KR20230089551A - Composition for forming separation layer, support base provided with separation layer, laminate, method of producing the same, and method of producing electronic component - Google Patents

Abstract

[Problem] A composition for forming a separation layer capable of forming a separation layer in a laminate having a separation layer between a support substrate and a substrate, with higher photoreactivity and improved separation of the support substrate from the laminate. provide etc.
[Solution] In a laminate 10 having a separation layer 2 and an adhesive layer 3 between a light-transmitting support base 1 and a substrate 4, light from the support base side A composition for forming a separation layer for forming a separation layer capable of separating a support substrate from a laminate by being altered in quality by irradiation, comprising a resin component (P) having a repeating unit represented by formula (p1). A composition for layer formation is employed. In general formula (p1), L ^P1 represents a divalent linking group. R ^P1 represents a condensed polycyclic aromatic group which may have a substituent.
[Tue 1]

Description

Composition for forming separation layer, support base with separation layer, laminate and method for manufacturing the same, and method for manufacturing electronic components PRODUCING ELECTRONIC COMPONENT}

The present invention relates to a composition for forming a separation layer, a support base with a separation layer, a laminate, a method for manufacturing the same, and a method for manufacturing an electronic component.

There are various types of semiconductor packages (electronic components) including semiconductor elements depending on the corresponding size, and there are, for example, WLP (Wafer Level Package), PLP (Panel Level Package), and the like.

As a technology of a semiconductor package, a fan doll technology and a fan-out type technology are mentioned. As a semiconductor package based on the fan doll technology, a fan doll WLP (Fan-in Wafer Level Package) or the like is known in which terminals at the end of a bare chip are rearranged in a chip area. As a semiconductor package based on fan-out technology, a fan-out wafer level package (WLP) or the like in which the terminals are rearranged outside the chip area is known.

In recent years, in particular, fan-out technology has been applied to a fan-out panel level package (PLP) in which semiconductor elements are arranged and packaged on a panel, and further integration, thinning, and miniaturization of semiconductor packages, etc. is attracting attention as a way to realize it.

In order to achieve miniaturization of a semiconductor package, it becomes important to make the thickness of the board|substrate in an assembled element thin. However, if the thickness of the substrate is reduced, its strength is reduced, making it easier to damage the substrate during semiconductor package manufacturing. In contrast, a laminate in which a substrate is bonded to a support substrate is employed.

In Patent Document 1, a light-transmitting support substrate and a substrate are bonded via a light-to-heat conversion layer (separation layer) provided on the support substrate side and an adhesive layer, and after processing the substrate, radiation is applied to the separation layer from the support substrate side Disclosed is a method of manufacturing a laminate by irradiating energy (light) to alter and decompose a separation layer, thereby separating a substrate after processing and a support substrate.

[Patent Document 1] Japanese Unexamined Patent Publication No. 2004-64040

As described in Patent Literature 1, when a semiconductor package is miniaturized by employing a laminate in which a support substrate is bonded to a substrate, separability of the support substrate from the laminate becomes a problem.

The present invention has been made in view of the above circumstances, and in a laminate having a separation layer between a support substrate and a substrate, a separation layer having higher photoreactivity and improved separation of the support substrate from the laminate is formed. It is an object to provide a composition for forming a separation layer that can be used, a support substrate with a separation layer using the same, a laminate, a manufacturing method thereof, and a manufacturing method of an electronic component.

In order to solve the above problems, the present invention adopts the following configuration.

That is, in the first aspect of the present invention, in a laminate having a separation layer between a support substrate through which light is transmitted and a substrate, the laminate is changed in quality by irradiation of light from the support substrate side, and the laminate is formed. A composition for forming a separation layer for forming the separation layer capable of separating the support gas from the separation layer, characterized in that it contains a resin component (P) having a repeating unit represented by the following general formula (p1), composition for formation.

[In formula, L ^P1 represents a divalent linking group. R ^P1 represents a condensed polycyclic aromatic group which may have a substituent.]

A second aspect of the present invention is a support substrate with a separation layer characterized by comprising a support substrate and a separation layer formed on the support substrate using the composition for forming a separation layer according to the first aspect. .

A third aspect of the present invention is a laminate having a separation layer between a support substrate that transmits light and a substrate, wherein the separation layer is formed by firing the composition for forming a separation layer according to the first aspect. It is a laminate characterized by being a chain.

A fourth aspect of the present invention is a method for manufacturing a laminate comprising a separation layer between a support substrate that transmits light and a substrate, wherein the first layer is disposed on at least one of the substrate and the support substrate. Having a separation layer forming step of forming the separation layer by applying a composition for forming a separation layer according to the embodiment and then firing it, and a lamination step of laminating the substrate and the support substrate through the separation layer It is characterized by the manufacturing method of a laminated body.

A fifth aspect of the present invention is to irradiate the separation layer with light through the supporting substrate to alter the quality of the separation layer after obtaining the laminate by the method for manufacturing the laminate according to the fourth aspect. A method of manufacturing an electronic component characterized by comprising a separation step of separating the support substrate from the layered body and a removal step of removing the separation layer attached to the substrate after the separation step.

According to the present invention, in a laminate having a separation layer between a support substrate and a substrate, for forming a separation layer capable of forming a separation layer with improved separation of the support substrate from the laminate due to higher photoreactivity. The composition, a support base with a separation layer using the same, a laminate, a manufacturing method thereof, and a manufacturing method of an electronic component can be provided.

[Fig. 1] It is a schematic diagram showing one embodiment of a laminate to which the present invention is applied.
[Fig. 2] It is a schematic process diagram explaining one embodiment of a method for manufacturing a laminate. Fig. 2(a) is a diagram explaining a separation layer forming process, and Fig. 2(b) is a diagram explaining a lamination process.
[ Fig. 3 ] It is a schematic process diagram explaining another embodiment of a method for manufacturing a laminate. Fig.3 (a) is a figure which shows the laminated body manufactured by the manufacturing method of 1st Embodiment, and Fig.3 (b) is a figure explaining the sealing process.
[ Fig. 4 ] It is a schematic process diagram explaining another embodiment of a method for manufacturing a laminate. Fig. 4 (a) is a diagram showing an encapsulated body manufactured by the manufacturing method of the second embodiment, Fig. 4 (b) is a diagram explaining a grinding step, and Fig. 4 (c) is a rewiring forming step. It is a diagram explaining
[ Fig. 5 ] It is a schematic process diagram explaining one embodiment of a method for manufacturing a semiconductor package (electronic component). Fig. 5 (a) is a diagram showing a laminate manufactured by the manufacturing method of the third embodiment, Fig. 5 (b) is a diagram explaining a separation step, and Fig. 5 (c) is a diagram illustrating a removal step It is an explanatory diagram.
[ Fig. 6 ] It is a schematic process chart explaining another embodiment of a method for manufacturing a semiconductor package (electronic component). Fig. 6 (a) is a schematic diagram showing another embodiment of a laminate to which the present invention is applied, Fig. 6 (b) is a diagram explaining a separation step, and Fig. 6 (c) is a diagram explaining a removal step am.

In this specification and the claims of this patent, "aliphatic" is defined as a relative concept with respect to aromatic, meaning a group or compound that does not have aromaticity.

"Alkyl group" shall include linear, branched, and cyclic monovalent saturated hydrocarbon groups unless otherwise specified. The same applies to the alkyl group in the alkoxy group.

"Alkylene group" shall include linear, branched, and cyclic divalent saturated hydrocarbon groups unless otherwise specified.

A "halogenated alkyl group" is a group in which some or all of the hydrogen atoms in the alkyl group are substituted with halogen atoms, and examples of the halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

A "fluorinated alkyl group" refers to a group in which some or all of the hydrogen atoms of an alkyl group are substituted with fluorine atoms.

A "repeating unit" means a monomer unit (monomer unit) constituting a high molecular compound (resin, polymer, copolymer).

When describing "it may have a substituent", both the case where a hydrogen atom (-H) is substituted with a monovalent group and the case where a methylene group (-CH ₂ -) is substituted with a divalent group are included.

"Styrene" is a concept that includes styrene and those in which hydrogen atoms at the α position of styrene are substituted with other substituents such as alkyl groups and halogenated alkyl groups. Incidentally, the α-position (carbon atom on α-position) refers to the carbon atom to which the benzene ring is bonded unless otherwise specified.

The alkyl group as the substituent at the α-position is preferably a linear or branched chain alkyl group, specifically, an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group , tert-butyl group, pentyl group, isopentyl group, neopentyl group) and the like.

In addition, the halogenated alkyl group as a substituent at α-position specifically includes a group in which part or all of the hydrogen atoms of the “alkyl group as a substituent at α-position” are substituted with halogen atoms. As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is especially preferable.

In this specification and claims of this patent, depending on the structure represented by the chemical formula, asymmetric carbon exists, and enantiomers and diastereomers may exist. In that case, those isomers are represented by a single chemical formula. Such isomers may be used alone or as a mixture.

(Composition for Forming Separation Layer)

In the composition for forming a separation layer according to the first aspect of the present invention, in a laminate having a separation layer between a light-transmitting support substrate and a substrate, the composition is altered by irradiation of light from the side of the support substrate. This is to form the separation layer capable of separating the support gas from the laminate. The composition for forming a separation layer of the present embodiment contains at least a resin component (P) having a repeating unit represented by general formula (p1).

1 shows an embodiment of a laminate to which the present invention is applied.

The laminate 10 shown in FIG. 1 includes a separation layer 2 and an adhesive layer 3 between a support substrate 1 and a substrate 4, and on the support substrate 1 a separation layer ( 2), the adhesive layer 3, and the substrate 4 are laminated in this order.

The supporting body 1 is made of a material that transmits light. Regarding the laminate 10, since the separation layer 2 is altered and decomposed by irradiating the separation layer 2 with light from the support substrate 1 side, the separation layer 2 is decomposed from the support substrate 10. (1) isolates.

The separation layer 2 in this layered product 10 can be formed using the composition for forming a separation layer of the present embodiment.

<Resin component (P)>

The resin component (P) (hereinafter also referred to as “component (P)”) is a resin component having a repeating unit represented by general formula (p1).

Component (P) has a condensed polycyclic aromatic group (R ^P1 ) which may have a substituent in the repeating unit. As a result, in the separation layer formed from the composition for forming a separation layer containing the component (P), the laser reactivity is enhanced, the photoreactivity is further enhanced, and the separation of the supporting substrate from the laminate is improved.

In addition, component (P) has a divalent linking group (L ^P1 ) in the repeating unit. For this reason, component (P) tends to change in quality (oxidation, etc.) by heating or the like. In the separation layer formed from the composition for forming a separation layer containing the component (P), the light absorption property is increased and the photoreactivity is excellent.

In FIG. 1, the laminate 10 having the separation layer 2 formed by using the composition for forming a separation layer containing component (P) is separated by irradiation of light from the support substrate 1 side. The layer 2 is altered and easily peeled off from the substrate 4, and the support substrate 1 is separated. In addition, when the separation layer 2 containing component (P) is peeled off from the substrate 4, there is little residue (residue) adhering to the substrate 4, and the removability from the substrate 4 is also good. In addition, component (P) has a divalent linking group (L ^P1 ) in the repeating unit, so that the separation layer 2 containing component (P) can increase heat resistance and also has high chemical resistance.

In addition, since the component (P) has strong laser reactivity, the separation layer 2 containing the component (P) can suppress laser damage, increase the laser intensity, and shorten the process time. can help

Component (P) may have other repeating units in addition to the repeating unit represented by general formula (p1).

<<repeating unit represented by general formula (p1)>>

Component (P) has a repeating unit represented by the following general formula (p1) (hereinafter also referred to as “repeating unit (p1)”).

[In formula, L ^P1 represents a divalent linking group. R ^P1 represents a condensed polycyclic aromatic group which may have a substituent.]

In the above formula (p1), the divalent linking group in L ^P1 may contain an aromatic ring, may contain a plurality of types of aromatic rings, or may contain a ring structure in which an aromatic ring and an aliphatic ring are condensed.

When the divalent linking group in L ^P1 contains an aromatic ring, the aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, still more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms.

Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; An aromatic heterocycle in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom; and the like. As a hetero atom in an aromatic heterocycle, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned. As an aromatic heterocycle, a pyridine ring, a thiophene ring, etc. are mentioned specifically,.

The number of aromatic rings in which the divalent linking group is included may be one or two or more, and two or more are preferable since photoreactivity is more excellent.

Alternatively, in the formula (p1), the divalent linking group in L ^P1 is preferably a divalent linking group containing a hetero atom. Examples of L ^p1 include linking groups in which various skeletons are introduced in order to impart desired characteristics.

Examples of the skeleton in the "linking group into which various skeletons are introduced" include naphthalene skeleton, anthracene skeleton, xanthene skeleton, fluorene skeleton, and bisphenol A skeleton.

Examples of L ^p1 include bisphenol-type ether linking groups, diol-type ether linking groups, dicarboxylic acid-type ester linking groups, Si-O linking groups, or repeating structures of these linking groups.

Examples of the bisphenols include bisphenol F, bisphenol A, bisphenol Z, biphenol, and polymers thereof.

As the diols concerned, ethylene glycol, propylene glycol, 1,6-hexanediol, neopentyl glycol, naphthalene diol (dihydroxynaphthalene), anthracene diol (dihydroxyanthracene), 2,2-bis(4-hydroxy phenyl) propane or polymers thereof; and the like.

Examples of the dicarboxylic acids include maleic acid, phthalic acid, hydrogenated phthalic acid, and terephthalic acid.

When bisphenol-type ether bonding group is selected as L ^p1 , it becomes easy to improve the flexibility of the film of component (P).

When an ether bond group of diols is selected as L ^p1 , the alkali solubility of component (P) can be easily adjusted. As the ether linking group of diols, a linking group into which a glycol skeleton is introduced is preferable. As a glycol skeleton, a propylene glycol skeleton is mentioned, for example.

When a Si-O bond group is selected as L ^p1 , it becomes easy to achieve a low dielectric constant of the molded article of component (P).

Preferable specific examples for L ^P1 (divalent linking group) in the formula (p1) are shown below. In the formulas below, * represents a bond bonded to a methylene group (CH ₂ ). n in the formula (L ^P1-9 ) represents the repeating number of the oxypropylene group.

In the formula (p1), R ^P1 is a condensed polycyclic aromatic group which may have a substituent.

The condensed polycyclic aromatic group in R ^P1 is a group obtained by removing one hydrogen atom from the condensed polycyclic aromatic ring. This condensed polycyclic aromatic ring may have a ring structure in which a plurality of aromatic rings are condensed, or a ring structure in which an aromatic ring and an aliphatic ring are condensed. Regarding the ring structure in which an aromatic ring and an aliphatic ring are condensed, the number of aromatic rings may be plural, the number of aliphatic rings may be plural, or the number of aromatic rings and aliphatic rings may be one each.

The number of rings constituting this condensed polycyclic aromatic ring is preferably 2 to 5, more preferably 2 to 3, still more preferably 3.

In the formula (p1), examples of the substituent that the condensed polycyclic aromatic group in R ^P1 may have include a hydroxyl group, a carboxy group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), an alkyloxycarbonyl group, an oxo group (=O), and the like.

In addition, the hydrocarbon group in the condensed polycyclic aromatic group in R ^P1 may have an ether bond in the middle of the hydrocarbon chain.

As R ^P1 , for example, a naphthalene ring, an azulene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a chrysene ring, a triphenylene ring, a perylene ring, an anthriquinone ring, or a naphthoquinone ring excluding one hydrogen atom. can lift

Among these, as R ^P1 , a group in which one hydrogen atom is removed from an anthriquinone ring or a naphthoquinone ring is preferable, and a group in which one hydrogen atom is removed from an anthraquinone ring is more preferable.

Preferable specific examples of the repeating unit (p1) are shown below. n1 in formula (p1-6) represents the repeating number of an oxypropylene group.

(P) The repeating unit (p1) which component has may be 1 type or 2 or more types may be sufficient as it.

The ratio of the repeating unit (p1) in component (P) is preferably 1 mol% or more, and may be 1 to 100 mol%, based on the total (100 mol%) of all repeating units constituting component (P).

When the component (P) has other repeating units in addition to the repeating unit (p1), the ratio of the repeating units (p1) in the component (P) is the sum of all repeating units constituting the component (P) (100 mol%), 1 to 99 mol% is preferable, 1 to 70 mol% is more preferable, and 1 to 50 mol% is still more preferable.

When the ratio of the repeating unit (p1) is equal to or greater than the lower limit of the above preferred range, the laser reactivity tends to be enhanced. On the other hand, if it is below the upper limit of the above preferable range, it becomes easy to balance with other repeating units.

≪Other repeating units≫

Component (P) may have other repeating units in addition to the repeating unit (p1) described above.

Examples of other repeating units include repeating units represented by general formula (p2) described later.

Regarding the repeating unit represented by the general formula (p2):

Component (P) is preferably a resin having, in addition to the repeating unit (p1) described above, a repeating unit represented by the following general formula (p2) (hereinafter also referred to as “repeating unit (p2)”).

[In formula, L ^P2 represents a divalent linking group. R ^P2 represents a monocyclic aromatic group which may have a substituent.]

The description of L ^P2 in the above formula (p2) is the same as the description of the divalent linking group in L ^P1 in the above formula (p1).

Preferable specific examples of L ^P2 (divalent linking group) include the same linking groups respectively represented by the above formulas (L ^P1-1 ) to (L ^P1-9 ).

In the formula (p2), the monocyclic aromatic group for R ^P2 is a hydrocarbon group having one aromatic ring. This aromatic ring may be a cyclic conjugated system having 4n+2 pi electrons.

Specific examples of the aromatic ring constituting the monocyclic aromatic group for R ^P2 include a benzene ring; A pyridine ring, a thiophene ring, a pyrrole ring, an imidazole ring, a furan ring, a thiazole ring, etc. are mentioned. Among these, as R ^P2 , a group in which one hydrogen atom is removed from the benzene ring is preferable.

When the hydrocarbon group represented by R ^P2 is substituted, examples of the substituent include a hydroxy group, a carboxy group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkoxy group (methoxy group, ethoxy group, propoxy group) groups, butoxy groups, etc.), alkyloxycarbonyl groups, and the like.

Preferred specific examples of the repeating unit (p2) are shown below. n2 in formula (p2-6) represents the repeating number of an oxypropylene group.

(P) When a component has a repeating unit (p2), 1 type or 2 or more types of repeating units may be sufficient as the repeating unit (p2).

When the component (P) has a repeating unit (p2), the ratio of the repeating unit (p2) in the component (P) is 1 to 1 to the total (100 mol%) of all repeating units constituting the component (P). 99 mol% is preferable, 30 to 99 mol% is more preferable, and 50 to 99 mol% is still more preferable.

When the ratio of the repeating unit (p2) is equal to or greater than the lower limit of the above preferred range, the photoreactivity is easily improved. On the other hand, if it is below the upper limit of the above preferable range, it becomes easy to balance with the repeating unit (p1).

In the composition for forming a separation layer of the present embodiment, component (P) is a resin having at least a repeating unit (p1).

Component (P) may be a resin composed only of the repeating unit (p1).

As a preferable (P) component, resin which has a repeating unit (p1) and a repeating unit (p2) is mentioned. In this case, the ratio (molar ratio) of the repeating unit (p1) to the repeating unit (p2) in the resin is preferably repeating unit (p1):repeating unit (p2) = 1:99 to 99:1, 1:99 -70:30 is more preferred, and 1:99 - 50:50 is still more preferred.

Alternatively, the component (P) may be a mixed resin of a resin having at least the repeating unit (p1) and a resin consisting only of the repeating unit (p2). In this case, the proportion of the repeating unit (p1) is preferably 1 to 99 mol%, more preferably 1 to 70 mol%, relative to the total (100 mol%) of all repeating units constituting the mixed resin. , more preferably 1 to 50 mol%. It is preferable that the ratio (molar ratio) of all repeating units (p1) and all repeating units (p2) constituting the mixed resin is all repeating units (p1):all repeating units (p2) = 1:99 to 99:1, , It is more preferably 1:99 to 70:30, and more preferably 1:99 to 50:50.

Component (P) has film-forming ability, and preferably has a molecular weight of 1000 or more. (P) When the molecular weight of the component is 1000 or more, the film-forming ability is improved. As for the molecular weight of component (P), 1000-30000 are more preferable, 1500-25000 are more preferable, 1500-20000 are especially preferable, and 2000-15000 are the most preferable.

When the molecular weight of component (P) is equal to or less than the upper limit of the above preferred range, the solubility of the composition for forming a separation layer in a solvent can be improved.

In addition, as a molecular weight of a resin component, the weight average molecular weight (Mw) of polystyrene conversion by GPC (gel permeation chromatography) shall be used.

As the component (P), for example, the GSP series (manufactured by Gunei Chemical Industry Co., Ltd.) with trade names of GSP-112, GSP-113, and GSP-117 can be used.

Further, as component (P), a resin produced by reacting amino antriquinone or amino naphthoquinone with amino phenols, amino naphthols or anilines and a compound having two epoxy groups in one molecule can also be used.

As amino phenols, 2-amino phenol, 3-amino phenol, 4-amino phenol, 4-amino-3-methyl phenol, 2-amino-4-methyl phenol, 3-amino-2-methyl phenol, 5-amino- 2-methyl phenol etc. are mentioned. Examples of amino naphthols include 1-amino-2-naphthol, 3-amino-2-naphthol, and 5-amino-1-naphthol.

As a compound which has two epoxy groups in 1 molecule, For example, bisphenol-type epoxy resins, such as a brand name EPICLON850, EPICLON830 (made by DIC Corporation), and jERYX-4000 (made by Mitsubishi Chemical Corporation); diol type epoxy resins such as DENACOL EX-211, DENACOL EX-212, DENACOL EX-810, DENACOL EX-830, DENACOL EX-911, DENACOL EX-920, and DENACOL EX-930 (manufactured by Nagase ChemteX Co., Ltd.); dicarboxylic acid ester type epoxy resins such as DENACOL EX-711, DENACOL EX-721 (manufactured by Nagase ChemteX Co., Ltd.) and jER191P (manufactured by Mitsubishi Chemical Corporation); Silicone type epoxy resins, such as X-22-163 and KF-105 (made by Shin-Etsu Chemical Co., Ltd.), etc. are mentioned.

The heat treatment temperature at the time of such a reaction is preferably 60°C or higher and 250°C or lower, and more preferably 80°C or higher and 180°C or lower.

The component (P) contained in the composition for forming a separation layer of the present embodiment may be one type or two or more types.

The content of component (P) in the composition for forming a separation layer of the present embodiment may be adjusted according to the thickness of the separation layer to be formed.

The content of component (P) in such a composition for forming a separation layer is preferably 1 to 100% by mass, more preferably 1 to 70% by mass, and 5 to 70% by mass, for example, based on the composition (100% by mass). 50 mass % is more preferable, and 10-50 mass % is especially preferable.

When the content of component (P) is equal to or greater than the lower limit of the above preferred range, the photoreactivity of the separation layer is more likely to be enhanced. In addition, it becomes easy to improve chemical resistance. On the other hand, if it is below the upper limit of said preferable range, it becomes easy to improve photoreactivity and peelability more.

<Other ingredients>

The composition for forming a separation layer of the present embodiment may further contain components (optional components) other than the component (P) described above.

Examples of such optional components include resins other than the component (P) shown below, thermal acid generator components, photoacid generator components, photosensitizer components, organic solvent components, surfactants, and sensitizers.

In the composition for forming a separation layer of the present embodiment, resins other than component (P) may be contained within a range not impairing the effects of the present invention.

Examples of resins other than component (P) include novolac-type phenol resins, resol-type phenol resins, hydroxystyrene resins, hydroxyphenylsilsesquioxane resins, hydroxybenzylsilsesquioxane resins, and phenol skeleton-containing An acrylic resin etc. are mentioned.

By using a novolac-type phenolic resin as a resin other than the component (P) in combination with the component (P), generation of voids due to heating is also easily suppressed.

≪Thermal acid generator≫

In the composition for forming a separation layer of the present embodiment, it is preferable to further contain a thermal acid generator (hereinafter also referred to as "component (T)").

When such a composition for forming a separation layer contains the component (T), oxidation of the separation layer is promoted by the action of the acid generated from the component (T) during heating during firing, etc., so that the separation layer is easily changed in quality by irradiation with light. (The photoreactivity of the separation layer can be increased).

Component (T) can be appropriately selected and used from known ones, and the temperature for generating the acid is preferably equal to or higher than the temperature at the time of prebaking the support substrate coated with the composition for forming a separation layer, and is 110°C or higher. It is more preferable, and it is more preferable that it is 130 degreeC or more.

Examples of the component (T) include trifluoromethane sulfonic acid salts, hexafluorophosphate salts, perfluorobutane sulfonate salts, boron trifluoride salts, and boron trifluoride ether complex compounds. As a preferable component (T), compounds comprising a cation moiety and an anion moiety shown below are exemplified.

[In formula (T-ca-1), R ^h01 to R ^h04 are each independently a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an aryl group, and at least one of R ^h01 to R ^h04 is an aryl group. The said alkyl group or aryl group may have a substituent. In formula (T-ca-2), R ^h05 to R ^h07 are each independently a group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms and an aryl group, and at least one of R ^h05 to R ^h07 is an aryl group am. The above alkyl group or aryl group may have a substituent.]

ㆍAbout the cationic part of component (T)

In the formula (T-ca-1), the alkyl group for R ^h01 to R ^h04 has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and 1 to 5 carbon atoms. A straight-chain or branched-chain alkyl group of is more preferable. Specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. are mentioned, Among these, a methyl group, An ethyl group is preferred.

The alkyl group in R ^h01 to R ^h04 may have a substituent. As this substituent, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, a cyclic group etc. are mentioned, for example.

The alkoxy group as a substituent of the alkyl group is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group, and a methoxy group An ethoxy group is more preferable.

As for the halogen atom as a substituent of an alkyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable.

The halogenated alkyl group as a substituent of the alkyl group is an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group, etc., in which some or all of the hydrogen atoms are substituted with the halogen atoms. can

A carbonyl group as a substituent of an alkyl group is a group (>C=O) that substitutes a methylene group (-CH ₂ -) constituting the alkyl group.

Examples of the cyclic group as a substituent for the alkyl group include an aromatic hydrocarbon group and an alicyclic hydrocarbon group (which may be polycyclic or monocyclic). Examples of the aromatic hydrocarbon group include the same as the aryl groups for R ^h01 to R ^h04 described later. In the alicyclic hydrocarbon group herein, as the monocyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from monocycloalkane is preferable. As said monocycloalkane, a C3-C6 thing is preferable, and a cyclopentane, a cyclohexane, etc. are mentioned specifically,. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from polycycloalkane is preferable, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among them, examples of the polycycloalkanes include polycycloalkanes having a polycyclic backbone of a bridge exchange system such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; A polycycloalkane having a polycyclic skeleton of a condensed ring system such as a cyclic group having a steroid skeleton is more preferable.

In the above formula (T-ca-1), the aryl group in R ^h01 to R ^h04 is a hydrocarbon group having at least one aromatic ring.

This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, still more preferably 6 to 15, and particularly preferably 6 to 12.

Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; An aromatic heterocycle in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom; and the like. As a hetero atom in an aromatic heterocycle, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned. As an aromatic heterocycle, a pyridine ring, a thiophene ring, etc. are mentioned specifically,.

As the aryl group for R ^h01 to R ^h04 , specifically, a group obtained by removing one hydrogen atom from the above aromatic hydrocarbon ring or aromatic heterocycle; A group obtained by excluding one hydrogen atom from an aromatic compound (for example, biphenyl, fluorene, etc.) containing two or more aromatic rings; A group in which one of the hydrogen atoms of the above aromatic hydrocarbon ring or aromatic heterocycle is substituted with an alkylene group (eg, benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, aryl alkyl groups such as a 2-naphthylethyl group, etc.); and the like. As for carbon number of the alkylene group couple|bonded with the said aromatic hydrocarbon ring or aromatic heterocyclic ring, it is preferable that it is 1-4, it is more preferable that it is 1-2, and it is especially preferable that it is 1. Among these, a group in which one hydrogen atom is removed from the above aromatic hydrocarbon ring or aromatic heterocycle, or a group in which one of the hydrogen atoms of the above aromatic hydrocarbon ring or aromatic heterocycle is substituted with an alkylene group is more preferable, and the above aromatic hydrocarbon ring A group in which one hydrogen atom is removed from , and a group in which one of the hydrogen atoms of the aromatic hydrocarbon ring is substituted with an alkylene group are more preferable.

The aryl group in R ^h01 to R ^h04 may have a substituent. As this substituent, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, a cyclic group, an alkyl carbonyloxy group etc. are mentioned, for example.

The alkyl group as a substituent for the aryl group is preferably an alkyl group having 1 to 5 carbon atoms, and is preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.

Descriptions of alkoxy groups, halogen atoms, halogenated alkyl groups, carbonyl groups, and cyclic groups as substituents for aryl groups are the same as those for alkoxy groups, halogen atoms, halogenated alkyl groups, carbonyl groups, and cyclic groups as substituents for alkyl groups described above.

In the alkylcarbonyloxy group as a substituent for the aryl group, the alkyl moiety preferably has 1 to 5 carbon atoms, and examples of the alkyl moiety include a methyl group, an ethyl group, a propyl group, an isopropyl group, and the like. Among these, a methyl group and an ethyl group are It is preferable, and a methyl group is more preferable.

However, in the formula (T-ca-1), at least one of R ^h01 to R ^h04 is an aryl group which may have a substituent.

Below, the specific example of the cation represented by the said formula (T-ca-1) is shown.

In the above formula (T-ca-2), the description of the alkyl group and the aryl group in R ^h05 to R ^h07 is the same as the description of the alkyl group and aryl group in R ^h01 to R ^h04 described above, respectively.

However, in the formula (T-ca-2), at least one of R ^h05 to R ^h07 is an aryl group which may have a substituent.

Below, the specific example of the cation represented by the said formula (T-ca-2) is shown.

ㆍAbout the anion part of component (T)

Examples of the anion moiety of component (T) include hexafluorophosphate anion, trifluoromethanesulfonate anion, perfluorobutanesulfonate anion, tetrakis(pentafluorophenyl)borate anion, and the like. .

Among these, hexafluorophosphate anion, trifluoromethanesulfonic acid anion, and perfluorobutane sulfonic acid anion are preferable, and hexafluorophosphate anion and trifluoromethanesulfonic acid anion are more preferable.

In the composition for forming a separation layer of the present embodiment, as component (T), for example, trade names San-Aid SI-45, SI-47, SI-60, SI-60L, SI-80, SI-80L, SI -100, SI-100L, SI-110, SI-110L, SI-145, I-150, SI-160, SI-180L, SI-B3, SI-B2A, SI-B3A, SI-B4, SI-300 (Above, manufactured by Sanshin Kagaku Kogyo Co., Ltd.); CI-2921, CI-2920, CI-2946, CI-3128, CI-2624, CI-2639, CI-2064 (manufactured by Nippon Soda Co., Ltd.); CP-66, CP-77 (manufactured by ADEKA Corporation); FC-520 (manufactured by 3M); K-PURE　TAG-2396, TAG-2713S, TAG-2713, TAG-2172, TAG-2179, TAG-2168E, TAG-2722, TAG-2507, TAG-2678, TAG-2681, TAG-2679, TAG-2689 , TAG-2690, TAG-2700, TAG-2710, TAG-2100, CDX-3027, CXC-1615, CXC-1616, CXC-1750, CXC-1738, CXC-1614, CXC-1742, CXC-1743, CXC -1613, CXC-1739, CXC-1751, CXC-1766, CXC-1763, CXC-1736, CXC-1756, CXC-1821, CXC-1802-60, CXC-2689 (above, manufactured by KING INDUSTRY), etc. A commercial product can be used.

The component (T) contained in the composition for forming a separation layer of the present embodiment may be one type or two or more types.

In the composition for forming a separation layer of the present embodiment, among the above, as the component (T), hexafluorophosphate, trifluoromethanesulfonic acid salt, and perfluorobutanesulfonic acid salt are preferred, and trifluoromethanesulfonic acid A salt is more preferred, and a quaternary ammonium salt of trifluoromethane sulfonic acid is still more preferred.

When the composition for forming a separation layer of the present embodiment contains component (T), the content of component (T) is preferably 0.01 to 20 parts by mass, and preferably 1 to 15 parts by mass, based on 100 parts by mass of component (P). Part is more preferable, and 2 to 10 parts by mass is even more preferable.

When the content of component (T) is within the above preferred range, it is easily changed in quality by light irradiation (photoreactivity of the separation layer can be improved). For example, by firing, a fired body capable of suitably absorbing light in a wavelength range of 600 nm or less can be easily formed. In addition, chemical resistance is also further improved.

≪Mine Generator≫

The composition for forming a separation layer of the present embodiment may further contain a photoacid generator.

Such a composition for forming a separation layer contains a photo-acid generator, as in the case of containing the component (T) as described above, by the action of an acid generated from the photo-acid generator by heating during firing or the like. Since the oxidation of the separation layer is accelerated, it is easily deteriorated by light irradiation (photoreactivity of the separation layer can be enhanced).

As the photo-acid generator, for example, onium salt-based acid generators such as sulfonium salts are preferred.

In the onium salt-based acid generator, sulfonium cations and iodonium cations are exemplified as preferable cation moieties.

In the onium salt-based acid generator, preferred anion moieties include tetrakis(pentafluorophenyl) borate ([B(C ₆ F ₅ ) ₄ ] ^- ); tetrakis[(trifluoromethyl)phenyl]borate ([B(C ₆ H ₄ CF ₃ ) ₄ ] ^- ); difluoro bis(pentafluorophenyl) borate ([(C ₆ F ₅ ) ₂ BF ₂ ] ^- ); trifluoro(pentafluorophenyl) borate ([(C ₆ F ₅ )BF ₃ ] ^- ); tetrakis(difluorophenyl) borate ([B(C ₆ H ₃ F ₂ ) ₄ ] ^- ); and the like. An anion represented by the following general formula (b0-2a) is also preferable.

[In formula, R ^bf05 is a fluorinated alkyl group which may have a substituent. nb ¹ is an integer of 1 to 5.]

In the formula (b0-2a), the fluorinated alkyl group for R ^bf05 preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 5 carbon atoms. Especially, as R ^bf05 , a C1-C5 fluorinated alkyl group is preferable, a C1-C5 perfluoroalkyl group is more preferable, and a trifluoromethyl group or a pentafluoroethyl group is still more preferable.

In the formula (b0-2a), nb ¹ is preferably an integer of 1 to 4, more preferably an integer of 2 to 4, and most preferably 3.

When nb ¹ is 2 or more, a plurality of R ^{bf05 '} s may be the same or different.

The photo-acid generator contained in the composition for forming a separation layer of the present embodiment may be one type or two or more types.

When the composition for forming a separation layer of the present embodiment contains a photoacid generator, the content of the photoacid generator is preferably 0.01 to 20 parts by mass, and preferably 1 to 15 parts by mass, based on 100 parts by mass of component (P). Part is more preferable, and 2 to 10 parts by mass is even more preferable.

When the content of the photo-acid generator is within the above preferred range, it is easily changed in quality by light irradiation (photoreactivity of the separation layer can be improved). For example, by firing, a fired body capable of suitably absorbing light in a wavelength range of 600 nm or less can be easily formed. In addition, chemical resistance is also further improved.

≪Photosensitizer Component≫

As the photosensitizer component (hereinafter also referred to as “component (C)”), for example, an esterification reaction between a phenolic hydroxyl group-containing compound represented by the following formula (c1) and a 1,2-naphthoquinonediazide sulfonic acid compound A product (hereinafter also referred to as "component (C1)") is mentioned as a suitable one.

Examples of 1,2-naphthoquinonediazide sulfonic acid compounds include 1,2-naphthoquinonediazide-5-sulfonyl compounds, 1,2-naphthoquinonediazide-4-sulfonyl compounds, and the like. , 1,2-naphthoquinonediazide-5-sulfonyl compounds are preferred.

Below, the suitable specific example of component (C1) is shown.

[In formula (c1-1), D ¹ to D ⁴ each independently represent a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group. At least one of D ¹ to D ⁴ represents a 1,2-naphthoquinonediazide-5-sulfonyl group.]

It is preferable that it is 50 to 70 %, and, as for the esterification rate of the said component (C1), it is more preferable that it is 55 to 65 %. When the esterification rate is 50% or more, the film reduction after alkali development is more suppressed, and the remaining film rate is increased. Storage stability improves more as the said esterification rate is 70 % or less.

"Esterification rate" as used herein means that D ¹ to D ⁴ in formula (c1-1) are substituted with 1,2-naphthoquinonediazide-5-sulfonyl groups in the compound represented by formula (c1-1). indicate the percentage of

The component (C1) is also preferable from the viewpoint of being very inexpensive and highly sensitive.

In addition, as component (C), other photosensitizer components (hereinafter, this is also referred to as "component (C2)") other than the component (C1) can be used.

As the component (C2), for example, the following phenolic hydroxyl group-containing compound ((c2-phe) component) and a 1,2-naphthoquinonediazide sulfonic acid compound (preferably 1,2-naphtho An esterification reaction product of a quinonediazide-5-sulfonyl compound or a 1,2-naphthoquinonediazide-4-sulfonyl compound) is mentioned as a suitable one.

As the component (c2-phe), for example, tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2 ,3,5-trimethylphenyl)-2-hydroxyphenyl methane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenyl methane, bis(4-hydroxy-3,5-dimethyl Phenyl)-3-hydroxyphenyl methane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenyl methane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxy hydroxyphenyl methane, bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxyphenyl methane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenyl methane, bis( 4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenyl methane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenyl methane, bis ( 4-hydroxy-2,5-dimethylphenyl) -2,4-dihydroxyphenyl methane, bis (4-hydroxyphenyl) -3-methoxy-4-hydroxyphenyl methane, bis (5-cyclohexyl -4-hydroxy-2-methylphenyl) -4-hydroxyphenyl methane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenyl methane, bis (5-cyclohexyl-4 -Hydroxy-2-methylphenyl)-2-hydroxyphenyl methane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3,4-dihydroxyphenyl methane, bis(2,3,5 -trimethyl-4-hydroxyphenyl)-2-hydroxyphenyl methane, 1-[1-(4-hydroxyphenyl) isopropyl]-4-[1,1-bis(4-hydroxyphenyl) ethyl] Benzene, 1-[1-(3-methyl-4-hydroxyphenyl)isopropyl]-4-[1,1-bis(3-methyl-4-hydroxyphenyl)ethyl]benzene, 2-(2, 3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4' -dihydroxyphenyl) propane, 2-(4-hydroxyphenyl)-2-(4'-hydroxyphenyl) propane, 2-(3-fluoro-4-hydroxyphenyl)-2-(3' -Fluoro-4'-hydroxyphenyl) propane, 2-(2,4-dihydroxyphenyl)-2-(4'-hydroxyphenyl) propane, 2-(2,3,4-trihydroxy Phenyl) -2- (4'-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (4'-hydroxy-3', 5'-dimethylphenyl) propane, Bis (2,3,4-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) methane, 2,3,4-trihydroxyphenyl-4'-hydroxyphenyl methane, 1,1 -Di(4-hydroxyphenyl) cyclohexane, 2,4-bis[1-(4-hydroxyphenyl)isopropyl]-5-hydroxyphenol, etc. are mentioned.

Component (C) contained in the composition for forming a separation layer of the present embodiment may be used alone or in combination of two or more.

In the composition for forming a separation layer of the present embodiment, among the above, it is preferable to use the component (C1) as the component (C).

When the composition for forming a separation layer of the present embodiment contains component (C), the content of component (C) is preferably 95 parts by mass or less, and 50 to 95 parts by mass, based on 100 parts by mass of component (P). It is more preferable, and 60-90 mass parts is still more preferable.

When the content of component (C) is within the above preferred range, the separation layer has higher photoreactivity.

≪Organic Solvent Component≫

The composition for forming a separation layer of the present embodiment may contain an organic solvent component (hereinafter also referred to as "component (S)") in order to adjust coating workability and the like.

Examples of the component (S) include linear hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, and tridecane; branched chain hydrocarbons of 4 to 15 carbon atoms; cyclic hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene, and tetrahydronaphthalene; p-menthane, o-menthane, m-menthane, diphenylmentane, 1,4-terpine, 1,8-terpine, bornane, norbornane, finan, thuzane, karan, longipolene, geraniol, Nerol, linalool, citral, citronerol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinen-1-ol, terpinene-4 Terpenes such as -ol, dihydroterpinyl acetate, 1,4-cineol, 1,8-cineol, borneol, carvone, ionone, thuyon, campol, d-limonene, l-limonene, and dipentene solvent; lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH ), methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; Polyhydric alcohols, such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; A compound having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, monomethyl ether of the polyhydric alcohol or compound having the ester bond, monoethyl ether, Derivatives of polyhydric alcohols such as monoalkyl ethers such as monopropyl ether and monobutyl ether or compounds having an ether bond such as monophenyl ether (among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) is preferred); Cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methoxypropyl acetate, methoxybutyl acetate, methyl pyrbate, ethyl pyrbate, methyl methoxypropionate, et esters such as ethyl oxypropionate; aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetol, and butylphenyl ether; and the like.

The component (S) contained in the composition for forming a separation layer of the present embodiment may be one type or two or more types.

In the composition for forming a separation layer of the present embodiment, the amount of component (S) used is not particularly limited, and is appropriately set at a concentration that can be applied to a support substrate or the like depending on the coating film thickness and applicability. Preferably, the total amount of the component (P) in the composition for forming a separation layer is 70% by mass or less, more preferably in the range of 10 to 50% by mass, based on the total mass (100% by mass) of the composition. (S) component is used.

«Surfactants»

The composition for forming a separation layer of the present embodiment may contain a surfactant in order to adjust coating workability and the like.

As surfactant, a silicone type surfactant and a fluorochemical surfactant are mentioned, for example. Examples of the silicone surfactant include BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, BYK-322, and BYK. -323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341, BYK-344, BYK-345, BYK-346, BYK-348, BYK-354, BYK-355 , BYK-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380, BYK-390 (above, manufactured by BYK Chemie) and the like can be used. As a fluorochemical surfactant, for example, F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, F-445, F- 446, F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F-483, F-484, F-486, F-487, F-172D, MCF-350SF, TF-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF-1126, TF-1130, TF- 1116SF, TF-1131, TF-1132, TF-1027SF, TF-1441, TF-1442 (above, manufactured by DIC Corporation); Polyfox series PF-636, PF-6320, PF-656, PF-6520 (above, manufactured by Omnova), etc. can be used.

The surfactant contained in the composition for forming a separation layer of the present embodiment may be one type or two or more types.

When the composition for forming a separation layer of the present embodiment contains a surfactant, the content of the surfactant is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 2 parts by mass, based on 100 parts by mass of component (P). , 0.03 to 1 part by mass is more preferred.

When the content of the surfactant is within the above preferred range, a separation layer having high flatness can be easily formed when the composition for forming a separation layer is applied onto a supporting substrate.

(supporting base with separation layer)

A support substrate with a separation layer according to a second aspect of the present invention includes a support substrate and a separation layer formed on the support substrate using the composition for forming a separation layer according to the first aspect.

The support substrate with a separation layer of this embodiment is equipped with the separation layer formed using the separation layer forming composition of the above-mentioned embodiment on a support substrate. Accordingly, the light reactivity and chemical resistance of such a support substrate with a separation layer are high.

<support gas>

The supporting substrate has a property of transmitting light. The support substrate is a member that supports the substrate and is bonded to the substrate through a separation layer. Therefore, as the support substrate, it is preferable to have strength required to prevent breakage or deformation of the substrate at the time of thinning of the encapsulation body, transport of the substrate, mounting on the substrate, and the like. Further, the support substrate preferably transmits light of a wavelength capable of altering the separation layer.

As the material of the support substrate, glass, silicone, acrylic resin, etc. are used, for example. As a shape of a support body, although a rectangle, circular shape, etc. are mentioned, for example, it is not limited to this.

Further, as the support body, for further high-density integration and improvement in production efficiency, a circular support body having an enlarged size or a large panel having a rectangular shape in a top view can be used.

<Separation layer>

The separation layer can be formed using the composition for forming a separation layer of the above-described embodiment, and is a layer made of a fired body formed by firing the resin component (P) contained in the composition for forming a separation layer. This separation layer is suitably changed in quality by absorbing light that passes through the supporting substrate and is irradiated.

Further, the separation layer may be a layer in which a material having no light-absorbing structure is blended within a range that does not impair the essential characteristics of the present invention, but is formed only of a light-absorbing material from the viewpoint of light reactivity and separability. It is desirable to be

A fired body here means what fired the composition containing (P) component.

This calcined body is formed by calcining a composition containing the component (P) in an atmospheric environment, that is, in an environment in which oxygen exists, and at least a part of the composition is carbonized. The fired body constituting the separation layer in the present embodiment can suitably absorb light in a wavelength range of 600 nm or less, and preferably has high chemical resistance.

The separation layer "degenerates" refers to a state in which the separation layer can be destroyed by receiving an external force or a state in which the adhesion between the separation layer and a contacting layer is reduced. The separation layer becomes brittle by absorbing light and loses strength or adhesiveness before being irradiated with light. The deterioration of such a separation layer occurs by causing decomposition by energy of absorbed light, change in steric arrangement, or dissociation of functional groups.

The thickness of the separation layer is preferably within a range of, for example, 0.05 μm or more and 50 μm or less, and more preferably 0.3 μm or more and 1 μm or less.

When the thickness of the separation layer is within the range of 0.05 μm or more and 50 μm or less, the desired change in quality can be caused to the separation layer by irradiation with light for a short period of time and light with low energy. Further, the thickness of the separation layer is particularly preferably within a range of 1 μm or less from the viewpoint of productivity.

For example, in the laminate 10 shown in FIG. 1, the surface of the separation layer in contact with the adhesive layer is preferably flat (no irregularities are formed), thereby facilitating formation of the adhesive layer. It is easily carried out, and also it becomes easy to adhere the support substrate and the substrate uniformly.

The support base body with a separation layer of this embodiment can be manufactured by similarly carrying out the operation of [separation layer formation process] mentioned later.

Since the support substrate with a separation layer of this embodiment is provided with a separation layer to which the composition for forming a separation layer of the above-described embodiment is applied, the laser reactivity is enhanced and the photoreactivity is further increased. Preferably, chemical resistance also increases.

(Laminate)

A laminate according to a third aspect of the present invention includes a separation layer between a light-transmitting support substrate and a substrate. This separation layer is a fired body of the composition for forming a separation layer of the above-described embodiment.

As shown in FIG. 1 , in the laminate 10 of this embodiment, a separation layer 2, an adhesive layer 3, and a substrate 4 are laminated in this order on a support base 1.

The description of the support base body 1 is the same as the description in the above <support base>.

Description of the separation layer 2 is the same as the description in the above <separation layer>.

<Adhesive layer>

The adhesive layer 3 is a layer for bonding the support substrate 1 and the substrate 4 together, and can be formed using a composition for forming an adhesive layer.

Examples of such a composition for forming an adhesive layer include those containing other components such as thermoplastic resins, diluents, and additives. The thermoplastic resin may be one or two or more of hydrocarbon resins (preferably cycloolefin polymers, etc.), acrylic-styrene resins, maleimide resins, elastomer resins, polysulfone resins, etc. can As a diluent, the thing similar to the said (S) component is mentioned. Examples of other components include additional resins for improving the performance of the adhesive layer, curable monomers, photoinitiators, plasticizers, adhesive aids, stabilizers, colorants, thermal polymerization inhibitors, surfactants, and the like.

The thickness of the adhesive layer 3 is preferably within a range of, for example, 0.1 μm or more and 50 μm or less, and more preferably 1 μm or more and 10 μm or less.

If the thickness of the adhesive layer is in the range of 0.1 μm or more and 50 μm or less, the support substrate 1 and the substrate 4 can be more favorably bonded. In addition, when the thickness of the adhesive layer is 1 μm or more, the substrate can be sufficiently fixed on the support substrate, and when the thickness of the adhesive layer is 10 μm or less, the adhesive layer can be easily removed in a subsequent removal step.

<substrate>

The substrate 4 is subjected to processes such as thinning and mounting in a state supported by the support base 1 . On the substrate 4, structures such as integrated circuits and metal bumps are mounted, for example.

As the substrate 4, a silicon wafer substrate is typically used, but it is not limited thereto, and a ceramic substrate, a thin film substrate, a flexible substrate, or the like may be used.

In this embodiment, the element is a semiconductor element or other element, and may have a single-layer or multi-layered structure. In addition, when the element is a semiconductor element, an electronic component obtained by dicing the sealing substrate becomes a semiconductor device.

Since the laminate of the above-described embodiment is provided with a separation layer to which the composition for forming a separation layer of the above-described embodiment is applied, the laser reactivity is enhanced and the photoreactivity is further increased (suitably altered by light irradiation), and the laminate is laminated. Separability of the supporting gas from the sieve is improved.

In addition, since the layered product of the embodiment is provided with a separation layer to which the composition for forming a separation layer of the above-described embodiment is applied, chemical resistance is increased. As a result, the laminate of the embodiment is less likely to be damaged by the influence of chemicals used in etching treatment, lithography treatment, and the like.

In the laminate of the above-described embodiment, the support substrate 1 and the separation layer 2 are adjacent to each other, but it is not limited to this, and another layer is added between the support substrate 1 and the separation layer 2. may be formed. In this case, the other layer may be made of a material that transmits light. According to this, it is possible to appropriately add a layer that imparts desirable properties and the like to the layered product 10 without obstructing the incidence of light to the separation layer 2 . Depending on the type of material constituting the separation layer 2, the wavelength of light that can be used is different. Therefore, the materials constituting the other layers do not need to transmit light of all wavelengths, and can be appropriately selected from materials that transmit light of a wavelength capable of deteriorating the material constituting the separation layer 2.

In addition, although the laminate of the above-described embodiment is equipped with an adhesive layer 3 for bonding the support base 1 and the substrate 4, it is not limited to this, and the support base 1 and the substrate 4 It may be provided with only the separation layer 2 in between. In this case, for example, a separation layer that also serves as an adhesive layer is used.

(Method of manufacturing laminated body)

A fourth aspect of the present invention is a method for manufacturing a laminate having a separation layer between a light-transmitting support substrate and a substrate, comprising a separation layer forming step and a lamination step.

<First Embodiment>

2 is a schematic process diagram illustrating one embodiment of a method for manufacturing a laminate. Fig. 2(a) is a diagram explaining a separation layer forming process, and Fig. 2(b) is a diagram explaining a lamination process.

In the method for producing a laminate of the present embodiment, a composition for forming a separation layer in which a resin component (component (P)) having a repeating unit represented by the general formula (p1) is dissolved in an organic solvent component (component (S)) It is being used. In addition, a composition for forming an adhesive layer in which a hydrocarbon resin is dissolved in component (S) is used.

[Separation layer formation process]

The separation layer forming step in the embodiment is a step of forming a separation layer by applying the composition for forming a separation layer according to the above-described embodiment to one side of a support substrate and then firing it.

In Fig. 2(a), the separation layer 2 is formed by applying the composition for forming a separation layer of the above-described embodiment onto a support substrate 1 and then firing it (that is, with a separation layer). A supporting body has been produced).

A method of applying the composition for forming a separation layer onto the support substrate 1 is not particularly limited, and examples thereof include spin coating, dipping, roller blade coating, spray coating, and slit coating.

In the separation layer forming step, the component (S) is removed from the coating layer of the composition for forming a separation layer applied on the support substrate 1 under a heating environment or a reduced pressure environment to form a film. Removal of component (S) can be performed, for example, by performing a bake treatment at a temperature condition of 80 to 150°C for 120 to 360 seconds.

Thereafter, in an atmospheric environment, a film obtained by removing component (S) from the above coated layer is fired to form a separation layer 2 made of a fired body.

The temperature at the time of firing the film obtained by removing the component (S) from the above coating layer is appropriately set depending on the type of component (P), and is preferably set to, for example, 200°C or higher, and is set to 250°C or higher. it is more preferable If the temperature during firing is at least the lower limit of the above preferred range, a separation layer capable of absorbing light in a wavelength range of 600 nm or less can be formed more stably.

The upper limit of the temperature during firing is not particularly limited, but is preferably, for example, 800°C or lower, and more preferably 600°C or lower.

The firing time is preferably 3 minutes or more and 3 hours or less, more preferably 3 minutes or more and 30 minutes or less. In this way, it is possible to reliably form a separation layer capable of absorbing light in a wavelength range of 600 nm or less.

[lamination process]

The lamination step in the embodiment is a step of laminating the support substrate on which the separation layer is formed and the substrate on which the separation layer is not formed via the separation layer and the adhesive layer.

In FIG. 2( b ), a support substrate 1 on which a separation layer 2 is formed and a substrate 4 on which the separation layer 2 is not formed are laminated via the separation layer 2 and the adhesive layer 3. Thus, a laminate 10 is obtained in which the support substrate 1, the separation layer 2, the adhesive layer 3, and the substrate 4 are stacked in this order.

As a specific method of the lamination step, the adhesive layer 3 is formed by applying a composition for forming an adhesive layer on the separation layer 2 and heating, and then the support substrate 1 and the substrate 4 are laminated. method of combining.

The method of applying the composition for forming an adhesive layer onto the separation layer 2 is not particularly limited, but may be carried out in the same manner as the method of applying the composition for forming a separation layer onto the support substrate 1 described above.

The baking treatment at the time of forming the adhesive layer 3 is performed by, for example, stepwise heating while raising the temperature, and the adhesive layer 3 is formed by removing component (S) from the composition for forming the adhesive layer.

The method of bonding the support substrate 1 and the substrate 4 is to place the substrate 4 at a predetermined position on the adhesive layer 3 and support it with a die bonder or the like while heating it in a vacuum (for example, at about 100° C.) It is performed by pressing the base 1 and the substrate 4.

According to the manufacturing method of the laminate of the first embodiment, since the separation layer is provided by applying the composition for forming a separation layer of the above-described embodiment, the laser reactivity becomes stronger and the photoreactivity becomes higher, so that the support substrate from the laminate Separability is improved. Preferably, a laminate with high chemical resistance can be manufactured.

In the manufacturing method of the laminate of the present embodiment described above, the separation layer 2 is formed on the support base 1, but is not limited to this, and the separation layer 2 is formed on the substrate 4 it may be

In the manufacturing method of the laminate of the present embodiment described above, although the adhesive layer 3 is formed on the separation layer 2, it is not limited to this, even if the adhesive layer 3 is formed on the substrate 4 do.

In addition, the separation layer 2 may be formed on both the support substrate 1 and the substrate 4. In this case, the support substrate 1 and the substrate 4, the separation layer 2, the adhesive layer (3) and bonding through the separation layer (2).

<Second Embodiment>

3 is a schematic process diagram illustrating another embodiment of a method for manufacturing a laminate. Fig.3 (a) is a figure which shows the laminated body manufactured by the manufacturing method of 1st Embodiment, and Fig.3 (b) is a figure explaining the sealing process.

The manufacturing method of the laminate of this other embodiment further includes a sealing step in addition to the separation layer forming step and the lamination step described above.

[Encapsulation process]

The sealing step in the embodiment is a step of producing a sealing body by sealing the substrate bonded to the support substrate through the adhesive layer with a sealing material after the lamination step.

In FIG. 3( b ), a sealing body 20 (laminated body) in which the entirety of the substrate 4 disposed on the adhesive layer 3 is sealed with a sealing material is obtained.

In the encapsulation step, for example, the encapsulant heated to 130 to 170 ° C. is supplied on the adhesive layer 3 so as to cover the substrate 4 while maintaining a high viscosity state, and by compression molding, the adhesive layer ( 3) The encapsulant 20 (laminate) on which the encapsulant layer 5 is provided is produced.

As the sealing material, for example, a composition containing an epoxy-based resin or a silicone-based resin can be used. It is preferable that the sealing material layer 5 is provided so as to cover all of the substrates 4 on the adhesive layer 3, rather than being provided for each substrate 4.

According to the method for manufacturing a laminate of the second embodiment, it is possible to suitably form a sealing substrate having a substrate (wiring layer) on the separation layer and the adhesive layer by applying the composition for forming a separation layer of the above-described embodiment.

<Third Embodiment>

4 is a schematic process diagram illustrating another embodiment of a method for manufacturing a laminate. Fig. 4 (a) is a diagram showing an encapsulated body manufactured by the manufacturing method of the second embodiment, Fig. 4 (b) is a diagram explaining a grinding step, and Fig. 4 (c) is a diagram illustrating rewiring formation. It is a diagram explaining the process.

The manufacturing method of the laminate of this other embodiment further includes a grinding step and a rewiring forming step in addition to the above separation layer forming step, lamination step, and sealing step.

[Grinding process]

The grinding process in the embodiment is a process of grinding the sealing material portion (sealing material layer 5) in the sealing body 20 after the sealing process so that a part of the substrate 4 is exposed.

Grinding of the sealing material portion is performed by scraping the sealing material layer 5 until it becomes substantially equivalent to the thickness of the substrate 4, as shown in FIG. 4(b), for example.

[Rewiring formation process]

The rewiring formation step in the embodiment is a step of forming the rewiring layer 6 on the exposed substrate 4 after the grinding step.

The redistribution layer is also called a redistribution layer (RDL), and is a thin-film wiring body constituting wiring connected to elements, and may have a single-layer or multi-layered structure. For example, in the redistribution layer, a dielectric (silicon oxide (SiO _x ), photosensitive resin such as photosensitive epoxy, etc.) and a conductor (a metal such as aluminum, copper, titanium, nickel, gold, silver, silver-tin alloy, etc.) The wiring may be formed by an alloy of), but is not limited thereto.

As a method of forming the redistribution layer 6, first, a dielectric layer made of silicon oxide (SiO _x ) or a photosensitive resin is formed on the sealing material layer 5. The dielectric layer made of silicon oxide can be formed by, for example, sputtering or vacuum deposition. The dielectric layer made of the photosensitive resin can be formed by applying the photosensitive resin onto the encapsulant layer 5 by a method such as spin coating, dipping, roller blade coating, spray coating, or slit coating.

Next, wiring is formed in the dielectric layer with a conductor such as metal.

As a method of forming the wiring, known semiconductor process methods such as lithography processing such as photolithography (resist lithography) and etching processing can be used, for example. Examples of such a lithography process include a lithography process using a positive resist material and a lithography process using a negative resist material.

In this way, when performing photolithography treatment, etching treatment, etc., the separation layer 2 is in an acid such as hydrofluoric acid, an alkali such as tetramethyl ammonium hydroxide (TMAH), or a resist solvent for dissolving the resist material. Exposed. In particular, in the fan-out technology, PGMEA, cyclopentanone, cycloheptanone, N-methyl-2-pyrrolidone (NMP) or cyclohexanone is used as the resist solvent.

However, by forming the separation layer using the composition for forming a separation layer of the above-described embodiment, the separation layer has high chemical resistance. For this reason, even if the separation layer is exposed to not only acids and alkalis but also resist solvents, it is difficult to dissolve or peel off.

In this way, on the sealing material layer 5, the redistribution layer 6 can be suitably formed.

According to the manufacturing method of the laminate of the third embodiment, the support substrate 1, the separation layer 2, the adhesive layer 3, the sealing material layer 5 covering the substrate 4, and the redistribution layer 6 ) can stably manufacture the laminate 30 formed by laminating in this order.

Such a laminate 30 is a laminate manufactured in a process based on a fan-out type technology in which terminals provided on the substrate 4 are mounted on a redistribution layer 6 extending out of the chip area.

In the manufacturing method of the laminate of this embodiment, it is possible to further form bumps or mount elements on the redistribution layer 6 . Mounting of elements on the redistribution layer 6 can be performed using, for example, a tip mounter or the like.

(Method of manufacturing electronic parts)

A method for manufacturing an electronic component according to a fifth aspect of the present invention includes a separation step and a removal step after obtaining a laminate according to the method for manufacturing a laminate according to the fourth aspect.

5 is a schematic process diagram illustrating an embodiment of a method for manufacturing a semiconductor package (electronic component). Fig. 5 (a) is a diagram showing a laminate manufactured by the manufacturing method of the third embodiment, Fig. 5 (b) is a diagram explaining a separation step, and Fig. 5 (c) is a diagram illustrating a removal step It is an explanatory diagram.

[Separation process]

In the separation step in the embodiment, light (arrow) is irradiated to the separation layer 2 through the support substrate 1 to change the quality of the separation layer 2, so that the laminate 30 is separated from the support substrate ( 1) is the process of separating.

As shown in Fig. 5(a), in the separation step, the separation layer 2 is changed in quality by irradiating the separation layer 2 with light (arrow) through the support substrate 1.

As a wavelength capable of changing the quality of the separation layer 2, a range of 600 nm or less is exemplified.

The type and wavelength of light to be irradiated may be appropriately selected according to the permeability of the support substrate 1 and the material of the separation layer 2, and examples include YAG laser, ruby laser, glass laser, YVO ₄ laser, and LD laser. , solid lasers such as fiber lasers, liquid lasers such as dye lasers, CO ₂ lasers, excimer lasers, Ar lasers, gas lasers such as He-Ne lasers, laser lights such as semiconductor lasers, free electron lasers, and non-laser lights. can As a result, the separation layer 2 is altered in quality, so that the support substrate 1 and the substrate 4 can be easily separated.

When irradiating a laser beam, the following conditions are mentioned as an example of laser beam irradiation conditions.

1.0 W or more and 5.0 W or less are preferable, and, as for the average output value of a laser beam, 3.0 W or more and 4.0 W or less are more preferable. 20 kHz or more and 60 kHz or less are preferable, and, as for the repetition frequency of a laser beam, 30 kHz or more and 50 kHz or less are more preferable. As for the scanning speed of a laser beam, 100 mm/s or more and 10000 mm/s or less are preferable.

After irradiating the separation layer 2 with light (arrow) to change the quality of the separation layer 2, as shown in FIG. 5(b), the support substrate 1 is separated from the laminate 30.

For example, the support base 1 and the substrate 4 are separated by applying force in a direction in which the support base 1 and the substrate 4 are separated from each other. Specifically, with one side of the support substrate 1 or the substrate 4 side (rewiring layer 6) being fixed to the stage, the other side being adsorbed and held by a separation plate provided with an adsorption pad such as a bellows pad, By lifting, the support substrate 1 and the substrate 4 can be separated.

The force applied to the laminate 30 may be appropriately adjusted depending on the size of the laminate 30 and the like, and is not limited thereto. By applying a force of about 49 N), the support substrate 1 and the substrate 4 can be suitably separated.

[Removal process]

The removal step in the embodiment is a step of removing the adhesive layer 3 and the separation layer 2 attached to the substrate 4 after the separation step.

In FIG. 5( b ), the adhesive layer 3 and the separation layer 2 are attached to the substrate 4 after the separation step. In this embodiment, the electronic component 40 shown in FIG. 5(c) is obtained by removing the adhesive layer 3 and the separation layer 2 adhering to the substrate 4 in the removal step.

As a method of removing the adhesive layer 3 attached to the substrate 4, for example, a method of removing residues of the adhesive layer 3 and the separation layer 2 using a cleaning solution or a method of irradiating plasma. can be heard

As the cleaning liquid, a cleaning liquid containing an organic solvent is preferably used. As the organic solvent, it is preferable to use an organic solvent blended in the composition for forming a separation layer and an organic solvent blended in the composition for forming an adhesive layer.

<Other embodiments>

6 is a schematic process diagram illustrating another embodiment of a method for manufacturing a semiconductor package (electronic component). Fig. 6 (a) is a schematic diagram showing another embodiment of a laminate to which the present invention is applied, Fig. 6 (b) is a diagram explaining a separation step, and Fig. 6 (c) is a diagram explaining a removal step am.

The laminate 50 of the embodiment shown in FIG. 6 (a) includes, from the outermost surface 51S side, a support substrate 51, a separation layer 52, a wiring layer 57, a substrate 54, a sealing material layer ( 55) are stacked in this order.

Description of the support base body 51 is the same as the description in the above <support base>.

The description of the separation layer 52 is the same as that of the above <separation layer>.

The wiring layer 57 is made of, for example, dielectric (silicon oxide (SiO _x ), photosensitive resin such as photosensitive epoxy), conductor (metal such as aluminum, copper, titanium, nickel, gold, silver, and silver-tin). alloys such as alloys) in which wiring is formed.

Description of the board|substrate 54 is the same as the description in <substrate> mentioned above.

Examples of the sealing material layer 55 include those formed using a composition containing an epoxy-based resin or a silicone-based resin.

The laminate 50 can be manufactured as follows, for example.

First, the separation layer 52 is formed on the surface opposite to the outermost surface 51S of the support substrate 51 . Formation of such a separation layer 52 may be performed in the same manner as in the above [separation layer forming step].

Next, a wiring layer 57 is formed on the surface of the separation layer 52 opposite to the support substrate 51 . The formation of such a wiring layer 57 may be performed in the same manner as in the above [rewiring formation step].

Next, a substrate 54 is bonded to the surface of the wiring layer 57 opposite to the separation layer 52 via, for example, a bump.

Then, the substrate 54 bonded to the wiring layer 57 is sealed with a sealing material so as to cover it, thereby forming a sealing material layer 55 . The formation of such a sealing material layer 55 may be performed in the same manner as in the above [sealing step]. In this way, the laminate 50 is manufactured.

As shown in Fig. 6(a) , in the separation step in the embodiment, the separation layer 52 is irradiated with light (arrow) through the support substrate 51 to change the quality of the separation layer 52.

After irradiating the separation layer 52 with light (arrow) to change the quality of the separation layer 52, as shown in FIG. 6(b), the support substrate 51 is separated from the laminate 50. The operation in this separation step may be performed in the same manner as the operation in the above [separation step].

As shown in FIG. 6(c) , in the removal step in the embodiment, the electronic component 60 is obtained by removing the separation layer 52 attached to the wiring layer 57 after the separation step. are losing

As a method of removing the separation layer 52 adhering to the wiring layer 57, for example, a method of irradiating plasma or a method of removing residues of the separation layer 52 using a cleaning solution is exemplified. As the plasma, oxygen plasma is suitably used.

In the electronic component manufacturing method of the present embodiment, processing such as solder ball formation, dicing, or oxide film formation may be further performed on the electronic component after the above removal step.

[Example]

Hereinafter, the present invention will be further described in detail by examples, but the present invention is not limited by these examples.

<Resin component>

As the resin component, Resin (P-1), Resin (P-2), Resin (P-3), Resin (Q-1), and Resin (Q-2) shown below were used.

Resin (P-1): A resin having a repeating unit (p12) represented by the following formula (p1-2) and a repeating unit (p22) represented by the following formula (p2-2). The weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 6000, and the molecular weight dispersion (Mw/Mn) was 1.62. The copolymerization composition ratio (ratio (molar ratio) of each repeating unit in the structural formula) determined by ¹³ C-NMR is repeating unit (p12)/repeating unit (p22) = 10/90.

Resin (P-2): A resin having a repeating unit (p12) represented by the following chemical formula (p1-2) and a repeating unit (p22) represented by the following chemical formula (p2-2). The weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 5500, and the molecular weight dispersion (Mw/Mn) was 1.60. The copolymerization composition ratio (ratio (molar ratio) of each repeating unit in the structural formula) determined by ¹³ C-NMR is repeating unit (p12)/repeating unit (p22) = 5/95.

Resin (P-3): A resin having a repeating unit (p16) represented by the following chemical formula (p1-6) and a repeating unit (p26) represented by the following chemical formula (p2-6). n1 = 3 in formula (p1-6) and n2 = 3 in formula (p2-6). The weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 2000, and the molecular weight dispersion (Mw/Mn) was 2.10. The copolymerization composition ratio (ratio (molar ratio) of each repeating unit in the structural formula) determined by ¹³ C-NMR is repeating unit (p16)/repeating unit (p26) = 50/50.

Resin (Q-1): A resin having a repeating unit (p21) represented by the following formula (p2-1). The weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 12000, and the molecular weight dispersity (Mw/Mn) was 2.10. The polymerization composition ratio (ratio (molar ratio) of repeating units in the structural formula) is repeating unit (p21) = 100.

Resin (Q-2): A resin having a repeating unit (p26) represented by the above formula (p2-6). The weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 2300, and the molecular weight dispersity (Mw/Mn) was 2.00. The polymerization composition ratio (ratio (molar ratio) of repeating units in the structural formula) is repeating unit (p26) = 100.

<Preparation of Composition for Forming Separation Layer>

(Examples 1-5, Comparative Examples 1-2)

Each component shown in Table 1 was mixed and dissolved to prepare a composition for forming a separation layer (resin component concentration: 20% by mass) in each case.

In Table 1, each symbol has the following meaning respectively. The numerical value in [ ] is the compounding amount (parts by mass).

(P)-1: Resin (P-1)

(P)-2: Resin (P-2)

(P)-3: Resin (P-3)

(P)-4: Resin (Q-1)

(P)-5: Resin (Q-2)

(T)-1: Thermal acid generator composed of a compound represented by the following formula (T-1)

(S)-1: propylene glycol monomethyl ether (PGME)

<Formation of Separation Layer>

On a bare glass support substrate (12 inches, 0.7 mm thick), each composition for forming a separation layer was spin-coated in each example, heated at a temperature of 100°C for 300 seconds, and then heated at a temperature of 150°C for 300 seconds. The solvent was removed by heating to form a film having a thickness of 1 μm.

Next, the formed film was baked under the conditions of 20 minutes at a temperature of 300° C. in an atmospheric environment to form a separation layer having a film thickness of 0.3 μm on the bare glass support substrate, thereby obtaining a support substrate with a separation layer. .

[Evaluation of Light Transmittance in Separation Layer]

In the above-described <formation of separation layer>, the film in a state before firing and the film (separation layer) formed using the composition for forming a separation layer in each example were measured using a spectroscopic analysis measuring device UV-3600 ( The transmittance (%) of light with a wavelength of 532 nm in each film formed on the bare glass support substrate was evaluated by irradiating light with a wavelength of 380 to 780 nm using a film manufactured by Shimadzu Seisakusho Co., Ltd. . Table 2 shows the results of this evaluation.

[Evaluation of laser reactivity in separation layer]

A laser beam having a wavelength of 532 nm was irradiated to the separation layer formed using the composition for forming a separation layer in each case under conditions of a scanning speed of 7200 mm/sec, a frequency of 40 kHz, an output (current value) of 24 A, and an irradiation pitch of 140 μm. By doing so, evaluation of laser reactivity was performed.

Evaluation of such laser reactivity is carried out by observing the state of the traces of the laser beam irradiated onto the separation layer using a microscope VHX-600 (manufactured by Keyence), and observing the size of the traces of the laser beam on the surface of the separation layer (diameter of laser imprint / m) by finding The evaluation criteria were set as follows. Table 2 shows the results of this evaluation.

Evaluation standard

(double-circle): The laser mark diameter was 160 micrometers or more.

○: The laser mark diameter was 150 μm or more and less than 160 μm.

(triangle|delta): The laser mark diameter was 100 micrometers or more and less than 150 micrometers.

Х: The laser mark diameter was less than 100 μm.

From the results shown in Table 2, all of the separation layers formed using the composition for forming a separation layer of Examples 1 to 5 had a light transmittance higher than that of the separation layer formed using the composition for forming a separation layer of Comparative Examples 1 to 2. It turns out that this low thing and the laser mark diameter are remarkably large.

That is, it was confirmed that the composition for forming a separation layer to which the present invention was applied had a higher photoreactivity and thus a separation layer with improved separation of the supporting substrate from the laminate could be formed.

<Manufacture of laminated body>

In the same manner as in <Formation of Separation Layer>, the composition for forming a separation layer of each Example was spin-coated on a bare glass support substrate (12 inches, 0.7 mm thick), respectively, at a temperature of 100° C. for 300 seconds. The solvent was removed by heating under conditions of 150° C. for 300 seconds to form a film. Then, the formed film was fired under the condition of 300 DEG C for 20 minutes in an atmospheric environment to form a separation layer having a thickness of 0.5 μm on the bare glass support substrate (separation layer forming step).

On the other hand, the adhesive composition TZNR (registered trademark) -A4012 (manufactured by Tokyo Oka Kyogo Co., Ltd.) was spin-coated on a semiconductor wafer substrate (12-inch, silicon), and each at a temperature of 90 ° C., 160 ° C., 220 ° C. for 4 minutes By baking, an adhesive layer having a film thickness of 50 µm was formed.

Next, the bare glass support substrate on which the separation layer is formed and the semiconductor wafer substrate on which the adhesive layer is formed are stacked so that the semiconductor wafer substrate, the adhesive layer, the separation layer and the bare glass support substrate are in this order, and under vacuum (5 Pa), and 215 degreeC conditions WHEREIN: It pressed for 2 minutes with the sticking pressure of 4000 kgf (about 39.2 kN). Thus, the bare glass support base and the semiconductor wafer substrate were laminated via the separation layer and the adhesive layer to obtain a laminate (lamination step).

After obtaining the laminate, a laser beam with a wavelength of 532 nm was applied to the separation layer from the support substrate side of the laminate under conditions of a scanning speed of 3000 mm/sec, a frequency of 40 kHz, an output (current value) of 24 A, and an irradiation pitch of 140 μm. was investigated (separation process). After that, washing removal of the adhesive layer was performed using p-menthane (removal step).

Through the above operation, it was confirmed that the support substrate was separated from the semiconductor wafer substrate provided with the laminate.

<Production Example (1) of Electronic Components>

In the same manner as in <Formation of Separation Layer>, the composition for forming a separation layer of each Example was spin-coated on a bare glass support substrate (12 inches, 0.7 mm thick), respectively, and held at 100° C. for 300 seconds. The solvent was removed by heating under conditions of 150° C. for 300 seconds to form a film. Next, the formed film was fired under the condition of 300° C. for 20 minutes in an atmospheric environment to form a separation layer having a thickness of 0.5 μm on the bare glass support substrate, thereby obtaining a support substrate with a separation layer (separation layer). layer forming process).

Then, on this separation layer, the adhesive composition TZNR (registered trademark) -A4012 (manufactured by Tokyo Oka Kogyo Co., Ltd.) was spin-coated, and baked at temperatures of 90°C, 160°C, and 220°C for 4 minutes each, An adhesive layer having a thickness of 50 µm was formed.

Next, using a die bonder (manufactured by TRESKY), the plate of the die bonder is heated to 150°C, and a 2 mm square silicon bare bear is placed on the adhesive layer at a pressure of 35 N for 1 second. Chips were pressed. After placing the bare chip made of silicon, it was heated at 200°C for 1 hour in a nitrogen atmosphere to obtain a laminate (lamination process).

The obtained laminate is placed on a plate heated to 50°C, and 12 g of sealing agent containing an epoxy resin is placed so as to cover the bare chip. A pressure of 1 ton was applied with a pressure plate heated by , and compression was performed for 5 minutes. In this way, the bare chip disposed on the adhesive layer was sealed with a sealing material to produce a sealed body (sealing step).

After manufacturing the encapsulation body, from the support substrate side of the encapsulation body, with respect to the separation layer, under the conditions of a scanning speed of 3000 mm/sec, a frequency of 40 kHz, an output (current value) of 24 A, and an irradiation pitch of 140 μm, a laser with a wavelength of 532 nm Light was irradiated (separation step). After that, washing removal of the adhesive layer was performed using p-menthane (removal step).

It was confirmed by the above operation that the support gas was separated from the sealing body. An electronic component was obtained as described above.

<Manufacture example of electronic parts (2)>

In the same manner as in <Formation of Separation Layer>, the composition for forming a separation layer of each Example was spin-coated on a bare glass support substrate (12 inches, 0.7 mm thick), and held at a temperature of 90° C. for 180 seconds. The solvent was removed by heating under conditions to form a film. Next, the formed film was fired under the condition of 300° C. for 10 minutes in an atmospheric environment to form a separation layer having a thickness of 0.35 μm on the bare glass support substrate, thereby obtaining a support substrate with a separation layer (separation layer). layer forming process).

Next, a wiring layer forming material (trade name: TMMR S2000) is applied on the separation layer, and baked in an atmospheric environment at 90° C. for 3 minutes to form a wiring layer having a thickness of 10 μm on the separation layer. Thus, a laminate was obtained.

After forming the wiring layer, a laser beam with a wavelength of 532 nm is irradiated from the side of the bare glass support base of the laminate to the separation layer under conditions of an irradiation amount of 200 mJ/cm ² , an output (current value) of 22 A, and an irradiation pitch of 80 μm. did. Next, it was immersed in propylene glycol monomethyl ether acetate (PGMEA) as a cleaning solution, and then baked at 90°C for 5 minutes. Subsequently, the supporting substrate was separated from the layered product by further repeating the firing under nitrogen atmosphere at 200°C for 60 minutes three times (separation step). Thereafter, oxygen plasma was irradiated to the surface of the wiring layer on the separation layer side (power: 2000 W, oxygen flow rate: 2000 sccm, pressure: 75 Pa, temperature: 50° C., irradiation time: 5 minutes) to remove the separation layer adhering to the wiring layer. (removal process).

It was confirmed by the above operation that the support substrate was separated from the laminate. An electronic component was obtained as described above.

1 support substrate, 2 separation layer, 3 adhesive layer, 4 substrate, 5 encapsulation layer, 6 redistribution layer, 10 laminate, 20 encapsulation, 30 laminate, 40 electronic component, 50 laminate, 51 support substrate, 52 separation layer, 54 board, 55 encapsulant layer, 57 wiring layer, 60 electronic component

Claims (10)

In a laminate having a separation layer between a support substrate and a substrate through which light is transmitted, the separation layer which is changed in quality by irradiation of light from the side of the support substrate and enables separation of the support substrate from the laminate As a composition for forming a separation layer to form,
A composition for forming a separation layer, comprising a resin component (P) having a repeating unit represented by the following general formula (p1).
[Tue 1]

[In formula, L ^P1 represents a divalent linking group. R ^P1 represents a condensed polycyclic aromatic group which may have a substituent.] The method of claim 1,
In a laminate having a separation layer and an adhesive layer between a support substrate and a substrate through which light is transmitted, the separation is made possible to separate the support substrate from the laminate by being changed in quality by irradiation of light from the side of the support substrate. As a composition for forming a separation layer for forming a layer,
A composition for forming a separation layer, comprising a resin component (P) having a repeating unit represented by the following general formula (p1).
[Tue 2]

[In formula, L ^P1 represents a divalent linking group. R ^P1 represents a condensed polycyclic aromatic group which may have a substituent.] According to claim 1 or claim 2,
The composition for forming a separation layer, wherein the resin component (P) further has a repeating unit represented by the following general formula (p2).
[Tue 3]

[In formula, L ^P2 represents a divalent linking group. R ^P2 represents a monocyclic aromatic group which may have a substituent.] The method according to any one of claims 1 to 3,
Further, a composition for forming a separation layer containing a thermal acid generator. a supporting body;
A separation layer formed on the support substrate using the composition for forming a separation layer according to any one of claims 1 to 4
A support substrate with a separation layer comprising: A laminate having a separation layer between a support substrate and a substrate that transmits light,
The separation layer is a sintered body of the composition for forming a separation layer according to any one of claims 1 to 4, a laminate. A method of manufacturing a laminate having a separation layer between a light-transmitting support substrate and a substrate,
A separation layer forming step of forming the separation layer by applying the composition for forming a separation layer according to any one of claims 1 to 4 on at least one of the substrate or the support substrate and then firing it;
A lamination process of laminating the substrate and the support substrate through the separation layer.
Having a method for producing a laminate. The method of claim 7,
The manufacturing method of the laminated body which further has the sealing process of manufacturing the sealing body by sealing the said board|substrate bonded to the said support substrate through the said separation layer with a sealing material after the said lamination process. The method of claim 8,
After the sealing step, a grinding step of grinding a portion of the sealing material in the sealing body so that a part of the substrate is exposed;
A redistribution forming step of forming redistribution on the exposed substrate after the grinding step.
The manufacturing method of the laminated body which further has. After obtaining a laminate by the method of manufacturing a laminate according to any one of claims 7 to 9, the separation layer is irradiated with light through the support substrate to degenerate the separation layer, thereby removing the above from the laminate. a separation step of separating a supporting gas;
After the separation step, a removal step of removing the separation layer attached to the substrate
A method of manufacturing an electronic component having a.

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