytic copper plating was performed by adjusting the thickness of the copper wiring to 4.0 μm±1.0 μm within the wafer.

The dry film resist was removed from the resulting copper wiring-patterned substrate. The removal of the dry film resist is performed by storing a resist stripping solution containing a predetermined amount of R100S (Mitsubishi Gas Chemical Co., Ltd.), R101 (Mitsubishi Gas Chemical Co., Ltd.), and pure water, and placing copper in a liquid bath heated to 40 ° C. The wiring-patterned substrate was immersed. Thus, a copper wiring-metal thin film-attached substrate was obtained.

Next, an insulating layer was formed on the obtained copper wiring-metal thin film-attached substrate. Using a 12-inch spin coater, a negative photosensitive insulating photosensitive material was spin-coated on the copper wiring-metal thin film substrate, followed by a drying process to obtain a substrate with a photosensitive insulating resin film having a thickness of 5 μm to 6 μm. rice field. Using a stepper type exposure machine, this was exposed under the condition of an exposure amount of 250 mJ/cm ² to form a circuit pattern on the above photosensitive insulating resin film. After that, after developing using a solvent developing machine, the photosensitive insulating resin film was cured by heat treatment at 230 ° C. or 280 ° C. shown in Table 1 for 2 hours using an inert gas oven, and the insulating layer-copper. A substrate with wiring was obtained.

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

Subsequently, dry film resist RY5110 (Showa Denko Materials Co., Ltd.) was applied to the metal thin film layer-attached substrate 2 using a vacuum laminator at an upper crimping part temperature of 110 ° C., a lower crimping part temperature of 40 ° C., and a pressure of 0.5 MPa. Lamination was carried out under the condition of a pressure bonding time of 90 seconds to obtain a substrate 2 with a dry film resist-metal thin film layer.
The substrate 2 with the dry film resist-metal thin film layer was exposed using a stepper type exposure machine at an exposure amount of 210 mJ/cm ² to form a circuit pattern on the dry film resist.
The patterned substrate was developed using a developing machine within 1 to 3 hours after the exposure to obtain a patterned substrate 2 . The development was carried out using a 1% aqueous solution of sodium hydrogen carbonate as a developer under conditions of a developer temperature of 30° C. and a development time of 30 seconds.

The resulting patterned substrate 2 was subjected to electrolytic copper plating treatment to form copper wiring between the patterns, thereby obtaining a copper wiring-patterned substrate 2 . In the electrolytic copper plating treatment, a solution containing predetermined amounts of an aqueous copper sulfate solution from Okuno Seiyaku Co., Ltd. and an additive NSV series was used as a plating solution. Further, electrolytic copper plating was performed by adjusting the thickness of the copper wiring to be 3.0 μm±1.0 μm.

The dry film resist was removed from the resulting copper wiring-patterned board 2 . The removal of the dry film resist is performed by storing a resist stripping solution containing a predetermined amount of R100S (Mitsubishi Gas Chemical Co., Ltd.), R101 (Mitsubishi Gas Chemical Co., Ltd.), and pure water, and placing copper in a liquid bath heated to 40 ° C. The wiring-patterned substrate was immersed. Thus, a copper wiring-metal thin film-attached substrate 2 was obtained.

Subsequently, the metal thin film layer of the obtained substrate 2 with copper wiring and metal thin film was etched to obtain the substrate 2 with copper wiring. 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 substrate 2 with copper wiring-metal thin film, and WLC-C2 (Mitsubishi Gas Chemical Co., Ltd.) was used as an etching solution for the titanium layer. T (Mitsubishi Gas Chemical Co., Ltd.) was used in a predetermined blending amount. By etching the metal thin film layer, the metal thin film between the copper wirings can be removed.

Subsequently, an insulating layer was formed on the obtained substrate 2 with copper wiring. A 12-inch spin coater was used to spin-coat a negative photosensitive insulating photosensitive material onto a substrate 2 with copper wiring, followed by a drying process to obtain a substrate 2 with a photosensitive insulating resin film having a thickness of 5 μm to 6 μm. . Using a stepper type exposure machine, this was exposed under the condition of an exposure amount of 250 mJ/cm ² to form a circuit pattern on the above photosensitive insulating resin film. After that, after developing using a solvent developing machine, the photosensitive insulating resin film was cured by heat treatment at 230 ° C. or 280 ° C. shown in Table 1 for 2 hours using an inert gas oven, and the insulating layer-copper. A substrate 2 with wiring was obtained.

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

Subsequently, dry film resist RY5110 (Showa Denko Materials Co., Ltd.) was applied to the metal thin film layer-attached substrate 3 using a vacuum laminator at an upper crimping part temperature of 110 ° C., a lower crimping part temperature of 40 ° C., and a pressure of 0.5 MPa. Lamination was carried out under the condition of a pressure bonding time of 90 seconds to obtain a substrate 3 with a dry film resist-metal thin film layer.
The substrate 3 with the dry film resist-metal thin film layer was exposed using a stepper type exposure machine at an exposure amount of 210 mJ/cm ² to form a circuit pattern on the dry film resist.
The patterned substrate was developed using a developing machine within 1 to 3 hours after the exposure to obtain a patterned substrate 3 . The development was carried out using a 1% aqueous solution of sodium hydrogen carbonate as a developer under conditions of a developer temperature of 30° C. and a development time of 30 seconds.

The resulting patterned substrate 3 was subjected to electrolytic copper plating treatment to form copper wiring between the patterns, thereby obtaining a copper wiring-patterned substrate 3 . In the electrolytic copper plating treatment, a solution containing predetermined amounts of an aqueous copper sulfate solution from Okuno Seiyaku Co., Ltd. and an additive NSV series was used as a plating solution. Further, electrolytic copper plating was performed by adjusting the thickness of the copper wiring to be 2.0 μm±1.0 μm.

The dry film resist was removed from the resulting copper wiring-patterned board 3 . The removal of the dry film resist is performed by storing a resist stripping solution containing a predetermined amount of R100S (Mitsubishi Gas Chemical Co., Ltd.), R101 (Mitsubishi Gas Chemical Co., Ltd.), and pure water, and placing copper in a liquid bath heated to 40 ° C. The wiring-patterned substrate 3 was immersed. Thus, a copper wiring-metal thin film-attached substrate 3 was obtained.

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

A chip with wiring was bonded to the substrate with the rewiring layer. Wiring chip CC80-0101JY (SiN) _Model1 (Walz Co., Ltd.; Copper bump height 15 μm, Suzugin solder thickness 8 μm) Si side was thinned to 200 μm thickness using a grind, and then a blade dicing device was used. After dicing to 7.3 mm square, an NCF film (Showa Denko Materials Co., Ltd.) was laminated on the wiring side using a vacuum laminator to obtain a chip with an NCF. Using a flip chip bonder, the obtained chip with NCF was press-bonded onto a substrate with a rewiring layer. Thereafter, heat treatment was performed to cure the NCF, thereby obtaining a substrate with a chip.

Subsequently, the chip-attached substrate was resin-sealed with a sealing resin W5MG (Showa Denko Materials Co., Ltd.) using a wafer level compression molding apparatus to obtain a resin-sealed substrate. After reflowing the resin-encapsulated substrate with a reflow device to connect the chip with wiring and the substrate with rewiring layer, heat treatment is performed at 150° C. for 4 hours to fully cure the encapsulating resin. Thus, a resin-encapsulated substrate was obtained. Resin sealing was performed at 150°C for 300 seconds, and reflow was performed at a maximum temperature of 275°C.

Subsequently, a process of separating the resin-encapsulated substrate from the support was performed. Using a laser irradiation device 5331 (ESI), the entire resin-sealed substrate was irradiated with a laser from the support side 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 the irradiation, the support was separated by making an incision at the interface between the cured film and the metal thin film layer to obtain a resin wafer.

Subsequently, the cured film remaining as a residue on the peeling surface of the obtained resin wafer was removed. Residues of the cured film were removed with a sheet-fed spin washer and a waste cloth partly moistened with pure water. Subsequently, the resin wafer was immersed for a predetermined time in a chemical solution (Dynastrip 7700, Dynaloy Corporation) heated to a predetermined temperature. After cooling the resin wafer, it was washed with acetone and dried to remove the residue of the cured film on the metal thin film layer. If the residue of the cured film cannot be easily removed in this step, the connection terminals cannot be exposed, resulting in short circuits between wirings, connection failures, and the like, leading to a decrease in yield.

Subsequently, the metal thin film layer was etched on the resin wafer to obtain a laminated resin package. WLC-C2 (Mitsubishi Gas Chemical Co., Ltd.) is used as an etchant for the copper layer of the resin wafer in a predetermined amount, and WLC-T (Mitsubishi Gas Chemical Co., Ltd.) is used as an etchant for the titanium layer. used in quantity.

The following evaluation criteria evaluated process adaptability about the above-mentioned laminated body production. In addition, laminates were produced at two levels of curing temperature of the insulating layer, 230° C. and 280° C., and suitability for the laminate production process of the present disclosure was confirmed. Table 1 shows the results.
-Evaluation criteria-
A. Through the production of the laminate described above, peeling of the metal thin film layer did not occur, the residue of the cured film could be removed, and each step could be performed without problems.
B: Although the metal thin film layer did not peel off, there was a problem in the removability of the residue of the cured film.
Peeling of the C metal thin film layer occurred, and there was also a problem in the removability of the residue of the cured film.

As shown in Table 1, the resin compositions of Examples 1 to 10 are superior in releasability from the support compared to the resin composition of Comparative Example 1, and the applicability evaluation at the time of preparation of the laminate is also It was good.
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 the applicability evaluation during production of the laminate was also better.

<Continuity evaluation of resin package>
Regarding the obtained resin package, the copper wiring, insulating layer, etc. are checked for cross-section and conduction due to the heat effect of the separation process, and it is evaluated whether deterioration of the copper wiring, insulating layer, etc. has occurred. did.

In order to confirm the cross section, the resin package was cut at any point using a blade dicing device, and after the cross section was polished with abrasive paper No. 2000 using a sample polishing device, the cross section was observed with an electron microscope. gone. As a result, in Examples 1 to 7, it was confirmed that there was no deterioration in the copper wiring and insulating layer. On the other hand, in Comparative Example 1, deterioration of a part of the insulating layer was confirmed.

In addition, conduction was confirmed using a probe for the resin package. In Examples 1 to 7, conduction between the semiconductor chip and the rewiring could be confirmed.

From the above points, it was found that in Examples 1 to 7, regardless of the curing temperature of the insulating layer, a semiconductor package can be manufactured while suppressing abnormalities during the process, deterioration during peeling, and the like.

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 chip 11 bump 20 sealing material 30 residue 100 semiconductor device

Claims (19)

A resin composition containing a polyimide precursor and used for the following treatments (a) to (c).
(a) forming a cured film of the resin composition on a support;
(b) producing a laminate on the cured film;
(c) separating the laminate from the support; 2. The resin composition according to claim 1, further comprising a solvent, and the content of said solvent is 50 parts by mass to 10000 parts by mass with respect to 100 parts by mass of the resin component. Said solvents include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, γ-butyrolactone, cyclopentanone, dimethylsulfoxide, dimethylimidazolidinone and N- 3. The resin composition according to claim 2, comprising at least one selected from the group consisting of formylpiperidine. 4. The resin composition according to any one of claims 1 to 3, wherein the cured film does not deteriorate after being heat-treated at 100°C to 400°C for 4 hours or less. 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).

(In general formula (1), X represents a tetravalent organic group and Y represents a divalent organic group. R ⁶ and R ⁷ each independently represent a hydrogen atom or a monovalent organic group. At least one of ^R6 and ^R7 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).

(In general formula (2), R ⁸ to R ¹⁰ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R ^x represents a divalent linking group.) 7. The resin composition according to any one of claims 1 to 6, further comprising a polymerizable monomer and a thermal polymerization initiator. The resin composition according to any one of claims 1 to 7, which is used for the following treatment (d).
(d) removing the residue of the cured film remaining on the laminate after being separated from the support; 9. The resin composition according to claim 8, wherein in (d), the residue of the cured film remaining on the laminate can be removed by solvent treatment. A step of preparing the resin composition according to any one of claims 1 to 9;
forming a cured film of the resin composition on a support;
A step of producing a laminate on the cured film;
separating the laminate from the support;
A method of manufacturing a laminate comprising: 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 25°C to 300°C. 12. The method for producing a laminate according to claim 10, wherein the support has a thickness of 100 μm to 10000 μm and a transmittance of 90% or more for light with a wavelength of 355 nm. The method for producing a laminate according to any one of claims 10 to 12, wherein the laminate is separated from the support after irradiating the cured film with an active energy ray to modify the cured film. 14. The method for producing a laminate according to any one of claims 10 to 13, further comprising a step of removing residues of the cured film remaining on the laminate after being separated from the support. The method for producing a laminate according to any one of claims 10 to 14, wherein the heating temperature for forming the cured film is 100°C to 450°C. 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. The laminate is a semiconductor device comprising a wiring layer, an insulating layer and a semiconductor chip,
The step of fabricating the laminate comprises: forming the wiring layer on the cured film; forming the insulating layer that insulates at least between the wiring layers; and disposing the semiconductor chip on the insulating layer. , and connecting the semiconductor chip to the wiring layer. The laminate further includes a sealing material that seals the semiconductor chip,
18. The method of manufacturing a laminate according to claim 17, wherein the step of fabricating the laminate further includes a step of sealing the semiconductor chip connected to the wiring layer. A cured film obtained by curing the resin composition according to any one of claims 1 to 9.

Images