TW202330721A - Composition for forming separation layer, support base provided with separation layer, laminate and method of producing the same, and method of producing electronic component capable of forming a separation layer in which photoreactivity is further improved - Google Patents

Abstract

The present invention provides a composition for forming a separation layer capable of forming a separation layer in which photoreactivity is further improved in a laminate provided with a separation layer between a support base and a substrate, such that the separation property of the support base from the laminate is improved. The composition for forming a separation layer of this invention is used for forming a separation layer in a laminate (10) provided with a separation layer (2) and an adhesive layer (3) between a support base (1) and a substrate (4) that transmits light. The separation layer can be denatured by irradiation of lights from the support base side to separate the support base from the laminate. The composition for forming the separation layer contains a resin component (P) having a repeating unit represented by the general formula (p1). In the general formula (p1), LP1 represents a divalent linking group, and RP1 represents a condensed polycyclic aromatic group which may have a substituent.

Description

Composition for forming separation layer, support substrate with separation layer, laminate and method for producing the same, and method for producing electronic parts

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

In the semiconductor package (electronic component) including the semiconductor element, there are various forms according to the corresponding size, for example, there are WLP (Wafer Level Package, wafer level package), PLP (Panel Level Package, panel level package) and so on. Examples of semiconductor packaging technologies include fan-in technology and fan-out technology. As a semiconductor package based on the fan-in technology, there is known a fan-in WLP (Fan-in Wafer Level Package) in which the terminals located at the end of the bare chip are relocated in the chip area. As a semiconductor package based on the fan-out technology, a fan-out WLP (Fan-out Wafer Level Package) in which the terminals are relocated outside the wafer area is known.

In recent years, especially fan-out technology has been used as a fan-out PLP (Fan-out Panel Level Package) that can be applied to arranging and packaging semiconductor elements on a panel, and can realize further high-integration in semiconductor packaging. The method of thinning, thinning and miniaturization has attracted attention.

In order to miniaturize a semiconductor package, it is important to reduce the thickness of the substrate in the mounted device. However, if the thickness of the substrate is reduced, its strength is reduced, and damage to the substrate is likely to occur during the manufacture of semiconductor packages. For this purpose, a laminate obtained by bonding a support base to a substrate is used. Patent Document 1 discloses a method in which a light-transmitting support base and a substrate are bonded via a light-to-heat conversion layer (separation layer) and an adhesive layer provided on the support base side, and after processing the substrate, Radiant energy (light) is irradiated to the separation layer from the side of the substrate to denature and decompose the separation layer, thereby separating the processed substrate from the support substrate to produce a laminate. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2004-64040

[Problem to be solved by the invention]

As described in Patent Document 1, when miniaturization of a semiconductor package is achieved by using a laminate obtained by bonding a support base to a substrate, detachability of the support base from the laminate becomes a problem. The present invention has been made in view of the above-mentioned circumstances, and its object is to provide a layered body having a separation layer between the support base and the substrate that can form a separation layer that can further improve the photoreactivity and improve the separability of the support base from the layered body. Composition for forming a separation layer of a layer, a support substrate with a separation layer using the same, a laminate, a method for producing the same, and a method for producing an electronic component. [Technical means to solve the problem]

In order to solve the above-mentioned problems, the present invention employs the following configurations. That is, the first aspect of the present invention is a composition for forming a separation layer, characterized in that it is used to form the separation layer in a laminate having a separation layer between a support base and a substrate that transmits light, and the separation The layer can be denatured by irradiation of light from the side of the support base to separate the support base from the laminate, and the composition for forming the separation layer contains a resin component having a repeating unit represented by the following general formula (p1): P).

[chemical 1] [In the formula, L ^P1 represents a divalent linking group; R ^P1 represents a condensed polycyclic aromatic group that 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 of the first aspect.

The third aspect of the present invention is a laminate characterized in that it has a separation layer between the support base and the substrate through which light passes, and the separation layer is the separation layer-forming composition of the first aspect. The fired body.

A fourth aspect of the present invention is a method of manufacturing a laminate, which is characterized in that it is a method of manufacturing a laminate provided with a separation layer between a support substrate through which light passes and a substrate, and the above-mentioned manufacturing method has the following steps: A separation layer forming step of forming the separation layer by applying the composition for forming the separation layer of the first aspect on at least one of the substrate or the support base, followed by firing, to form the separation layer; and a layering step and laminating the aforementioned substrate and the aforementioned support base via the aforementioned separation layer.

The fifth aspect of the present invention is a method of manufacturing electronic parts, which is characterized by the following steps: a separation step, after the laminate is obtained by using the method for manufacturing the laminate of the fourth aspect, separating the laminate through the support substrate. irradiating light to the separation layer to denature the separation layer, whereby the support substrate is separated from the laminate; and a removing step of removing the separation layer attached to the substrate after the separation step. [Effect of Invention]

According to the present invention, it is possible to provide a composition for forming a separation layer capable of forming a separation layer in which the photoreactivity is further improved in a laminate provided with a separation layer between a support base and a substrate, thereby improving the separation property of the support base from the laminate, A support substrate with a separation layer using the same, a laminate, a method for manufacturing the same, and a method for manufacturing electronic components.

In this specification and the scope of this patent application, the so-called "aliphatic" is a relative concept relative to aromatic, and its definition refers to groups, compounds, etc. that do not have aromaticity. "Alkyl" includes linear, branched and cyclic monovalent saturated hydrocarbon groups unless otherwise specified. The same applies to the alkyl group in the alkoxy group. Unless otherwise specified, the "alkylene group" includes linear, branched and cyclic divalent saturated hydrocarbon groups. A "halogenated alkyl group" is a group in which a part or all of the hydrogen atoms of an alkyl group are replaced by a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. "Fluorinated alkyl group" refers to a group in which some or all of the hydrogen atoms of the alkyl group are replaced by fluorine atoms. The so-called "repeating unit" refers to the monomer unit (monomeric unit) that constitutes a polymer compound (resin, polymer, copolymer). When described as "may have a substituent", both the case of substituting a hydrogen atom (-H) with a monovalent group and the case of substituting a methylene group (-CH ₂ -) with a divalent group are included.

The so-called "styrene" includes the concept of styrene and the α-position hydrogen atom of styrene is substituted by other substituents such as alkyl group and halogenated alkyl group. In addition, the so-called α-position (carbon atom at α-position) refers to the carbon atom to which the benzene ring is bonded, unless otherwise specified.

The above-mentioned alkyl group as a substituent at the α position is preferably a straight-chain or branched-chain alkyl group, specifically, an alkyl group having 1 to 5 carbon atoms (methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl) etc. Furthermore, specific examples of the halogenated alkyl group as the substituent at the α-position include groups in which some or all of the hydrogen atoms in the above-mentioned “alkyl group as the substituent at the α-position” are substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable.

In this specification and the patent scope of this application, according to the structure shown in the chemical formula, there may be chiral carbon, enantiomer and diastereomer. In this case, the isomers are represented by one chemical formula. These isomers may be used alone or as a mixture.

(Composition for Separation Layer Formation) The composition for forming a separation layer according to the first aspect of the present invention is used to form the separation layer in a laminate having a separation layer between a light-transmitting support base and a substrate, and the separation layer can pass from the support base side. Denatured by exposure to light so that the aforementioned support substrate is separated from the aforementioned laminated body. The composition for separation layer formation of this embodiment contains the resin component (P) which has the repeating unit represented by General formula (p1) at least.

FIG. 1 shows an embodiment of a laminate to which the present invention is applied. The laminated body 10 shown in FIG. 1 includes a separation layer 2 and an adhesive layer 3 between a support base 1 and a substrate 4 , and the separation layer 2 , the adhesive layer 3 , and the substrate 4 are sequentially stacked on the support base 1 . The support base 1 is formed of a material that transmits light. In the laminate 10 , the separation layer 2 is denatured and decomposed by irradiating light from the support substrate 1 side to the separation layer 2 , so that the support substrate 1 is separated from the laminate 10 . The separation layer 2 in this laminated body 10 can be formed using the composition for separation layer formation of this embodiment.

<Resin Component (P)> The resin component (P) (hereinafter also referred to as "(P) component") is a resin component having a repeating unit represented by the general formula (p1). (P) A component has a condensed polycyclic aromatic group (R ^P1 ) which may have a substituent in a repeating unit. Thereby, in the separation layer formed from the separation layer-forming composition containing the (P) component, the laser reactivity is enhanced, the photoreactivity is further improved, and the separation property of the support substrate from the laminate is improved. Moreover, (P) component has a divalent linking group (L ^P1 ) in a repeating unit. Therefore, the (P) component is easily denatured (oxidized, etc.) by heating or the like. In the separation layer formed from the composition for separation layer formation containing the said (P)component, the absorption of light improves and it is excellent in photoreactivity.

In FIG. 1 , in a laminate 10 having a separation layer 2 formed using a composition for forming a separation layer containing (P) component, the separation layer 2 is denatured by irradiation with light from the side of the support substrate 1 and is easily detached from the substrate 4. The ground peels off, and the supporting matrix 1 is separated. Moreover, when the separation layer 2 containing (P) component peels off from the board|substrate 4, there is little adhesion residue (residue) on the board|substrate 4, and the removability from the board|substrate 4 is also favorable. In addition, since the (P) component has a divalent linking group (L ^P1 ) in the repeating unit, the separation layer 2 containing the (P) component has improved heat resistance and further has high chemical resistance. In addition, since the laser reactivity of the (P) component is strong, the laser damage of the separation layer 2 containing the (P) component is suppressed, and the laser intensity can be increased, and the process time can be shortened.

(P)component may have another repeating unit other than the repeating unit represented by general formula (p1).

"Repeating unit represented by general formula (p1)" The component (P) has a repeating unit represented by the following general formula (p1) (hereinafter also referred to as "repeating unit (p1)").

[Chem 2] [In the formula, L ^P1 represents a divalent linking group; R ^P1 represents a condensed polycyclic aromatic group that may have a substituent]

In the aforementioned formula (p1), the divalent linking group in L ^P1 may include an aromatic ring, may include multiple types of aromatic rings, or may include a ring structure formed by condensing an aromatic ring and an aliphatic ring. When the divalent linking group in L ^P1 includes 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 Mode. The number of carbon atoms in the aromatic ring is preferably 5-30, more preferably 5-20, still more preferably 6-15, especially preferably 6-12. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocyclic rings in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced by heteroatoms; and the like. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom, and the like. Specific examples of the aromatic heterocycle include a pyridine ring, a thiophene ring, and the like. The number of aromatic rings included in the divalent linking group may be one, or two or more, and two or more aromatic rings are preferred because of better photoreactivity.

Alternatively, in the aforementioned formula (p1), the divalent linking group in L ^P1 is preferably a divalent linking group containing a heteroatom. In order to impart desired properties, as L ^p1 , linking groups introduced with various skeletons can be mentioned. Examples of the skeleton in the aforementioned "linking group introduced with various skeletons" include naphthalene skeleton, anthracene skeleton, Skeleton, fenugreek skeleton, bisphenol A skeleton, etc.

As L ^p1 , for example, an ether bonded group of bisphenols, an ether bonded group of diols, an ester bonded group of dicarboxylic acids, an Si-O bonded group, or repetitions of these bonded groups can be mentioned. structure etc.

Examples of the bisphenols include bisphenol F, bisphenol A, bisphenol Z, biphenol, or polymers thereof. Examples of the diols include ethylene glycol, propylene glycol, 1,6-hexanediol, neopentyl glycol, naphthalene diol (dihydroxynaphthalene), anthracene diol (dihydroxyanthracene), 2,2- Bis(4-hydroxyphenyl)propane or its polymers, etc. Examples of the dicarboxylic acids include maleic acid, phthalic acid, hydrogenated phthalic acid, and terephthalic acid.

In the case where an ether bonded group of bisphenols is selected as L ^p1 , it is easy to improve the flexibility of the (P) component film formation. When the ether bond group of diols is selected as L ^p1 , the alkali solubility of (P) component can be adjusted easily. As the ether linkage group of diols, a linkage group into which a diol skeleton has been introduced is preferable. As a diol skeleton, a propylene glycol skeleton is mentioned, for example. When the Si—O bonding group is selected as L ^p1 , it is easy to achieve low dielectric of the (P) component molding.

A preferred specific example of L ^P1 (divalent linking group) in the aforementioned formula (p1) is shown below. In the following formula, * represents a bond to a methylene group (CH ₂ ). n in the chemical formula ( ^LP1-9 ) represents the repeating number of oxypropylene.

[Chem 3]

In the aforementioned 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. The condensed polycyclic aromatic ring may be a ring structure formed by condensing a plurality of aromatic rings, or may be a ring structure formed by condensing an aromatic ring and an aliphatic ring. In the ring structure formed by condensation of an aromatic ring and an aliphatic ring, the number of aromatic rings may be plural, the number of aliphatic rings may also be plural, and each of the aromatic ring and the aliphatic ring may be one. The number of rings constituting the condensed polycyclic aromatic ring is preferably 2 to 5, more preferably 2 to 3, and still more preferably 3.

In the aforementioned formula (p1), examples of the substituents that the condensed polycyclic aromatic group in R ^P1 may have include hydroxyl, carboxyl, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.), alkoxy groups (methoxy, ethoxy, propoxy, butoxy, etc.), alkyloxycarbonyl, pendant oxy (=O), etc. Also, 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, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, A group obtained by removing one hydrogen atom from a ring, a triphenylene ring, a perylene ring, an anthraquinone ring, or a naphthoquinone ring. Among them, R ^P1 is preferably a group obtained by removing one hydrogen atom from an anthraquinone ring or a naphthoquinone ring, more preferably a group obtained by removing one hydrogen atom from an anthraquinone ring.

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

[chemical 4]

[chemical 5]

(P) The repeating unit (p1) which a component has may be 1 type, and may be 2 or more types. The ratio of the repeating unit (p1) in the component (P) is preferably 1 mol% or more relative to the total (100 mol%) of all repeating units constituting the (P) component, and may be 1 to 100 mol Ear%.

When the component (P) has other repeating units in addition to the repeating unit (p1), the ratio of the repeating unit (p1) in the component (P) to the total of all the repeating units constituting the component (P) (100 mo mol%), preferably 1 to 99 mol%, more preferably 1 to 70 mol%, still more preferably 1 to 50 mol%. When the ratio of the repeating unit (p1) is more than the lower limit of the aforementioned preferred range, the laser reactivity is likely to be enhanced. On the other hand, when it is below the upper limit of the aforementioned preferable range, it is easy to obtain balance with other repeating units.

"Other repeating units" The (P) component may be a component having another repeating unit in addition to the above-mentioned repeating unit (p1). As another repeating unit, the repeating unit etc. which are represented by the general formula (p2) mentioned later are mentioned, for example.

Regarding the repeating unit represented by the general formula (p2): The component (P) is preferably a resin having a repeating unit represented by the following general formula (p2) (hereinafter also referred to as "repeating unit (p2)") in addition to the above-mentioned repeating unit (p1).

[chemical 6] [In the formula, L ^P2 represents a divalent linking group; R ^P2 represents a monocyclic aromatic group that may have a substituent]

In the above formula (p2), the description about L ^P2 is the same as the description about 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 as those represented by the above chemical formulas (L ^P1 -1) to (L ^P1 -9).

In the aforementioned formula (p2), the monocyclic aromatic group in R ^P2 is a hydrocarbon group having one aromatic ring. The aromatic ring may be a cyclic conjugated system with 4n+2 π electrons. Specific examples of the aromatic ring constituting the monocyclic aromatic group in R ^P2 include a benzene ring; a pyridine ring, a thiophene ring, a pyrrole ring, an imidazole ring, a furan ring, and a thiazole ring. Among them, R ^P2 is preferably a group obtained by removing one hydrogen atom from a benzene ring.

When the hydrocarbon group represented by R ^P2 above is substituted, examples of the substituent include hydroxyl group, carboxyl group, halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), alkoxy group (methoxy group, ethoxy group, etc.), radical, propoxy, butoxy, etc.), alkyloxycarbonyl, etc.

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

[chemical 7]

When the (P) component has a repeating unit (p2), the repeating unit (p2) may be one type or two or more types. When the (P) component has a repeating unit (p2), the ratio of the repeating unit (p2) in the (P) component is preferable to the total (100 mol%) of all the repeating units constituting the (P) component It is 1-99 mol%, More preferably, it is 30-99 mol%, More preferably, it is 50-99 mol%. When the ratio of a repeating unit (p2) is more than the lower limit of the said preferable range, it becomes easy to improve photoreactivity. On the other hand, when it is below the upper limit of the said preferable range, it becomes easy to acquire the balance with a repeating unit (p1).

In the composition for separation layer formation of this embodiment, (P)component is resin which has a repeating unit (p1) at least. The (P) component may be a resin composed of only the repeating unit (p1). As preferable (P) component, the 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)=1:99～99:1, More preferably, it is 1:99-70:30, More preferably, it is 1:99-50:50.

Alternatively, the component (P) may be a mixed resin of a resin having at least a repeating unit (p1) and a resin consisting of only the repeating unit (p2). In this case, the ratio of the repeating unit (p1) is preferably 1 to 99 mol%, more preferably 1 to 70 mol%, based on the total (100 mol%) of all repeating units constituting the mixed resin %, and more preferably 1 to 50 mol%. The ratio (molar ratio) of all repeating units (p1) to all repeating units (p2) constituting the mixed resin is preferably all repeating units (p1):all repeating units (p2)=1:99～99:1, more Preferably it is 1:99-70:30, and more preferably it is 1:99-50:50.

The component (P) has film-forming ability, and preferably has a molecular weight of 1,000 or more. Film forming ability improves by making the molecular weight of (P)component 1000 or more. (P) The molecular weight of the component is more preferably 1,000-30,000, still more preferably 1,500-25,000, particularly preferably 1,500-20,000, most preferably 2,000-15,000. The solubility to the solvent of the composition for separation layer formation improves by making the molecular weight of (P)component below the upper limit of the said preferable range. In addition, as the molecular weight of a resin component, the weight average molecular weight (Mw) in terms of polystyrene obtained by GPC (gel permeation chromatography) was used.

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

In addition, as the (P) component, aminoanthraquinone or aminonaphthoquinone, aminophenols, aminonaphthols or anilines, and a compound having two epoxy groups in one molecule can also be used. The resin produced by the reaction. Examples of aminophenols include 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-amino-3-methylphenol, 2-amino-4-methylphenol, 3-aminophenol, -Amino-2-methylphenol, 5-amino-2-methylphenol, etc. Examples of aminonaphthols include 1-amino-2-naphthol, 3-amino-2-naphthol, 5-amino-1-naphthol and the like. Examples of compounds having two epoxy groups in one molecule include bisphenol-type epoxy compounds with trade names of EPICLON 850, EPICLON 830 (manufactured by DIC Corporation), jERYX-4000 (manufactured by Mitsubishi Chemical Corporation) and the like. Resin; DENACOL EX-211, DENACOL EX-212, DENACOL EX-810, DENACOL EX-830, DENACOL EX-911, DENACOL EX-920, DENACOL EX-930 (manufactured by Nagase Chemtex Co., Ltd.) and other diol-type epoxies Resin; Dicarboxylate type epoxy resins such as DENACOL EX-711, DENACOL EX-721 (manufactured by Nagase Chemtex Co., Ltd.), jER191P (manufactured by Mitsubishi Chemical Co., Ltd.); X-22-163, KF-105 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and other polysiloxane epoxy resins, etc. The heat treatment temperature during the above reaction is preferably set at 60°C to 250°C, more preferably at 80°C to 180°C.

The (P) component contained in the composition for separation layer formation of this embodiment may be 1 type, and may be 2 or more types. What is necessary is just to adjust content of the (P)component in the composition for separation layer formation of this embodiment according to the thickness etc. of the separation layer to be formed. The content of the component (P) in the composition for forming a separation layer is, for example, preferably 1 to 100 mass %, more preferably 1 to 70 mass %, based on the composition (100 mass %), Furthermore, it is more preferable that it is 5-50 mass %, and it is especially preferable that it is 10-50 mass %. When content of (P)component is more than the lower limit of the said preferable range, it becomes easy to improve the photoreactivity of a separation layer. In addition, it is also easy to improve chemical resistance. On the other hand, photoreactivity and releasability are more likely to be improved as it is below the upper limit of the said preferable range.

＜Other ingredients＞ The composition for separation layer formation of this embodiment may further contain components (optional components) other than the above-mentioned (P)component. Examples of the optional components include resins other than the (P) component shown below, thermal acid generator components, photoacid generator components, photosensitizer components, organic solvent components, surfactants, sensitizers, and the like.

The composition for separation layer formation of this embodiment may contain resins other than (P)component in the range which does not impair the effect of this invention. Examples of resins other than the component (P) include novolak-type phenolic resins, resol-type phenolic resins, hydroxystyrene resins, hydroxyphenyl silsesquioxane resins, and hydroxybenzyl silsesquioxane resins. Resin, acrylic resin containing phenol skeleton, etc. By using the novolak-type phenolic resin which is resin other than (P) component together with (P) component, generation|occurrence|production of the void by heating can also be suppressed easily.

"Thermal Acid Generator" In the composition for forming a separation layer according to the present embodiment, it is preferable to further contain a thermal acid generator (hereinafter also referred to as "component (T)"). By making the composition for forming the separation layer contain (T) component, the oxidation of the separation layer is promoted by the action of the acid generated by the (T) component when heating during firing, etc. Denatured by irradiation (can improve the photoreactivity of the separation layer).

The component (T) can be appropriately selected from known components, and the temperature for generating an acid is preferably higher than the temperature at which the support base coated with the composition for forming a separation layer is prebaked, More preferably, it is 110°C or higher, and still more preferably, it is 130°C or higher. Examples of the above-mentioned (T) component include trifluoromethanesulfonate, hexafluorophosphate, perfluorobutanesulfonate, boron trifluoride salt, boron trifluoride ether complex, and the like. As a preferable (T) component, the compound which consists of the cation part and anion part shown below is mentioned.

[chemical 8] [In the formula (T-ca-1), R ^h01 -R ^h04 are each independently selected from the group consisting of a hydrogen atom, an alkyl group with 1 to 20 carbon atoms and an aryl group, and among R ^h01 -R ^h04 At least one of them is an aryl group; the aforementioned alkyl or aryl group may have a substituent; in formula (T-ca-2), R ^h05 to R ^h07 are each independently selected from an alkyl group having 1 to 20 carbon atoms and aryl groups, at least one of R ^h05 to R ^h07 is an aryl group; the aforementioned alkyl or aryl groups may have substituents]

・In the aforementioned formula (T-ca-1) regarding the cationic portion of the component (T), the alkyl group in R ^h01 to R ^h04 has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more It is preferably a straight-chain or branched alkyl group having 1-5 carbon atoms, more preferably a straight-chain or branched-chain alkyl group having 1-5 carbon atoms. Specifically, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc., among them, Methyl and ethyl are preferred.

The alkyl groups in R ^h01 to R ^h04 may have substituents. Examples of the substituent include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and a cyclic group.

The alkoxy group as the substituent of the alkyl group is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, The tertiary butoxy group is further preferably a methoxy group or an ethoxy group. Examples of the halogen atom as the substituent of the alkyl group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, among which a fluorine atom is preferred. The halogenated alkyl group as the substituent of the alkyl group includes an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a n-butyl group, a tert-butyl group, etc., in which a part or all of the hydrogen atoms are replaced. A group obtained by substituting the aforementioned halogen atoms. The carbonyl group which is a substituent of an alkyl group is a group which substitutes the methylene group ( _-CH2- ) which comprises an alkyl group (>C=O). The cyclic group as the substituent of the alkyl group includes an aromatic hydrocarbon group and an alicyclic hydrocarbon group (which may be polycyclic or monocyclic). Examples of the aromatic hydrocarbon group here include the same ones as the aryl groups in R ^h01 to R ^h04 described later. Among the alicyclic hydrocarbon groups here, a monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane is preferably a monocycloalkane having 3 to 6 carbon atoms, and specific examples thereof include cyclopentane, cyclohexane, and the like. Also, the polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycyclic alkane, and the polycyclic alkane is preferably a polycyclic alkane having 7 to 30 carbon atoms. . Among them, as the polycycloalkane, more preferably: adamantane, nor-alkane, iso-alkane, tricyclodecane, tetracyclododecane, etc. have polycyclic skeletons with cross-linked ring systems; Polycycloalkanes containing polycyclic skeletons of condensed ring systems such as cyclic groups of steroid skeletons.

In the aforementioned formula (T-ca-1), the aryl groups in R ^h01 to R ^h04 are hydrocarbon groups having at least one 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 number of carbon atoms in the aromatic ring is preferably 5-30, more preferably 5-20, still more preferably 6-15, especially preferably 6-12. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocyclic rings in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced by heteroatoms; and the like. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom, and the like. Specific examples of the aromatic heterocycle include a pyridine ring, a thiophene ring, and the like. Specific examples of the aryl group in R ^h01 to R ^h04 include: a group obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocyclic ring; A group obtained by removing one hydrogen atom from an aromatic compound (such as biphenyl, fennel, etc.); a group obtained by replacing one hydrogen atom of the aforementioned aromatic hydrocarbon ring or aromatic heterocycle with an alkylene group (for example, benzyl arylalkyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.) etc. The number of carbon atoms in the alkylene group bonded to the aforementioned aromatic hydrocarbon ring or aromatic heterocyclic ring is preferably 1-4, more preferably 1-2, especially preferably 1. Among them, a group obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocyclic ring, or a group obtained by removing one hydrogen atom of the aforementioned aromatic hydrocarbon ring or aromatic heterocyclic ring by an alkylene group is more preferable. The substituted group is more preferably a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring, or a group obtained by substituting one hydrogen atom of the aromatic hydrocarbon ring with an alkylene group.

Aryl groups in R ^h01 to R ^h04 may have a substituent. Examples of the substituent include 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 alkylcarbonyloxy group and the like.

The alkyl group as the substituent of the aryl group is preferably an alkyl group having 1 to 5 carbon atoms, and is preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. Explanations about alkoxyl, halogen atom, halogenated alkyl, carbonyl, and cyclic group as substituents of aryl group and the above-mentioned alkoxyl, halogen atom, halogenated alkyl, carbonyl, The description of the cyclic group is the same. In the alkylcarbonyloxy group used as the substituent of the aryl group, the number of carbon atoms in the alkyl part is preferably 1 to 5, and examples of the alkyl part include methyl, ethyl, propyl, isopropyl, etc. Among them, methyl and ethyl are preferred, and methyl is more preferred.

However, in the aforementioned formula (T-ca-1), at least one of R ^h01 to R ^h04 is an aryl group which may have a substituent. Specific examples of the cation represented by the aforementioned formula (T-ca-1) are shown below.

[chemical 9]

In the aforementioned formula (T-ca-2), the descriptions about the alkyl and aryl groups in R ^h05 to R ^h07 are the same as the descriptions about the alkyl and aryl groups in R ^h01 to R ^h04 described above, respectively.

However, in the aforementioned formula (T-ca-2), at least one of R ^h05 to R ^h07 is an aryl group which may have a substituent. Specific examples of the cation represented by the aforementioned formula (T-ca-2) are shown below.

[chemical 10]

・About the anion part of (T) component Examples of the anion portion of the component (T) include hexafluorophosphate anion, trifluoromethanesulfonate anion, perfluorobutanesulfonate anion, tetrakis(pentafluorophenyl)borate anion, and the like. Among them, hexafluorophosphate anion, trifluoromethanesulfonate anion, and perfluorobutanesulfonate anion are preferable, and hexafluorophosphate anion and trifluoromethanesulfonate anion are more preferable.

In the composition for forming a separation layer according to this embodiment, as the component (T), for example, San-Aid SI-45, SI-47, SI-60, SI-60L, SI-80, and SI-80L can be used. , 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 (manufactured by Sanshin Chemical Industry Co., Ltd. above); 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 Co., Ltd.); FC-520 (manufactured by 3M Corporation); 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- Commercially available products such as 1756, CXC-1821, CXC-1802-60, and CXC-2689 (the above are manufactured by KING INDUSTRY).

The (T) component contained in the composition for separation layer formation of this embodiment may be 1 type, and may be 2 or more types. In the composition for forming a separation layer according to the present embodiment, among the above, the component (T) is preferably hexafluorophosphate, trifluoromethanesulfonate, or perfluorobutanesulfonate, and more preferably trifluoromethanesulfonate. Sulfonate, and more preferably the quaternary ammonium salt of trifluoromethanesulfonic acid. When the composition for forming a separation layer according to this embodiment contains component (T), the content of component (T) is preferably 0.01 to 20 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of component (P). 15 parts by mass, more preferably 2 to 10 parts by mass. If the content of component (T) is within the aforementioned preferable range, denaturation is likely to occur due to light irradiation (the photoreactivity of the separation layer can be improved). For example, a fired body that can suitably absorb light in a wavelength range of 600 nm or less can be easily formed by firing. In addition, chemical resistance is further improved.

"Photoacid Generator" The composition for separation layer formation of this embodiment may further contain a photoacid generator. By containing the photoacid generator, the above composition for forming a separation layer utilizes the acid generated by the photoacid generator during heating during firing, etc., similarly to the case of containing the component (T) as described above. The role of the separation layer is to promote the oxidation, so it is easy to denature due to light irradiation (it can improve the photoreactivity of the separation layer). As a photoacid generator, for example, onium salt-type acid generators, such as a perium salt, are mentioned preferably.

Preferable cation moieties in onium salt-based acid generators include perium cations and iodonium cations.

Preferable anion moieties among onium salt-based acid generators include tetrakis(pentafluorophenyl)borate ([B(C ₆ F ₅ ) ₄ ] ^- ); tetrakis[(trifluoromethyl)benzene base]borate ([B(C ₆ H ₄ CF ₃ ) ₄ ] ^- ); difluorobis(pentafluorophenyl)borate ([(C ₆ F ₅ ) ₂ BF ₂ ] ^- ); Fluorophenyl)borate ([(C ₆ F ₅ )BF ₃ ] ^- ); Tetrakis(difluorophenyl)borate ([B(C ₆ H ₃ F ₂ ) ₄ ] ^- ), etc. Moreover, an anion represented by the following general formula (b0-2a) is also preferable.

[chemical 11] [In the formula, R ^bf05 is a fluorinated alkyl group that may have a substituent; nb ¹ is an integer of 1 to 5]

In the aforementioned formula (b0-2a), the fluorinated alkyl group in R ^bf05 preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 5 carbon atoms . Among them, R ^bf05 is preferably a fluorinated alkyl group having 1 to 5 carbon atoms, more preferably a perfluoroalkyl group having 1 to 5 carbon atoms, still more preferably a trifluoromethyl group or a pentafluoroethyl group. In the aforementioned formula (b0-2a), nb ¹ is preferably an integer of 1-4, more preferably an integer of 2-4, most preferably 3. When nb ¹ is 2 or more, a plurality of R ^bf05 may be the same or different.

The photoacid generator contained in the composition for separation layer formation of this embodiment may be 1 type, and may be 2 or more types. When the composition for forming a separation layer according to this embodiment contains a photoacid generator, the content of the photoacid generator is preferably 0.01 to 20 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the (P) component. 15 parts by mass, more preferably 2 to 10 parts by mass. If the content of the photoacid generator is within the aforementioned preferred range, denaturation will easily occur due to light irradiation (the photoreactivity of the separation layer can be improved). For example, a fired body that can suitably absorb light in a wavelength range of 600 nm or less can be easily formed by firing. In addition, chemical resistance is further improved.

"Sensitizer Ingredients" As the sensitizer component (hereinafter also referred to as "component (C)"), for example, a compound having a phenolic hydroxyl group represented by the following chemical formula (c1) and 1,2-diazidonaphthoquinone sulfonic acid The esterification reaction product of the compound (hereinafter also referred to as "component (C1)") is a preferred component.

[chemical 12]

Examples of the 1,2-diazidonaphthoquinone sulfonic acid compound include 1,2-diazidonaphthoquinone-5-sulfonyl compound, 1,2-diazidonaphthoquinone-4-sulfonyl compound, Acyl compounds, etc., preferably 1,2-diazidonaphthoquinone-5-sulfonyl compounds.

Preferred specific examples of the (C1) component are shown below.

[chemical 13] [In formula (c1-1), D ¹ to D ⁴ each independently represent a hydrogen atom or 1,2-diazidonaphthoquinone-5-sulfonyl group; at least one of D ¹ to D ⁴ represents 1,2-diazidonaphthoquinone-5-sulfonyl]

The esterification rate of the aforementioned (C1) component is preferably 50-70%, more preferably 55-65%. When the esterification rate is 50% or more, film loss after alkali development can be further suppressed, and the remaining film rate can be improved. Storage stability improves further that this esterification rate is 70 % or less. The so-called "esterification rate" here refers to the compound represented by the aforementioned formula (c1-1), which means that D ¹ to D ⁴ in the formula (c1-1) are replaced by 1,2-diazidonaphthoquinone- The ratio of 5-sulfonyl substitution. The above-mentioned (C1) component is also preferable from the viewpoint that it is very inexpensive and can achieve high sensitivity.

Moreover, as (C)component, other photosensitizer components other than the said (C1)component (it may also be called "(C2)component" hereafter.) can be used. As the (C2) component, for example, the following phenolic hydroxyl group-containing compound ((c2-phe) component) and 1,2-diazidonaphthoquinone sulfonic acid compound (preferably 1,2- The esterification reaction product of naphthoquinonediazidoquinone-5-sulfonyl compound or 1,2-naphthoquinonediazidoquinone-4-sulfonyl compound) is a preferred component.

Examples of the (c2-phe) component include tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxyphenylmethane) -2,3,5-trimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy -3,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2 ,5-Dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-2,5 -Dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2, 5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, bis(4- Hydroxyphenyl)-3-methoxy-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl -4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, bis(5- Cyclohexyl-4-hydroxy-2-methylphenyl)-3,4-dihydroxyphenylmethane, bis(2,3,5-trimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane , 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-trihydroxyphenyl)-2-(4'-hydroxyphenyl) ) propane, 2-(2,3,4-trihydroxyphenyl)-2-(4'-hydroxy-3',5'-dimethylphenyl)propane, bis(2,3,4-trihydroxy Phenyl)methane, bis(2,4-dihydroxyphenyl)methane, 2,3,4-trihydroxyphenyl-4'-hydroxyphenylmethane, 1,1-bis(4-hydroxyphenyl)cyclo Hexane, 2,4-bis[1-(4-hydroxyphenyl)isopropyl]-5-hydroxyphenol, etc.

The (C) component contained in the composition for separation layer formation of this embodiment may be used individually by 1 type, and may use it in combination of 2 or more types. In the composition for separation layer formation of this embodiment, among the above-mentioned, it is preferable to use (C1) component as (C)component. When the composition for forming a separation layer according to the present embodiment contains component (C), the content of component (C) is preferably 95 parts by mass or less, more preferably 50 to 95 parts by mass, relative to 100 parts by mass of component (P). parts by mass, and more preferably 60 to 90 parts by mass. If the content of component (C) is within the aforementioned preferred range, the photoreactivity of the separation layer can be further improved.

"Organic Solvent Composition" The separation layer-forming composition of the present embodiment may contain an organic solvent component (hereinafter also referred to as "(S) component") for the purpose of adjusting coating workability and the like. As the component (S), for example, straight-chain hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, and tridecane are mentioned; Branched-chain hydrocarbons with 4 to 15 carbon atoms; cyclic hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, naphthalene, decalin, tetrahydronaphthalene, etc.; p-menthane, o-menthane, m-menthane Alkanes, diphenylmenthane, 1,4-terpene diol, 1,8-terpene diol, thalane, northane, pinane, thujane, carane, longifolene, geraniol, orange Arthyl alcohol, linalool, citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinene-1-ol , terpinene-4-ol, dihydroterpinyl acetate, 1,4-cineole, 1,8-cineole, borneol, carvone, ionone, thujone, camphor, d-limonene , l-limonene, dipentene and other terpene solvents; γ-butyrolactone and other lactones; acetone, methyl ethyl ketone, cyclohexanone (CH), methyl n-amyl ketone, methyl iso Amyl ketone, 2-heptanone and other ketones; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and other polyols; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoethylene Ester, or compounds with ester bonds such as dipropylene glycol monoacetate, monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, etc. Derivatives of polyols such as phenyl ether and other compounds with ether bonds (among them, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred); dioxane and the like Cyclic ethers, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methoxypropyl acetate, methoxybutyl acetate, methyl pyruvate , ethyl pyruvate, methyl methoxy propionate, ethyl ethoxy propionate and other esters; anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, Aromatic organic solvents such as dibenzyl ether, phenetole ether, and butyl phenyl ether, etc. The (S) component contained in the composition for separation layer formation of this embodiment may be 1 type, and may be 2 or more types.

In the separation layer-forming composition of this embodiment, the usage-amount of (S) component is not specifically limited, It can set suitably according to coating film thickness and coatability within the concentration which can apply|coat to a support base etc.. The total amount of the above-mentioned (P) component in the composition for forming a separation layer is preferably 70% by mass or less, more preferably 10 to 50% by mass, based on the total mass (100% by mass) of the composition. Use the (S) component within the range.

"Surfactant" The separation layer-forming composition of the present embodiment may contain a surfactant for the purpose of adjusting coating workability and the like. Examples of the surfactant include silicone-based surfactants and fluorine-based surfactants. As silicone-based surfactants, BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, BYK- 322, 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 (the above are manufactured by BYK Chemie), etc. As the fluorine-based 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 (the above are manufactured by DIC Co., Ltd.); PolyFox series PF-636, PF-6320, PF-656, PF- 6520 (the above are manufactured by Omnova), etc.

The surfactant contained in the composition for forming a separation layer according to the present embodiment may be one type, or two or more types. When the composition for forming a separation layer according to this 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 the component (P). part, more preferably 0.03 to 1 part by mass. When the content of the surfactant is within the aforementioned preferable range, a separation layer with high flatness can be easily formed when the composition for forming a separation layer is applied to a support substrate.

(Support substrate with separation layer) The support base with a separation layer of the second aspect of the present invention includes: a support base; and a separation layer formed on the support base using the composition for forming a separation layer of the first aspect. In the support substrate with a separation layer of the present embodiment, the separation layer formed using the composition for forming a separation layer of the above-mentioned embodiment is provided on the support substrate. Therefore, photoreactivity and chemical resistance are improved in the above-mentioned support substrate with a separation layer.

＜Support substrate＞ The support matrix has the property of allowing light to pass through. The supporting base system is a member that supports the substrate and is bonded to the substrate through the separation layer. Therefore, it is preferable that the support base has strength necessary for preventing damage or deformation of the substrate during thinning of the sealing body, transportation of the substrate, mounting on the substrate, and the like. In addition, the support substrate preferably transmits light of a wavelength capable of denaturing the separation layer. As the material of the supporting base, for example, glass, silicon, acrylic resin, or the like can be used. Examples of the shape of the support base include rectangles, circles, and the like, but are not limited thereto. In addition, as the support base, for further high-density integration and improvement of production efficiency, a base obtained by enlarging the size of the circular support base, or a large panel with a quadrangular shape in plan view can also be used.

＜Separation layer＞ The separation layer can be formed using the separation layer-forming composition of the above-mentioned embodiment, and is a layer formed of a fired body formed by firing the resin component (P) contained in the separation layer-forming composition. The separation layer is suitably denatured by absorbing light irradiated through the support substrate. Furthermore, the separation layer may be a layer obtained by blending a material not having a light-absorbing structure within the range not impairing the essential characteristics of the present invention, but from the viewpoint of photoreactivity and separation, it is preferable to use only Formed from light-absorbing materials.

The fired body referred to here refers to a product obtained by firing a composition containing (P)component. This firing system is formed by firing a composition containing the component (P) in an air atmosphere, that is, an atmosphere where 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 so-called "denaturation" of the separation layer refers to a phenomenon in which the separation layer becomes a state of being destroyed by external force, or a state in which the adhesive force between the layers in contact with the separation layer is reduced. The separation layer becomes brittle by absorbing light, and loses its strength or adhesiveness before being irradiated with light. The above-mentioned denaturation of the separation layer occurs by generation of decomposition due to energy of absorbed light, change of stereo configuration, dissociation of functional groups, and the like.

The thickness of the separation layer is, for example, preferably in the range of 0.05 μm to 50 μm, more preferably in the range of 0.3 μm to 1 μm. If the thickness of the separation layer is in the range of not less than 0.05 μm and not more than 50 μm, the desired denaturation of the separation layer can be produced by short-time light irradiation and low-energy light irradiation. Also, from the viewpoint of productivity, the thickness of the separation layer is preferably within a range of 1 μm or less.

For example, in the laminated body 10 shown in FIG. 1 , the surface of the side of the separation layer that is in contact with the adhesive layer is preferably flat (no unevenness is formed), so that the formation of the adhesive layer can be easily performed, and the adhesive layer can be easily formed. The support base is evenly attached to the substrate.

The support substrate with a separation layer of this embodiment can be produced by performing the same operation as the operation of the [separation layer forming step] described later.

Since the support substrate with a separation layer of this embodiment is provided with a separation layer obtained by applying the composition for forming a separation layer of the above-mentioned embodiment, laser reactivity is enhanced and photoreactivity is further improved. Preferably, chemical resistance is also improved.

(laminated body) The laminate of the third aspect of the present invention includes a separation layer between the support base and the substrate through which light is transmitted. This separation layer is a fired body of the composition for separation layer formation of the above-mentioned embodiment. As shown in FIG. 1 , in the laminated body 10 of this embodiment, a separation layer 2 , an adhesive layer 3 , and a substrate 4 are sequentially laminated on a support base 1 .

The description about the supporting base 1 is the same as that described in the above <Supporting base>. The description of the separation layer 2 is the same as that of the above-mentioned <separation layer>.

＜Bonding layer＞ The adhesive layer 3 is a layer for bonding the support base 1 and the substrate 4 together, and can be formed using a composition for forming an adhesive layer. Examples of the composition for forming an adhesive layer include compositions containing other components such as thermoplastic resins, diluents, and additives. As the thermoplastic resin, as long as it exhibits adhesive force, hydrocarbon resins (preferably cycloolefin polymers, etc.), acrylic-styrene resins, maleimide resins, elastomer resins, polyester resins, etc. One or two or more of resins, etc. Examples of the diluent include the same components as the above-mentioned (S) component. Other components include additional resins for improving the performance of the adhesive layer, curable monomers, photopolymerization initiators, plasticizers, adhesive auxiliary agents, stabilizers, colorants, thermal polymerization inhibitors, and surface active agents. agent etc.

The thickness of the bonding layer 3 is, for example, preferably in the range of 0.1 μm to 50 μm, more preferably 1 μm to 10 μm. If the thickness of the adhesive layer is in the range of 0.1 μm to 50 μm, the support base 1 and the substrate 4 can be bonded together more favorably. In addition, by making the thickness of the adhesive layer 1 μm or more, the substrate can be sufficiently fixed on the support base, and by making the thickness of the adhesive layer 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 supporting base 1 . Structures such as integrated circuits and metal bumps are mounted on the substrate 4 . As the substrate 4, typically, a silicon wafer substrate can be used, but not limited thereto, and a ceramic substrate, film substrate, flexible substrate, etc. can also be used.

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

Since the layered body of the above-mentioned embodiment is provided with the separation layer obtained by applying the composition for forming a separation layer of the above-mentioned embodiment, the laser reactivity is enhanced, and the photoreactivity is further improved (denatured appropriately by light irradiation), The detachability of the support matrix from the laminate is improved. In addition, since the laminate of the embodiment is provided with the separation layer obtained by applying the separation layer-forming composition of the above-mentioned embodiment, chemical resistance is improved. Thereby, the laminated body of embodiment is less likely to be damaged by the influence of the chemical etc. used for etching process, photolithography process, etc.

In the laminate of the above embodiment, the support base 1 and the separation layer 2 are adjacent to each other, but the present invention is not limited to this, and another layer may be further formed between the support base 1 and the separation layer 2 . In this case, the other layers may be made of a material that transmits light. Accordingly, it is possible to appropriately add a layer that imparts preferable properties to the laminate 10 without hindering the incidence of light on the separation layer 2 . The wavelength of light that can be used differs depending on the type of material constituting the separation layer 2 . Therefore, the material constituting the other layer does not need to transmit light of all wavelengths, and can be appropriately selected from materials that transmit light of a wavelength capable of denaturing the material constituting the separation layer 2 .

In addition, the laminate of the above-described embodiment includes the adhesive layer 3 for bonding the support base 1 and the substrate 4 , but is not limited thereto, and only the separation layer 2 may be provided between the support base 1 and the substrate 4 . In this case, for example, a separation layer that also functions as an adhesive layer can be used.

(Manufacturing method of laminated body) A fourth aspect of the present invention is a method for manufacturing a laminate having a separation layer between a support base through which light is transmitted and a substrate, and includes a separation layer forming step and a lamination step.

<First Embodiment> Fig. 2 is a schematic step diagram illustrating an embodiment of a method for manufacturing a laminate. Fig. 2(a) is a diagram illustrating a separation layer forming step, and Fig. 2(b) is a diagram illustrating a lamination step. In the method for producing a laminate of this embodiment, a separation layer formed by dissolving a resin component ((P) component) having a repeating unit represented by the above general formula (p1) in an organic solvent component ((S) component) is used. with composition. Moreover, the composition for adhesive layer formation which the hydrocarbon resin melt|dissolved in (S) component was used.

[Separation layer formation step] The separation layer forming step in the embodiment is a step of applying the composition for forming a separation layer in the above embodiment on one side of the support substrate, followed by firing, thereby forming a separation layer. In Fig. 2(a), the composition for forming a separation layer according to the above-mentioned embodiment is coated on a support substrate 1, and then fired to form a separation layer 2 (that is, a support substrate with a separation layer is produced). .

The method of applying the separation layer-forming composition onto the support substrate 1 is not particularly limited, and examples thereof include methods such as spin coating, dipping, roll doctor blade, spray coating, and slit coating.

In the separation layer forming step, the component (S) is removed from the coating layer of the separation layer forming composition applied on the support substrate 1 under a heating environment or a reduced pressure environment to form a film. The removal of (S) component can be performed, for example by performing a baking process for 120 to 360 seconds under the temperature condition of 80-150 degreeC. Then, the film obtained by removing the (S) component from the above-mentioned coating layer is fired in an air atmosphere to form the separation layer 2 made of the fired body.

The temperature at the time of firing the film obtained by removing the (S) component from the aforementioned coating layer can be appropriately set according to the type of (P) component, for example, it is preferably set at 200°C or higher, more preferably at Above 250°C. If the temperature at the time of firing is not less than the lower limit of the above-mentioned preferred range, the separation layer capable of absorbing light in the wavelength range of 600 nm or less can be formed more stably. The upper limit of the temperature at the time of firing is not particularly limited, for example, it is preferably set to 800°C or lower, more preferably 600°C or lower.

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

[Stacking steps] The lamination step in the embodiment is a step of laminating the support base 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), the support base 1 with the separation layer 2 formed and the substrate 4 without the separation layer 2 are laminated with the separation layer 2 and the adhesive layer 3 interposed therebetween, and the support base 1, the separation layer 2, and the adhesive layer 3 are obtained. 1. A laminate 10 formed by stacking substrates 4 in sequence.

As a specific method of the lamination step, the method of applying the composition for forming an adhesive layer on the separation layer 2 and heating to form the adhesive layer 3, and then bonding the support base 1 and the substrate 4 together .

The method of applying the subsequent layer-forming composition to the separation layer 2 is not particularly limited, and it may be carried out in the same manner as the above-mentioned method of applying the separation layer-forming composition to the support substrate 1 . The baking process at the time of forming the adhesive layer 3 is performed, for example, by stepwise heating while raising the temperature, and the adhesive layer 3 is formed by removing the (S) component from the adhesive layer forming composition.

The method of bonding the support base 1 and the substrate 4 is carried out as follows: the substrate 4 is placed at a predetermined position on the adhesive layer 3, and while heating under vacuum (for example, about 100° C.), a die bonder or the like is used to bond the substrate 4 to the substrate 4. The support base 1 and the substrate 4 are crimped.

According to the manufacturing method of the laminated body of the first embodiment, the separation layer is provided using the composition for forming the separation layer of the above-mentioned embodiment, therefore, the laser reactivity is enhanced, the photoreactivity is further improved, and the distance between the support substrate and the laminated body is improved. Separation. It is preferable that a laminate with high chemical resistance can be produced.

In the method for manufacturing the laminate of the present embodiment described above, the separation layer 2 is formed on the support base 1 , but the present invention is not limited thereto, and the separation layer 2 may also be formed on the substrate 4 . In the manufacturing method of the laminated body of the present embodiment described above, the adhesive layer 3 is formed on the separation layer 2 , but the present invention is not limited thereto, and the adhesive layer 3 may also be formed on the substrate 4 . Also, the separation layer 2 may be formed on both the support base 1 and the substrate 4 , and in this case, the support base 1 and the substrate 4 are bonded via the separation layer 2 , the adhesive layer 3 , and the separation layer 2 .

<Second Embodiment> Fig. 3 is a schematic step diagram illustrating another embodiment of a method for manufacturing a laminate. Fig. 3(a) is a diagram showing a laminate manufactured by the manufacturing method of the first embodiment, and Fig. 3(b) is a diagram illustrating a sealing step. The manufacturing method of the laminated body of said other embodiment further has a sealing process in addition to the said separation layer formation process and a lamination process.

[Sealing procedure] The sealing step in the embodiment is a step of sealing the aforementioned substrate bonded to the aforementioned support base via the aforementioned adhesive layer with a sealing material after the aforementioned lamination step, to produce a sealed body. In FIG. 3( b ), a sealed body 20 (laminated body) in which the entirety of the substrate 4 arranged on the adhesive layer 3 is sealed with a sealing material is obtained.

In the sealing step, for example, a sealing material heated to 130-170°C is supplied onto the adhesive layer 3 so as to cover the substrate 4 while maintaining a high-viscosity state, and compression-molded to form on the adhesive layer 3 The sealing body 20 (laminated body) provided with the sealing material layer 5 is provided.

As the sealing material, for example, a composition containing an epoxy-based resin or a silicone-based resin can be used. The sealing material layer 5 is preferably provided in such a manner as to cover all the substrates 4 on the adhesive layer 3 , rather than being provided on each substrate 4 respectively.

According to the method for producing a laminate of the second embodiment, the sealing substrate having the substrate (wiring layer) on the separation layer and the adhesive layer can be suitably formed by applying the separation layer-forming composition of the above-mentioned embodiment.

<Third Embodiment> Fig. 4 is a schematic step diagram illustrating another embodiment of a method for manufacturing a laminate. Fig. 4(a) is a diagram showing a sealing body manufactured by the manufacturing method of the second embodiment, Fig. 4(b) is a diagram illustrating a grinding step, and Fig. 4(c) is a diagram illustrating a rewiring formation step map. The method for manufacturing a laminate according to the above-mentioned other embodiment further includes a grinding step and a rewiring forming step in addition to the above-mentioned separation layer forming step, lamination step, and sealing step.

[Grinding steps] The grinding step in the embodiment is a step of grinding the sealing material portion (sealing material layer 5 ) in the sealing body 20 so that a part of the substrate 4 is exposed after the aforementioned sealing step. Grinding of the sealing material portion is performed by grinding the sealing material layer 5 to a thickness substantially equal to that of the substrate 4 as shown in FIG. 4( b ), for example.

[Rewiring Formation Step] The rewiring formation step in the embodiment is a step of forming a rewiring layer 6 on the aforementioned exposed substrate 4 after the aforementioned grinding step. The redistribution layer is also called RDL (Redistribution Layer: Redistribution Layer), which is the wiring body of the film that forms the wiring connected to the device, and can have a single-layer or multiple-layer structure. For example, the rewiring layer can also be made of conductors (aluminum, copper, titanium, nickel, gold, silver and other metals and silver-tin alloys and other alloys) on dielectrics (silicon oxide (SiO _x ), photosensitive epoxy resin A layer obtained by forming wiring on a photosensitive resin, etc.), but is not limited thereto.

As a method of forming the rewiring layer 6 , first, a dielectric layer such as silicon oxide (SiO _x ) or photosensitive resin is formed on the sealing material layer 5 . The dielectric layer formed of silicon oxide can be formed by, for example, sputtering, vacuum evaporation, or the like. The dielectric layer formed of a photosensitive resin can be formed by coating the photosensitive resin on the sealing material layer 5 by a method such as spin coating, dipping, roll blade, spray coating, or slit coating.

Next, wiring is formed on the dielectric layer using a conductor such as metal. As a method of forming wiring, for example, known semiconductor process methods such as photolithography (resist lithography) and etching can be used. Examples of such lithography include lithography using a positive resist material and lithography using a negative resist material.

When performing photolithography and etching in this way, the separation layer 2 is exposed to an acid such as hydrofluoric acid, a base such as tetramethylammonium hydroxide (TMAH), or a resist solvent for dissolving a resist material. In particular, in the fan-out technique, PGMEA, cyclopentanone, cycloheptanone, N-methyl-2-pyrrolidone (NMP), cyclohexanone, or the like can be used as a resist solvent. However, the separation layer has high chemical resistance by forming the separation layer using the separation layer-forming composition of the above-mentioned embodiment. Therefore, even if the separation layer is exposed not only to an acid or an alkali but also to a resist solvent, it is unlikely to be dissolved or peeled off. In this way, the rewiring layer 6 can be suitably formed on the sealing material layer 5 .

According to the manufacturing method of the laminated body of the third embodiment, the laminated body 30 in which the support base 1, the separation layer 2, the adhesive layer 3, the sealing material layer 5 covering the substrate 4, and the rewiring layer 6 are sequentially laminated can be stably manufactured . The laminated body 30 described above is a laminated body produced in the process of mounting the terminals provided on the substrate 4 to the rewiring layer 6 extending beyond the wafer area, based on the fan-out technique.

In the manufacturing method of the laminated body of this embodiment, the formation of a bump or the mounting of an element can further be performed on the rewiring layer 6 . Mounting of components on the rewiring layer 6 can be performed using, for example, a mounter or the like.

(Manufacturing method of electronic parts) In the manufacturing method of the electronic component of the 5th aspect of this invention, after obtaining a laminated body by the manufacturing method of the laminated body of the said 4th aspect, it has a separation process and a removal process.

FIG. 5 is a schematic diagram illustrating one embodiment of a method of 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 illustrating a separation step, and Fig. 5(c) is a diagram illustrating a removal step .

[Separation step] The separation step in the embodiment is a step of irradiating light (arrow) to the separation layer 2 through the support substrate 1 to denature the separation layer 2 , thereby separating the support substrate 1 from the laminate 30 .

As shown in FIG. 5( a ), in the separation step, the separation layer 2 is denatured by irradiating light (arrow) to the separation layer 2 via the support substrate 1 . Examples of wavelengths capable of denaturing the separation layer 2 include, for example, a range of 600 nm or less. The type and wavelength of the irradiated light can be appropriately selected according to the permeability of the support substrate 1 and the material of the separation layer 2. For example, YAG laser, ruby laser, glass laser, YVO ₄ laser, LD laser can be used Solid lasers such as fiber lasers, liquid lasers such as pigment lasers, gas lasers such as CO ₂ lasers, excimer lasers, Ar lasers, He-Ne lasers, semiconductor lasers, and free electron lasers Such as laser light, non-laser light. Thereby, the separation layer 2 can be denatured, and the support base 1 and the substrate 4 can be easily separated.

When irradiating laser light, the following conditions can be mentioned as an example of laser light irradiation conditions. The average output value of laser light is preferably from 1.0 W to 5.0 W, more preferably from 3.0 W to 4.0 W. The repetition frequency of the laser light is preferably not less than 20 kHz and not more than 60 kHz, more preferably not less than 30 kHz and not more than 50 kHz. The scanning speed of the laser light is preferably more than 100 mm/s and less than 10000 mm/s.

After the separation layer 2 is denatured by irradiating light (arrow) to the separation layer 2 , the support substrate 1 is separated from the laminate 30 as shown in FIG. 5( b ). For example, the support base 1 and the substrate 4 are separated by applying a force in a direction in which the support base 1 and the substrate 4 separate from each other. Specifically, while one of the support base 1 or the substrate 4 side (rewiring layer 6) is fixed on the table, the other is separated by a suction pad such as a bellows pad. The support base 1 and the substrate 4 can be separated by pulling up the plate while being sucked and held. The force applied to the laminated body 30 can be appropriately adjusted according to the size of the laminated body 30, and is not limited. For example, if it is a laminated body with a diameter of about 300 mm, it can be applied by applying 0.1 to 5 kgf (0.98 to 49 N ) to properly separate the support base 1 from the substrate 4 by a left and right force.

[remove procedure] The removal step in the embodiment is a step of removing the adhesive layer 3 and the separation layer 2 adhering to the substrate 4 after the aforementioned separation step. In FIG. 5( b ), after the separation step, the adhesive layer 3 and the separation layer 2 are attached to the substrate 4 . 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 board|substrate 4 in a removal process.

As a method of removing the adhesive layer 3 etc. attached to the board|substrate 4, the method of removing the residue of the adhesive layer 3 and the separation layer 2 using a washing|cleaning liquid, or the method of irradiating plasma are mentioned, for example. As the cleaning solution, it is preferable to use a cleaning solution containing an organic solvent. As an organic solvent, it is preferable to use the organic solvent prepared in the composition for separation layer formation, and the organic solvent prepared in the composition for adhesive layer formation.

＜Other Embodiments＞ FIG. 6 is a schematic step diagram illustrating another embodiment of a method of 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 illustrating a separation step, and Fig. 6(c) is a diagram illustrating a removal step .

In the laminated body 50 of the embodiment shown in FIG. 6( a ), a support base 51 , a separation layer 52 , a wiring layer 57 , a substrate 54 , and a sealing material layer 55 are laminated in order from the outermost surface 51 s side.

The description about the supporting base 51 is the same as the description in the above-mentioned <supporting base>. The description of the separation layer 52 is the same as that of the above-mentioned <separation layer>.

The wiring layer 57 can be, for example, made of a conductor (a metal such as aluminum, copper, titanium, nickel, gold, silver, and an alloy such as silver-tin alloy) and a dielectric (silicon oxide (SiO _x ), photosensitive epoxy resin, etc. A layer obtained by forming wiring on a photosensitive resin, etc.). The description of the substrate 54 is the same as the description of the above-mentioned <substrate>. As for the sealing material layer 55, the layer formed using the composition containing epoxy resin or silicone resin is mentioned, for example.

The laminated body 50 can be manufactured as follows, for example. First, the separation layer 52 is formed on the side of the supporting base 51 opposite to the outermost surface 51s. The formation of the separation layer 52 may be performed in the same manner as in the above [separation layer formation step]. Next, a wiring layer 57 is formed on the side of the separation layer 52 opposite to the supporting base 51 . The above-mentioned formation of the wiring layer 57 may be performed in the same manner as in the above-mentioned [rewiring formation step]. Next, the substrate 54 is bonded to the surface of the wiring layer 57 on the side opposite to the separation layer 52 via, for example, bumps. Next, it seals with a sealing material so that the board|substrate 54 bonded to the wiring layer 57 may be covered, and the sealing material layer 55 is formed. What is necessary is just to perform the formation of the said sealing material layer 55 similarly to the said [sealing process]. Thereby, the laminated body 50 was manufactured.

As shown in FIG. 6( a ), in the separation step in the embodiment, the separation layer 52 is denatured by irradiating light (arrow) to the separation layer 52 via the support substrate 51 . After the separation layer 52 is denatured by irradiating light (arrow) to the separation layer 52 , the support substrate 51 is separated from the laminate 50 as shown in FIG. 6( b ). The operation in the above-mentioned separation step may be performed in the same manner as the operation in the above-mentioned [separation step].

As shown in FIG. 6( c ), in the removal step in the embodiment, after the aforementioned separation step, the separation layer 52 attached to the wiring layer 57 is removed, whereby an electronic component 60 is obtained. 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 are mentioned. As the aforementioned plasma, it is preferable to use oxygen plasma.

In the method of manufacturing an electronic component according to this embodiment, after the above-mentioned removal step, the electronic component may be further subjected to processes such as formation of solder balls, dicing, or formation of an oxide film. [Example]

Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited to these examples.

＜Resin composition＞ 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 chemical formula (p1-2) and a repeating unit (p22) represented by the following chemical formula (p2-2). The weight-average molecular weight (Mw) calculated by GPC measurement in terms of standard polystyrene was 6000, and the molecular weight dispersion (Mw/Mn) was 1.62. The copolymer 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) calculated by GPC measurement in terms of standard polystyrene was 5500, and the molecular weight dispersion (Mw/Mn) was 1.60. The copolymer 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.

[chemical 14]

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 the chemical formula (p1-6), and n2=3 in the chemical formula (p2-6). The weight-average molecular weight (Mw) in terms of standard polystyrene obtained by GPC measurement was 2000, and the molecular weight dispersion (Mw/Mn) was 2.10. The copolymer composition ratio (the 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.

[chemical 15]

Resin (Q-1): A resin having a repeating unit (p21) represented by the following chemical formula (p2-1). The weight-average molecular weight (Mw) calculated by GPC measurement in terms of standard polystyrene was 12,000, and the molecular weight dispersion (Mw/Mn) was 2.10. The polymerization composition ratio (the ratio of repeating units in the structural formula (molar ratio)) is repeating unit (p21)=100.

[chemical 16]

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

<Preparation of composition for separation layer> (Examples 1-5, Comparative Examples 1-2) Each component shown in Table 1 was mixed and dissolved, and the composition for separation layer formation of each example was prepared (resin component concentration: 20 mass %).

[Table 1] resin composition Thermal acid generator (T) Organic solvent component (S) Example 1 (P)-1 [100] - (T)-1 [10] (S)-1 [440] Example 2 (P)-2 [100] - (T)-1 [10] (S)-1 [440] Example 3 (P)-3 [100] - (T)-1 [10] (S)-1 [440] Example 4 (P)-3 [70] (P)-4 [30] (T)-1 [10] (S)-1 [440] Example 5 (P)-3 [40] (P)-4 [60] (T)-1 [10] (S)-1 [440] Comparative example 1 - (P)-4 [100] (T)-1 [10] (S)-1 [440] Comparative example 2 - (P)-5 [100] (T)-1 [10] (S)-1 [440]

In Table 1, each abbreviation has the following meanings respectively. The value in [ ] is the preparation 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: A thermal acid generator formed from a compound represented by the following chemical formula (T-1) (S)-1: Propylene glycol monomethyl ether (PGME)

[chemical 17]

＜Formation of separation layer＞ On a bare glass support substrate (12 inches, thickness 0.7 mm), each example of the separation layer-forming composition was spin-coated, heated at a temperature of 100°C for 300 seconds, and then heated at a temperature of 150°C and heating for 300 seconds to remove the solvent and form a film with a film thickness of 1 μm. Next, the formed film was fired at 300°C for 20 minutes in an atmospheric environment, and a separation layer with a film thickness of 0.3 μm was formed on the bare glass support substrate, thereby obtaining the support of the attached separation layer matrix.

[Evaluation of light transmittance in separation layer] For the film in the state before firing and the film (separation layer) in the state after firing, which were formed using the composition for forming a separation layer of each example in the above <Formation of the separation layer>, using a spectroscopic analyzer UV -3600 (manufactured by Shimadzu Corporation) irradiates light with a wavelength of 380 to 780 nm, thereby evaluating the transmittance (%) of light with a wavelength of 532 nm of each film formed on a bare glass support substrate. The evaluation results are shown in Table 2.

[Evaluation of laser reactivity in separation layer] For the separation layer formed using the separation layer-forming composition of each example, under the conditions of scanning speed of 7200 mm/sec, frequency of 40 kHz, output (current value) of 24 A, and irradiation pitch of 140 μm, the irradiation wavelength Laser light at 532 nm is used to evaluate laser reactivity. The evaluation of the above-mentioned laser reactivity was carried out by observing the state of traces of laser light irradiated to the separation layer using a microscope VHX-600 (manufactured by Keyence Co., Ltd.), and obtaining the traces of laser light on the surface of the separation layer. The size (laser indentation diameter/μm). Evaluation criteria were set as follows. The evaluation results are shown in Table 2. Evaluation benchmark ◎: The diameter of the laser indentation is 160 μm or more. ○: The diameter of the laser indentation is 150 μm or more and less than 160 μm. Δ: The diameter of the laser indentation is 100 μm or more and less than 150 μm. ×: The diameter of the laser indentation is less than 100 μm.

[Table 2] Composition for forming a separation layer Resin composition (mixing mass ratio) separation layer Light transmittance (%) laser reactivity Laser indentation diameter (μm) Laser evaluation Example 1 Resin (P-1) 100% 34.9 176.9 ◎ Example 2 Resin (P-2) 100% 30.0 184.7 ◎ Example 3 Resin (P-3) 100% 33.2 195.3 ◎ Example 4 Resin (P-3)/Resin (Q-1)=70/30 30.9 185.6 ◎ Example 5 Resin (P-3)/Resin (Q-1)=40/60 32.8 178.4 ◎ Comparative example 1 Resin (Q-1) 100% 48.6 107.6 △ Comparative example 2 Resin (Q-2) 100% 35.0 120.5 △

As can be seen from the results shown in Table 2, compared with the separation layer formed using the separation layer-forming composition of Comparative Examples 1-2, the separation layer formed using the separation layer-forming composition of Examples 1-5 has a higher light intensity. The transmittances are all low, and the laser indentation diameters are all remarkably large. That is, it was confirmed that according to the composition for forming a separation layer of the present invention, a separation layer in which the photoreactivity was further improved and the separation property of the support substrate from the layered body was improved can be formed.

＜Manufacture of laminates＞ Using the same method as above <formation of the separation layer>, the composition for forming the separation layer of each embodiment was spin-coated on the bare glass support substrate (12 inches, thickness 0.7 mm) at a temperature of 100 ° C. Heating was performed for 300 seconds, followed by heating at a temperature of 150° C. for 300 seconds to remove the solvent and form a film. Next, the formed film was fired at 300° C. for 20 minutes in an air environment to form a separation layer with a thickness of 0.5 μm on the bare glass support substrate (separation layer formation step). On the other hand, the adhesive composition TZNR (registered trademark)-A4012 (manufactured by Tokyo Ohka Industry Co., Ltd.) was spin-coated on a semiconductor wafer substrate (12 inches, silicon) at 90°C, 160°C, and 220°C. Bake at each temperature for 4 minutes to form an adhesive layer with a film thickness of 50 μm. Next, the above-mentioned bare glass support substrate formed with a separation layer and the semiconductor wafer substrate formed with an adhesive layer are laminated in a manner of semiconductor wafer substrate, adhesive layer, separation layer, and bare glass support substrate in sequence, and placed in a vacuum Under the condition of 215°C (5 Pa), press with an attachment pressure of 4000 kgf (about 39.2 kN) for 2 minutes. In this way, the bare glass support base and the semiconductor wafer substrate are laminated via the separation layer and the adhesive layer to obtain a laminate (lamination step).

After obtaining the laminate, from the support substrate side of the laminate, the separation layer was irradiated with a wavelength of Laser light at 532 nm (separation step). Thereafter, the adhesive layer was washed and removed using p-menthane (removal step). It was confirmed that the support base was separated from the semiconductor wafer substrate included in the laminate through the above operations.

＜Manufacturing example of electronic parts (1)＞ Using the same method as above <formation of the separation layer>, the composition for forming the separation layer of each embodiment was spin-coated on the bare glass support substrate (12 inches, thickness 0.7 mm) at a temperature of 100 ° C. Heating was performed for 300 seconds, followed by heating at a temperature of 150° C. for 300 seconds to remove the solvent and form a film. Next, the formed film was fired at 300°C for 20 minutes in an atmospheric environment to form a separation layer with a thickness of 0.5 μm on the bare glass support substrate, thereby obtaining a support substrate with a separation layer ( separation layer forming step). Then, the adhesive composition TZNR (registered trademark)-A4012 (manufactured by Tokyo Ohka Industry Co., Ltd.) was spin-coated on the separation layer, and baked at 90°C, 160°C, and 220°C for 4 minutes each to form a film Adhesive layer with a thickness of 50 μm. Next, use a die bonder (manufactured by Tresky Co.), heat the board of the die bonder to 150°C, and press a 2 mm square silicon bare chip on the aforementioned adhesive layer with a pressure of 35 N for 1 second. After disposing the bare silicon wafer, it was heated at 200° C. for 1 hour under a nitrogen atmosphere to obtain a laminate (lamination step).

The obtained laminate was placed on a plate heated to 50°C, and 12 g of a sealant containing epoxy resin was placed so as to cover the bare chip. For the device, apply a pressure of 1 ton using a pressing plate heated to 130°C, and compress for 5 minutes. In this way, the bare wafer disposed on the adhesive layer is sealed with a sealing material to produce a sealing body (sealing step).

After the sealing body was fabricated, the separation layer was irradiated with a wavelength of Laser light at 532 nm (separation step). Thereafter, the adhesive layer was washed and removed using p-menthane (removal step). It was confirmed that the support base was separated from the sealing body through the above operations. Electronic parts were obtained as described above.

＜Manufacturing example of electronic parts (2)＞ Using the same method as above <formation of the separation layer>, the composition for forming the separation layer of each embodiment was spin-coated on a bare glass support substrate (12 inches, 0.7 mm in thickness) at a temperature of 90° C. and 180° C. The solvent was removed by heating for a few seconds, and a film was formed. Next, the formed film was fired at 300°C for 10 minutes in an atmospheric environment to form a separation layer with a thickness of 0.35 μm on the bare glass support substrate, thereby obtaining a support substrate with a separation layer ( separation layer forming step). Next, a material for forming a wiring layer (trade name TMMR S2000) was coated on the aforementioned separation layer, and fired at 90° C. for 3 minutes in an atmospheric environment to form a 10 μm-thick layer on the separation layer. Wiring layer to obtain a laminated body.

After the wiring layer was formed, the separation layer was irradiated with a wavelength of 532 nm from the bare glass support substrate side of the laminate under the conditions of an irradiation dose of 200 mJ/cm ² , an output (current value) of 22 A, and an irradiation pitch of 80 μm. laser. Next, after immersing in propylene glycol monomethyl ether acetate (PGMEA) as a cleaning solution, it baked at 90 degreeC and 5 minutes. Next, firing under the conditions of 200° C. and 60 minutes was repeated three times under a nitrogen atmosphere to separate the support base from the laminate (separation step). Then, irradiate oxygen plasma (2000 W power, 2000 sccm oxygen flow rate, 75 Pa pressure, 50°C temperature, 5 minutes irradiation time) on the separation layer side of the wiring layer to adhere to the wiring layer. Removal of the separated layer (removal step). It was confirmed that the support matrix was separated from the laminate through the above operations. Electronic parts were obtained as described above.

1: Support matrix 2: Separation layer 3: the next layer 4: Substrate 5: Sealing material layer 6: Rewiring layer 10: laminated body 20: sealing body 30: laminated body 40:Electronic parts 50: laminated body 51: Support matrix 51S: the most superficial 52: Separation layer 54: Substrate 55: sealing material layer 57: Wiring layer 60:Electronic parts

FIG. 1 is a schematic view showing an embodiment of a laminate to which the present invention is applied. Fig. 2 is a schematic step diagram illustrating an embodiment of a method for manufacturing a laminate. Fig. 2(a) is a diagram illustrating a separation layer forming step, and Fig. 2(b) is a diagram illustrating a lamination step. Fig. 3 is a schematic step diagram illustrating another embodiment of a method for manufacturing a laminate. Fig. 3(a) is a diagram showing a laminate manufactured by the manufacturing method of the first embodiment, and Fig. 3(b) is a diagram illustrating a sealing step. Fig. 4 is a schematic step diagram illustrating another embodiment of a method for manufacturing a laminate. Fig. 4(a) is a diagram showing a sealing body manufactured by the manufacturing method of the second embodiment, Fig. 4(b) is a diagram illustrating a grinding step, and Fig. 4(c) is a diagram illustrating a rewiring formation step map. FIG. 5 is a schematic diagram illustrating one embodiment of a method of 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 illustrating a separation step, and Fig. 5(c) is a diagram illustrating a removal step . FIG. 6 is a schematic step diagram illustrating another embodiment of a method of 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 illustrating a separation step, and Fig. 6(c) is a diagram illustrating a removal step .

1: Support matrix

2: Separation layer

3: the next layer

4: Substrate

10: laminated body

Claims (10)

A composition for forming a separation layer for forming the separation layer in a laminate having a separation layer between a support substrate and a substrate that transmits light, wherein the separation layer can be formed by irradiation of light from the support substrate side Denatured so that the above-mentioned support matrix is separated from the above-mentioned layered body, the above-mentioned separation layer-forming composition contains a resin component (P) having a repeating unit represented by the following general formula (p1), [Chem. 1] [wherein L ^P1 represents a divalent linking group; R ^P1 represents a condensed polycyclic aromatic group which may have a substituent]. The composition for forming a separation layer according to Claim 1, which is used to form the separation layer in a laminate having a separation layer and an adhesive layer between a support base and a substrate that allow light to pass through, and the separation layer can be formed by the support from the above-mentioned The above-mentioned support substrate is separated from the above-mentioned layered body by denaturation due to irradiation of light on the substrate side, and the above-mentioned composition for forming a separation layer contains a resin component (P) having a repeating unit represented by the following general formula (p1), [Chem. 2] [wherein L ^P1 represents a divalent linking group; R ^P1 represents a condensed polycyclic aromatic group which may have a substituent]. The composition for forming a separation layer according to claim 1 or 2, wherein the above-mentioned resin component (P) further has a repeating unit represented by the following general formula (p2), [Chem.3] [wherein L ^P2 represents a divalent linking group; R ^P2 represents a monocyclic aromatic group which may have a substituent]. The composition for forming a separation layer according to any one of claims 1 to 3, further comprising a thermal acid generator. A support matrix with a separation layer, which has: supporting matrix; and A separation layer formed on the above support substrate using the composition for forming a separation layer according to any one of claims 1 to 4. A laminate having a separation layer between a support base and a substrate through which light passes, The separation layer is a fired body of the composition for forming a separation layer according to any one of claims 1 to 4. A method for manufacturing a laminate, which is a method for manufacturing a laminate provided with a separation layer between a support base and a substrate through which light passes, the above-mentioned manufacturing method has the following steps: A separation layer forming step of applying the composition for forming a separation layer according to any one of claims 1 to 4 on at least one of the above-mentioned substrate or the above-mentioned support base, and then firing, thereby forming the above-mentioned separation layer layers; and A lamination step of laminating the substrate and the support base with the separation layer interposed therebetween. The method for manufacturing a laminate according to claim 7, further comprising a sealing step: after the lamination step, sealing the substrate bonded to the support base via the separation layer with a sealing material to produce a sealed body. The method for manufacturing a laminate as claimed in claim 8, which further has the following steps: a grinding step of grinding a part of the sealing material in the sealing body so that a part of the substrate is exposed after the sealing step; and A rewiring forming step, which is to form a rewiring on the above-mentioned exposed substrate after the above-mentioned grinding step. A method of manufacturing an electronic component, comprising the following steps: A separation step, after obtaining the laminated body by using the method for manufacturing a laminated body according to any one of Claims 7 to 9, irradiating light to the above-mentioned separation layer through the above-mentioned support substrate to denature the above-mentioned separation layer, whereby the above-mentioned support the matrix is separated from the laminate; and In the removal step, after the separation step, the separation layer attached to the substrate is removed.