JP2019183030A - Composition for detachment, method for detaching adhesive, and manufacturing method of electronic component - Google Patents

Abstract

To provide a composition for detachment capable of preventing generation of residue derived from an adhesive on a substrate.SOLUTION: There is provided a composition for detachment for detaching an adhesive, containing a first solvent and a second solvent, in which the first solvent is a hydrocarbon-based solvent, the second solvent is a solvent satisfying logP/logP<1, wherein octanol/water partition coefficient (logP) of the first solvent is logP, and (logP) of the second solvent is logP.SELECTED DRAWING: None

Description

  The present invention relates to a peeling composition, a method for peeling an adhesive, and a method for manufacturing an electronic component.

There are various types of semiconductor packages (electronic components) including semiconductor elements depending on the corresponding sizes, such as WLP (Wafer Level Package) and PLP (Panel Level Package).
The semiconductor package technology includes fan-in technology and fan-out technology. As a semiconductor package based on the fan-in type, there is known a fan-in type WLP (Fan-in Wafer Level Package) in which terminals at the end of the bare chip are rearranged in a chip area. As a semiconductor package based on the fan-out type technology, a fan-out type WLP (Fan-out Wafer Level Package) in which the terminals are rearranged outside the chip area is known.

  In recent years, especially fan-out technology has been applied to fan-out PLP (Fan-out Panel Level Package) in which semiconductor elements are placed on a panel and packaged. It attracts attention as a method that can realize thinning and miniaturization.

  In order to reduce the size of the semiconductor package, it is important to reduce the thickness of the substrate in the element to be incorporated. However, when the thickness of the substrate is reduced, the strength is reduced, and the substrate is likely to be damaged when the semiconductor package is manufactured. On the other hand, the laminated body which bonded the support body to the board | substrate is employ | adopted.

  The substrate and the support are bonded together using an adhesive or the like. After thinning the substrate to which the support is attached, the support is peeled off before dicing the substrate, and the support is removed from the substrate.

  For example, Patent Document 1 describes that in a semiconductor device manufacturing process, a temporary bonding layer for manufacturing a semiconductor device having a release layer and an adhesive layer is provided between a support and a substrate. In Patent Document 1, after the substrate pattern is subjected to processing such as circuit pattern formation, the support is removed from the substrate by bringing a release solvent composed of a hydrocarbon-based or ether-based single solvent into contact with the temporary bonding layer. ing.

JP 2014-72451 A

  Here, in manufacturing a semiconductor device, from the viewpoint of suitability of the entire process and reliability of the obtained semiconductor device, when the substrate is peeled from the support, no component derived from the adhesive remains on the substrate. It is preferable.

  Such a technical demand is further increased in a process for obtaining a semiconductor package with high efficiency. On the other hand, for example, there is a concern that the conventional stripping solvent as described in Patent Document 1 still cannot prevent the generation of the residue derived from the adhesive, and the development of a technique for stripping the adhesive with higher accuracy has been developed. It has been demanded.

  This invention is made | formed in view of said problem, and makes it a subject to provide the composition for peeling which can prevent that the residue derived from an adhesive agent generate | occur | produces on a board | substrate.

In order to solve the above problems, the present invention employs the following configuration.
That is, the first aspect of the present invention is a stripping composition for stripping an adhesive, which contains a first solvent and a second solvent, and the first solvent is a hydrocarbon solvent. , and the second solvent is octanol / water partition coefficient of said first solvent (logP _ow) and _{logP OW1,} when the second solvent logP _ow was _{logP OW2,} the _logP ow2 / logP ow1 _<1 It is a peeling composition which is a solvent to fill.

  A second aspect of the present invention is a method for peeling the adhesive from a substrate to which the adhesive has been adhered, wherein the peeling composition according to the first aspect is brought into contact with the adhesive to bond the adhesive. This is a method of peeling the adhesive, including a dissolving step of dissolving the agent.

  According to a third aspect of the present invention, there is provided a separation step of separating the support from the laminate in which the support, the adhesive layer, and the substrate are laminated in this order, and an adhesive that adheres to the substrate after the separation step And a dissolving step in which the adhesive is dissolved by bringing the peeling composition according to the first aspect into contact therewith.

  ADVANTAGE OF THE INVENTION According to this invention, the composition for peeling which can prevent that the residue derived from an adhesive agent generate | occur | produces on a board | substrate can be provided.

It is a figure explaining the outline of the method of peeling the adhesive agent concerning one Embodiment of this invention. It is a figure explaining the outline of the separation process in the method of peeling the adhesive concerning one embodiment of the present invention. It is a figure explaining the one part outline of the manufacturing method of the laminated body which can apply the method of peeling the adhesive agent concerning one Embodiment of this invention. It is a figure explaining a part of process in the manufacturing method of the laminated body which can apply the method of peeling the adhesive concerning one Embodiment of this invention. It is a figure explaining a part of process in the manufacturing method of the laminated body which can apply the method of peeling the adhesive concerning one Embodiment of this invention.

In the present specification and claims, “aliphatic” is a relative concept with respect to aromatics, and is defined to mean groups, compounds, etc. that do not have aromaticity.
Unless otherwise specified, the “alkyl group” includes linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group.
The “alkylene group” includes linear, branched, and cyclic divalent saturated hydrocarbon groups unless otherwise specified.
The “halogenated alkyl group” is a group in which part or all of the hydrogen atoms of the alkyl group are substituted with 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” or “fluorinated alkylene group” refers to a group in which part or all of the hydrogen atoms of an alkyl group or alkylene group are substituted with fluorine atoms.
“Structural unit” means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).
In the case of “may have a substituent” or “may have a substituent”, the case where a hydrogen atom (—H) is substituted with a monovalent group, and the case of a methylene group (—CH ₂ And-) with a divalent group.
“Exposure” is a concept including general irradiation of radiation.

“Structural unit derived from hydroxystyrene” means a structural unit formed by cleavage of an ethylenic double bond of hydroxystyrene. “A structural unit derived from a hydroxystyrene derivative” means a structural unit formed by cleavage of an ethylenic double bond of a hydroxystyrene derivative.
“Hydroxystyrene derivative” is a concept including those in which the hydrogen atom at the α-position of hydroxystyrene is substituted with another substituent such as an alkyl group or an alkyl halide group, and derivatives thereof. These derivatives include those in which the hydrogen atom of the hydroxy styrene of the hydroxystyrene which may be substituted with a substituent at the α-position is substituted with an organic group; the hydrogen atom at the α-position is substituted with a substituent The thing etc. which the substituents other than a hydroxyl group couple | bonded with the benzene ring of good hydroxystyrene are mentioned. The α-position (α-position carbon atom) means a carbon atom to which a benzene ring is bonded unless otherwise specified.
Examples of the substituent for substituting the hydrogen atom at the α-position of hydroxystyrene include the same substituents as those mentioned as the substituent at the α-position in the α-substituted acrylic ester.

The alkyl group as a substituent at the α-position is preferably a linear or branched alkyl group, specifically, an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group). , N-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group) and the like.
Specific examples of the halogenated alkyl group as the substituent at the α-position include groups in which part or all of the hydrogen atoms of the above-mentioned “alkyl group as the substituent at the α-position” are substituted with a halogen atom. It is done. 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.
Specific examples of the hydroxyalkyl group as a substituent at the α-position include a group in which part or all of the hydrogen atoms of the “alkyl group as the substituent at the α-position” are substituted with a hydroxyl group. 1-5 are preferable and, as for the number of the hydroxyl groups in this hydroxyalkyl group, 1 is the most preferable.

<Peeling composition for peeling adhesive>
The stripping composition for stripping the adhesive according to the first aspect of the present invention contains a first solvent and a second solvent. Wherein the first solvent is a hydrocarbon solvent, the second solvent is octanol / water partition coefficient of said first solvent (logP _ow) and _{logP OW1,} and the second solvent logP _ow a _{logP OW2} At this time, the solvent satisfies logP _ow2 / logP _ow1 <1.

≪First solvent≫
The first solvent is a hydrocarbon solvent. The “hydrocarbon solvent” is a solvent made of a compound (hydrocarbon) composed of carbon atoms and hydrogen atoms. The hydrocarbon solvent as the first solvent is not particularly limited, and examples thereof include terpene hydrocarbon solvents, alkane hydrocarbon solvents, aromatic hydrocarbon solvents, and the like.

Examples of terpene hydrocarbon solvents include p-menthane, o-menthane, m-menthane, diphenylmentane, bornane, norbornane, pinane, tsujang, kalan, longifolene, thuyon, d-limonene, l-limonene, dipentene. , Fencan, α-terpinene, β-terpinene, γ-terpinene, α-pinene, β-pinene, abiethane and the like.
Among these, as the terpene solvent, p-menthane, d-limonene, l-limonene, dipentene and pinane are preferably used, and p-menthane and d-limonene are more preferably used. In particular, when the adhesive contains a hydrogenated styrene-based elastomer, it is preferable to use p-menthane, limonene, dipentene and pinane as the terpene solvent. By using these terpene solvents, it is possible to obtain a peeling composition capable of rapidly dissolving an adhesive containing a hydrogenated styrene elastomer. Moreover, if p-menthane is used as the terpene solvent, a peeling composition that can dissolve the adhesive containing the hydrogenated styrene elastomer more quickly can be obtained.

  When p-menthane is used as the terpene solvent, the ratio of p-menthane cis form and trans form may be adjusted. Thereby, the dissolution rate of the adhesive containing the hydrogenated styrene-based elastomer can be adjusted. For example, the dissolution rate of the adhesive containing hydrogenated styrenic elastomer by p-menthane can be increased by making the ratio of the trans isomer of p-menthan higher than that of the cis isomer. Therefore, the cleaning property with p-menthane for an adhesive containing a hydrogenated styrene elastomer can be further increased.

The alkane-based hydrocarbon solvent may be linear, branched, or cyclic. Examples of the hydrocarbon solvent for the linear or branched alkane include linear or branched alkanes having 4 to 20 carbon atoms, such as butane, pentane, 2-methylbutane, and 3-methylpentane. Hexane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, octane, 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, nonane, isononane, methyloctane, decane, undecane, Examples include dodecane, 2,2,4,6,6-pentamethylheptane, tridecane, pentadecane, tetradecane, and hexadecane. Examples of hydrocarbon solvents for cyclic alkanes include cyclic alkanes having 4 to 20 carbon atoms, such as monocycloalkanes such as cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, and cyclooctane; decalin and the like And the like.
Among these, as the alkane hydrocarbon solvent, ethylcyclohexane and decalin are preferable.

  Examples of the aromatic hydrocarbon type include benzene, naphthalene, tetrahydronaphthalene and the like.

  The hydrocarbon solvent preferably removes impurities having a boiling point higher than that of the hydrocarbon solvent by, for example, distillation. Thereby, when the adhesive is removed by washing, it is possible to prevent the high-boiling impurities contained in the hydrocarbon solvent from remaining as residues on the substrate.

≪Second solvent≫
The second solvent is a solvent satisfying (logP _ow2 / logP _ow1 ) <1, where octanol / water partition coefficient (logP _ow ) of the first solvent is logP _ow1 and logP _{ow of} the second solvent is logP _ow2. It is.

The octanol / water partition coefficient ( _logPow ) is an effective parameter that can characterize its hydrophilicity / hydrophobicity for a wide range of compounds. In general, the distribution coefficient can be obtained by calculation without experimentation. When _logPow increases to the plus side across 0, the hydrophobicity increases, and when the absolute value increases on the minus side, water solubility increases (high polarity). _logPow has a negative correlation with the water solubility of organic compounds, and is widely used as a parameter for estimating hydrophilicity / hydrophobicity of organic compounds.

In the stripping compositions of this actual embodiment, said first solvent logP _ow a _{logP OW1,} when the logP _ow of the second solvent and _{logP OW2,} satisfy _{<1 (logP ow2 / logP ow1} ). That is, the second solvent has a lower logP _ow than the first solvent _{(logP ow2} <logP _ow1). Therefore, the second solvent is a solvent having a higher polarity than the first solvent.
_The value of _(logP ow2 / logP ow1) is more preferably less than 0.9, more preferably less than 0.8. In _addition, it may take a negative value of the value _(logP ow2 / logP ow1).
Even if it is a case where the peeling composition of this embodiment contains the polymer containing a nitrogen atom etc. by containing the 2nd solvent whose polarity is higher than the 1st solvent in addition to the 1st solvent, it is adhesion It is possible to prevent the generation of residues derived from the agent.

The second _solvent, as long as it has a _{(logP ow2 / logP ow1) <} logP ow2 satisfying 1 is not particularly limited, preferably includes a non-hydrocarbon solvent. Here, the “non-hydrocarbon solvent” refers to a solvent having at least one hetero atom (atom other than C and H) in addition to a carbon atom and a hydrogen atom. Examples of the hetero atoms that the non-hydrocarbon solvent has include an oxygen atom, a nitrogen atom, and a sulfur atom. Among these, as a hetero atom which a non-hydrocarbon solvent has, an oxygen atom and a nitrogen atom are preferable, and an oxygen atom is more preferable.
Here, when a non-hydrocarbon solvent is included as the second solvent, _logPow2 is preferably 3.0 or less, more preferably 2.8 or less, and further preferably 2.5 or less. preferable.
In addition, the lower limit value of _logPow2 of the second solvent can be appropriately set according to the adhesive to be used, but can be set to −3.0 or more from the viewpoint of compatibility with the first solvent, for example.

More specifically, the second solvent is preferably a solvent containing at least one structure selected from the group consisting of an ester bond, an ether bond, a ketone group, an amide bond, and a hydroxy group.
Specific examples include 1,4-terpine, 1,8-terpine, geraniol, nerol, linalool, citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinene-1 -Terpene solvents such as ol, terpinen-4-ol, dihydroterpinyl acetate, 1,4-cineol, 1,8-cineol, borneol, carvone, yonon, camphor; lactones such as γ-butyrolactone; acetone, Ketones such as methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isopentyl ketone and 2-heptanone; polyvalent amines such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol Coles; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, or propylene glycol monoacetate, monomethyl ether, monoethyl ether of the polyhydric alcohol or the compound having an ester bond , Derivatives of polyhydric alcohols such as monoalkyl ethers such as monopropyl ether and monobutyl ether or compounds having an ether bond such as monophenyl ether (in these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) is preferred); cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate , Esters such as butyl acetate, methoxybutyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate; anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl Examples include aromatic organic solvents such as phenyl ether; amide solvents such as N-methylpyrrolidone, dimethylformamide, diethylformamide, and dimethylacetamide.
Among them, a solvent containing at least one structure selected from the group consisting of an ester bond, an ether bond and a ketone group is preferable, and butyl acetate, PGMEA, 2-heptanone and the like are preferable.

The second _solvent, if _{(logP ow2 / logP ow1) <} 1 a solvent satisfying may include hydrocarbon solvents. For example, the hydrocarbon solvent mentioned as a specific example of the first solvent can be used as the second solvent according to the _logPow1 of the first solvent. For example, when a hydrocarbon solvent is used as the second solvent, the combination of the hydrocarbon solvent of the first solvent and the hydrocarbon solvent of the second solvent is the hydrocarbon solvent exemplified in the above << first solvent >>. 2 or more types selected from The combination is preferably at least two selected from the group consisting of terpene hydrocarbon solvents and alkane hydrocarbon solvents, and selected from the group consisting of terpene hydrocarbon solvents and cyclic alkane hydrocarbon solvents. It is more preferable that there are two or more kinds. As such an example, the example which is 2 or more types selected from the group which consists of p-menthane, decalin, ethylcyclohexane, and D-limonene is mentioned.

  1 type may be sufficient as a 2nd solvent and 2 or more types may be sufficient as it. The second solvent preferably contains a non-hydrocarbon solvent, and more preferably a combination of a non-hydrocarbon solvent and a hydrocarbon solvent. That is, it is more preferable that the stripping composition of the present embodiment contains two or more hydrocarbon solvents and one or more non-hydrocarbon solvents. More preferably, the stripping composition of this embodiment includes two types of hydrocarbon solvents and one type of non-hydrocarbon solvent.

  In the non-hydrocarbon solvent, the ratio of the non-hydrocarbon solvent to the entire solvent (100% by mass) contained in the stripping composition is preferably 1 to 20% by mass, and 5 to 10% by mass. More preferably.

  Further, when the stripping composition of the present embodiment includes one kind of hydrocarbon solvent as the second solvent, the mass of the hydrocarbon solvent as the first solvent and the hydrocarbon solvent as the second solvent. Examples of the ratio include 1: 9 to 9: 1, preferably 3: 7 to 7: 3, and more preferably 1: 6 to 6: 1.

≪Optional ingredient≫
The stripping composition of this embodiment may contain an arbitrary component in addition to the first solvent and the second solvent. Although arbitrary components are not specifically limited, For example, surfactant is mentioned.

When the peeling composition of this embodiment contains a surfactant, examples of the surfactant include nonionic surfactants and silicon surfactants.
Examples of nonionic surfactants include acetylene glycol surfactants, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan fatty acid esters, and the like. Among these, acetylene glycol surfactants and polyoxyethylene alkyl ethers are more preferable.
The acetylene glycol surfactant is available as a commercial product, and examples thereof include Surfinol series manufactured by Air Products and Chemicals (USA). Specifically, Surfinol 104E, Surfinol 420, Surfinol 440, Surfinol 465, Surfinol 485, etc. are mentioned.

  Polyoxyethylene alkyl ethers are available as commercial products. For example, Neugen series manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Softanol series manufactured by Nippon Shokubai Co., Ltd., and Fine Surf Series manufactured by Aoki Yushi Kogyo Co., Ltd. Etc. Specifically, Neugen XL-40, Neugen XL-80, Neugen TDS-50, Neugen TDS-70, Softanol 30, Softanol 50, Softanol 70, Softanol 90, Fine Surf TD-70, Fine Surf TD-75, Fine Surf TD-80 etc. are mentioned.

Examples of the silicon-based surfactant include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, and aralkyl-modified polymethylalkylsiloxane.
Silicon-based surfactants are available as commercial products, and examples thereof include BYK-331, BYK-310, and BYK-322 manufactured by Big Chemie Japan.

When the peeling composition of this embodiment contains a surfactant, the surfactant may be one type or two or more types.
When the stripping composition of the present embodiment contains a surfactant, the total proportion of the surfactant is preferably added within a range of 0.1% by mass or more and 10% by mass or less. More preferably, it is added within the range of 1% by mass or more and 5% by mass or less. If the addition amount of the surfactant is in the range of 0.1% by mass or more and 10% by mass or less, the surfactant can be suitably dissolved in the solvent.

≪Adhesive≫
The stripping composition of this embodiment is used for stripping the adhesive. Although the adhesive agent used as the application object of the peeling composition of this embodiment is not specifically limited, In the manufacturing process of a semiconductor, the adhesive agent used in order to adhere | attach a board | substrate and a support body is illustrated preferably.
Examples of such an adhesive include a polymer having a structural unit (u11) derived from a monomer (m11) containing a maleimide skeleton (hereinafter, also referred to as “polymer (P1)”), and a hydrogenated styrene-based adhesive. An adhesive containing an elastomer (hereinafter also referred to as “polymer (P2)”) and the like is preferable.

(Polymer (P1))
The adhesive to which the stripping composition of this embodiment is applied preferably contains a polymer (P1) having a structural unit (u11) derived from a monomer (m11) containing a maleimide skeleton.
[Structural unit (u11)
The structural unit (u11) is a structural unit derived from the monomer (m11) containing a maleimide skeleton. Examples of the monomer (m11) containing a maleimide skeleton include a monomer represented by the following general formula (m11).

［式中、Ｒ^ｍ１１ 〜Ｒ^ｍ１３ は、それぞれ独立に、水素原子、又は炭素数１〜２０の有機基を表し、該有機基は酸素原子、窒素原子、硫黄原子、およびハロゲン原子を含んでもよい。］

[Wherein, R ^{m11 to} R ^m13 each independently represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and the organic group may include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. . ]

In the general formula (m11), the organic group represented by R ^m11 or R ^m12 is preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom.

As the organic group represented by R ^m13 in the general formula (m11), a linear or branched alkyl group, an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, an aralkyl group, or a maleimide group Organic groups having are preferred. R ^m13 is more preferably an alkyl group, an aliphatic cyclic hydrocarbon group, or an aromatic hydrocarbon group, and more preferably an aliphatic cyclic hydrocarbon group.
The linear or branched alkyl group, aliphatic cyclic hydrocarbon group, or aromatic hydrocarbon group may have a substituent.

The linear alkyl group for R ^m13 preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 12 carbon atoms. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decanyl group, undecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group, A pentadecyl group, a hexadecyl group, an isohexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a heicosyl group, a docosyl group, and the like can be given.
The branched alkyl group for R ^m13 preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and still more preferably 3 to 10 carbon atoms. Specifically, 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1- Examples thereof include a methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.
Among these, linear or branched alkyl group of R ^m13, a methyl group is preferable.

Examples of the substituent in the linear or branched alkyl group of R ^m13 include a halogen atom, a halogenated alkyl group, and a cyclic group in R ^m13 described later. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.

Examples of maleimide group-containing monomers in which the organic group represented by R ^m13 is a linear or branched alkyl group include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, and N-isopropyl. Maleimide, Nn-butylmaleimide, N-isobutylmaleimide, N-sec-butylmaleimide, N-tert-butylmaleimide, Nn-pentylmaleimide, Nn-hexylmaleimide, Nn-heptylmaleimide, Nn-octylmaleimide, N-laurylmaleimide, N-stearylmaleimide and the like can be mentioned. Among these, N-methylmaleimide is preferable from the viewpoint of industrial supply stability and heat resistance.

Examples of the aliphatic cyclic hydrocarbon group for R ^m13 include an aliphatic hydrocarbon group containing a ring in the structure. The aliphatic hydrocarbon group containing a ring in this structure includes an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), and one of the hydrogen atoms of the aliphatic hydrocarbon ring is alkylene. And a group substituted with a group. The alkylene group preferably has 1 to 4 carbon atoms. The aliphatic hydrocarbon ring preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The aliphatic hydrocarbon ring may be polycyclic or monocyclic.
As the monocyclic aliphatic hydrocarbon ring, those having 3 to 8 carbon atoms are preferable, and specific examples include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane and the like. preferable.
The polycyclic aliphatic hydrocarbon ring preferably has 7 to 30 carbon atoms, and specifically has a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Polycycloalkane; polycycloalkane having a polycyclic skeleton of a condensed ring system such as a ring having a steroid skeleton is more preferable.

Among them, the cyclic aliphatic hydrocarbon group for R ^m13 is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane or polycycloalkane, and a group obtained by removing one or more hydrogen atoms from a monocycloalkane. More preferably, a group obtained by removing one hydrogen atom from a monocycloalkane is further preferred, and a group obtained by removing one hydrogen atom from cyclopentane or cyclohexane is particularly preferred.
Specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like, among which a cyclohexyl group is preferable.

The aromatic hydrocarbon group for R ^m13 is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 5 to 20 carbon atoms, still more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 10 carbon atoms. However, the carbon number does not include the carbon number in the substituent.
Specific examples of the aromatic ring of the aromatic hydrocarbon group in R ^m13 include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or an aromatic group in which a part of carbon atoms constituting these aromatic rings is substituted with a hetero atom. Group heterocycle and the like. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom.
Specifically, the aromatic hydrocarbon group for R ^m13 is a group obtained by removing one hydrogen atom from the aromatic ring (aryl group: for example, phenyl group, naphthyl group, etc.), and one of the hydrogen atoms of the aromatic ring is an alkylene group. (For example, arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.) and the like. The alkylene group (alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.
Especially, as an aromatic hydrocarbon group in ^Rm13 , a phenyl group and a methylphenyl group are preferable, and a phenyl group is more preferable.

Examples of the substituent in the aliphatic cyclic hydrocarbon group or aromatic hydrocarbon group represented by R ^m13 include an alkyl group, a halogen atom, and a halogenated alkyl group.
The alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
As the halogenated alkyl group as a substituent, a part or all of hydrogen atoms such as an alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group, and the like And a group substituted with a halogen atom.

Examples of maleimide group-containing monomers in which the organic group represented by R ^m13 is an aliphatic cyclic hydrocarbon group include N-cyclopropylmaleimide, N-cyclobutylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N -Cycloheptylmaleimide, N-cyclooctylmaleimide, etc. are mentioned. Among these, N-cyclohexylmaleimide is preferable from the viewpoint of industrial supply stability and heat resistance.

Examples of maleimide group-containing monomers in which the organic group represented by R ^m13 has an aromatic hydrocarbon group include N-phenylmaleimide, Nm-methylphenylmaleimide, N-o-methylphenylmaleimide, and Np- Examples include methylphenylmaleimide. Among these, N-phenylmaleimide is preferable from the viewpoint of industrial supply stability and heat resistance.

  Besides these, as maleimide group-containing monomers, N-benzylmaleimide, N-phenethylmaleimide, 1-methyl-2,4-bismaleimidebenzene, N, N′-m-phenylenebismaleimide, N, N′— p-phenylene bismaleimide, N, N′-m-toluylene bismaleimide, N, N′-4,4-biphenylene bismaleimide, N, N′-4,4- (3,3′-dimethyl-biphenylene) Bismaleimide, N, N′-4,4- (3,3′-dimethyldiphenylmethane) bismaleimide, N, N′-4,4- (3,3′-diethyldiphenylmethane) bismaleimide, N, N′- 4,4-diphenylmethane bismaleimide, N, N′-4,4-diphenylpropane bismaleimide, N, N′-3,3′-diphenylsulfone bis Reimido, N, include N'-4,4-diphenyl ether bismaleimide.

  Examples of the structural unit (u11) derived from the monomer (m11) include structural units represented by the following general formula (u11).

［式中、Ｒ^ｕ１３は、炭素数１〜２０の有機基を表す。］

[ ^Wherein R ^u13 represents an organic group having 1 to 20 carbon atoms. ]

^Examples of the organic group represented by R ^u13 include the same organic groups represented by R ^m13 in the general formula (m11).
Specific examples of the structural unit (u11) are shown below.

The structural unit (u11) contained in the polymer (P1) may be one type or two or more types.
The proportion of the structural unit (u11) in the component (P1) is, for example, 10 to 90 mol% with respect to the total (100 mol%) of all the structural units constituting the polymer (P1). In one embodiment, the proportion of the structural unit (u11) in the component (P1) is preferably 1 to 20 mol%, more preferably 5 to 15 mol%. Moreover, in one aspect | mode, 20-80 mol% is preferable and, as for the ratio of the structural unit (u11) in a polymer (P1), 40-70 mol% is more preferable. The proportion of the structural unit (u11) can be appropriately selected depending on the properties required for the adhesive. The structural unit (u11) has a function of improving the heat resistance of the adhesive.

[Other structural units]
The polymer (P1) may have other structural units in addition to the structural unit (u11). Examples of other structural units include structural units derived from alkyl (meth) acrylates, structural units derived from cycloolefins, and structural units derived from styrene.

-Structural unit derived from alkyl (meth) acrylate (u12)
The polymer (P1) may have a structural unit (u12) derived from a (meth) acrylic acid alkyl ester. “(Meth) acryl” means at least one of acrylic or methacrylic.
The (meth) acrylic acid alkyl ester may be an acrylic long-chain alkyl ester containing a linear or branched alkyl group having 15 to 20 carbon atoms. An acrylic alkyl ester containing a branched alkyl group may be used.

  As the acrylic long-chain alkyl ester, an acrylic acid alkyl ester whose alkyl group is an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, an n-eicosyl group, or the like Examples include methacrylic acid alkyl esters.

  Examples of the acrylic alkyl ester containing an alkyl group having 1 to 14 carbon atoms include known acrylic alkyl esters used in conventional (meth) acrylic adhesives. For example, acrylic acid alkyl ester or methacrylic acid whose alkyl group is methyl group, ethyl group, propyl group, butyl group, 2-ethylhexyl group, isooctyl group, isononyl group, isodecyl group, dodecyl group, lauryl group, tridecyl group, etc. Examples include alkyl esters.

When the polymer (P1) has a structural unit (u12), the structural unit (u12) may be one type or two or more types.
The proportion of the structural unit (u12) in the polymer (P1) is, for example, 10 to 90 mol% with respect to the total (100 mol%) of all the structural units constituting the polymer (P1). In one embodiment, the proportion of the structural unit (u12) in the polymer (P1) is preferably 20 to 70 mol%, more preferably 40 to 60 mol%. The proportion of the structural unit (u12) can be appropriately selected according to the properties required for the adhesive. The structural unit (u12) has a function of improving the flexibility and crack resistance of the adhesive.

-Structural units derived from cycloolefin (u13)
The polymer (P1) may have a structural unit (u13) derived from cycloolefin.

  Examples of the structural unit (u13) include structural units represented by the following general formula (u13).

［式中、Ｒ^ｕ１３１〜Ｒ^ｕ１３４は、それぞれ独立に、炭素数１〜３０の有機基又は水素原子を表す。ｎは、０〜２の整数である。］

[ ^Wherein , R ^{u131 to} R ^u134 each independently represents an organic group having 1 to 30 carbon atoms or a hydrogen atom. n is an integer of 0-2. ]

In the general formula (u13), ^examples of the organic group ^represented by R ^{u131 to} R ^{u134 include} an organic group having an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, or a carboxy group. Group, an organic group having a heterocycle, and the like.
The alkyl group in R ^{u131 to} R ^u134 is preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, Examples thereof include a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.
^Examples of the alkenyl group in R ^{u131 to} R ^u134 include an allyl group, a pentenyl group, and a vinyl group.
^Examples of the alkynyl group for R ^{u131 to} R ^u134 include an ethynyl group.
^Examples of the alkylidene group in R ^{u131 to} R ^u134 include a methylidene group and an ethylidene group.
^Examples of the aryl group in R ^{u131 to} R ^u134 include a phenyl group, a naphthyl group, and an anthracenyl group.
^Examples of the aralkyl group in R ^{u131 to} R ^u134 include a benzyl group and a phenethyl group.
^Examples of the alkaryl group in R ^{u131 to} R ^u134 include a tolyl group and a xylyl group.
^Examples of the cycloalkyl group in R ^{u131 to} R ^u134 include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
^Examples of the organic group having a heterocycle in R ^{u131 to} R ^u134 include an organic group having an epoxy group and an organic group having an oxetanyl group.

The organic group in R ^{u131 to} R ^u134 is preferably an alkyl group from the viewpoint of synthesis. The alkyl group preferably has 1 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 3 carbon atoms.
Moreover, it is also preferable that any one or more of R ^{u131 to} R ^u134 is a hydrogen atom.
Among the above, the organic group in R ^{u131 to} R ^u134 is preferably a combination of an alkyl group and a hydrogen atom, and any one of R ^{u131 to} R ^u134 is preferably an alkyl group, and the remaining three are preferably hydrogen atoms. .

In the organic groups represented by R ^{u131 to} R ^u134 , one or more hydrogen atoms may be substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  In said formula (u13), n is an integer of 0-2, 0 or 1 is preferable and 0 is more preferable.

  Specific examples of the structural unit (u22) are shown below.

  Among them, the structural unit (u13) is preferably a structural unit represented by any one of the above formulas (u13-2) to (u13-6), and any one of the formulas (u13-3) to (u13-6). Is more preferable, and the structural unit represented by the formula (u13-4) or (u13-6) is more preferable.

When the polymer (P1) has the structural unit (u13), the structural unit (u13) may be one type or two or more types.
The proportion of the structural unit (u13) in the polymer (P2) is, for example, 10 to 90 mol% with respect to the total (100 mol%) of all the structural units constituting the polymer (P1). In one embodiment, the proportion of the structural unit (u13) in the polymer (P1) is more preferably 20 to 80 mol%, further preferably 30 to 60 mol%. The proportion of the structural unit (u13) can be appropriately selected depending on the properties required for the adhesive. The structural unit (u13) has a function of improving the peelability of the adhesive.

-Structural units derived from styrene (St)
The polymer (P1) may have a structural unit (St) derived from styrene. Since styrene does not deteriorate even in a high temperature environment of 200 ° C. or higher, the structural unit (St) has a function of improving the heat resistance of the adhesive.

The proportion of the structural unit (St) in the polymer (P1) is, for example, 10 to 50 mol% with respect to the total (100 mol%) of all the structural units constituting the polymer (P1).
In the adhesive composition of this embodiment, as the component (P2), one type may be used alone, or two or more types may be used in combination.

  The polymer (P1) preferably has at least one structural unit selected from the group consisting of the structural unit (u11) and the structural units (u12), (u13), and (St). Among them, since the heat resistance is easily increased and an adhesive that can be easily removed by the peeling composition of the present embodiment is obtained, the structural unit (u11) and the structural unit (u12) or the structural unit (u13) are included. Is preferred.

  The content ratio of the polymer (P1) in the adhesive is preferably 50% by mass or less, more preferably 5% by mass or more and 50% by mass or less, with respect to the total amount (100% by mass) of the polymer components contained in the adhesive. 10 mass% or more and 40 mass% or less are more preferable.

  When the content ratio of the component (P1) is equal to or less than the upper limit value of the preferable range, in addition to heat resistance, adhesion is further improved. If it is more than the lower limit of the above preferred range, all of heat resistance, adhesion and die bonding properties are improved.

(Hydrogenated styrene elastomer: polymer (P2))
The adhesive to which the peeling composition of this embodiment is applied may contain a hydrogenated styrene-based elastomer (polymer (P2)).

  The “hydrogenated styrenic elastomer” is a hydrogenated product of a block copolymer of styrene and a conjugated diene. Hydrogenated styrenic elastomers are unlikely to be altered by decomposition, polymerization, or the like. For this reason, the stability with respect to the heat | fever of an adhesive agent can be improved by using a hydrogenated styrene-type elastomer. Moreover, the tolerance to the resist solvent of an adhesive agent can be improved.

  The hydrogenated styrene-based elastomer may be a diblock polymer obtained by polymerizing one end of an elastomer block into a styrene block, or a triblock polymer obtained by polymerizing both ends of an elastomer block into a styrene block. A hydrogenated styrene-based elastomer that is a triblock polymer can bring high heat resistance to the adhesive.

  Examples of the hydrogenated styrene-based elastomer include polystyrene-poly (ethylene / propylene) block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), and styrene-butadiene- Butylene-styrene block copolymer (SBBS) and hydrogenated products thereof; styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (styrene-isoprene-styrene block copolymer) (SEPS) ), Hydrogenated styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS).

  Examples of commercially available products that can be used as hydrogenated styrene elastomers include “Septon (trade name)” manufactured by Kuraray Co., Ltd., “Hibler (trade name)” manufactured by Kuraray Co., Ltd., and “Tuftec (trade name)” manufactured by Asahi Kasei Corporation. , “Dynalon (trade name)” manufactured by JSR Corporation.

  More specifically, for example, as styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), Septon 4033 (manufactured by Kuraray Co., Ltd.) and Septon 4044 (manufactured by Kuraray Co., Ltd.); having a reactive polystyrene-based hard block, Septon V9827 (manufactured by Kuraray Co., Ltd.) as a reaction-crosslinking type styrene-ethylene-butylene-styrene block copolymer; Septon HG252 as polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene block copolymer (SEEPS-OH: terminal hydroxyl group-modified) (Manufactured by Kuraray Co., Ltd.); as polystyrene-poly (ethylene / propylene) block copolymer (SEP), Septon 2004 (manufactured by Kuraray Co., Ltd.); Beauty, styrene - ethylene / butylene - triblock copolymer of styrene as (SEBS), Tuftec H1051 (manufactured by Asahi Kasei Chemicals Corporation) and the like.

  The hydrogenated styrene elastomer includes a structural unit derived from styrene (structural unit (St)) as a structural unit. The structural unit (St) may have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxyalkyl group having 1 to 5 carbon atoms, an acetoxy group, and a carboxy group.

  The content of the structural unit (St) in the hydrogenated styrene-based elastomer is more preferably in the range of 14% by mass to 50% by mass, and in the range of 17% by mass to 50% by mass. Is more preferable. Furthermore, the hydrogenated styrene elastomer preferably has a mass average molecular weight in the range of 40,000 or more and 200,000 or less.

  A plurality of types of hydrogenated styrenic elastomers may be mixed and used. In this case, at least one of the plurality of types of hydrogenated styrene-based elastomer has a content of the structural unit (St) in the range of 14% by mass or more and 50% by mass or less, or a mass average molecular weight of 40, More preferably, it is in the range of not less than 000 and not more than 200,000.

  For example, when the adhesive contains a plurality of types of hydrogenated styrene-based elastomer, for example, Septon 4033 of Septon (trade name) manufactured by Kuraray Co., Ltd., whose content of the structural unit (St) is 30% by mass, When Septon 2063 of Septon (trade name) having a unit (St) content of 13% by mass is mixed at a mass ratio of 1: 1, the content of the structural unit (St) with respect to the entire elastomer contained in the adhesive is 21 to 21. 22% by mass, and therefore 14% by mass or more. Moreover, for example, when the structural unit (St) is 10% by mass and 60% by mass are mixed at a mass ratio of 1: 1, the mass becomes 35% by mass, and the content of the structural unit (St) is 14% by mass or more. It is in the range of 50% by mass or less. The adhesive may be in this form. When the adhesive contains a plurality of hydrogenated styrenic elastomers, the plurality of types of hydrogenated styrenic elastomers all contain a structural unit (St) within the above range, and a mass average within the above range. Most preferred is molecular weight.

  The content of the structural unit (St) of the hydrogenated styrene elastomer in the adhesive is in the range of 14% by mass or more and 50% by mass or less, and the mass average molecular weight of the hydrogenated styrene elastomer is 40,000 or more, When it is in the range of 200,000 or less, the residue derived from the hydrogenated styrene-based elastomer can be suitably removed from the substrate by the stripping composition of the present embodiment. Further, when the content of the structural unit (St) and the mass average molecular weight are within the above ranges, a resist solvent (eg, PGMEA, PGME, etc.), an acid (exposed) when the substrate is subjected to a resist lithography process. Excellent resistance to hydrofluoric acid and the like and alkali (TMAH and the like). That is, it is an adhesive with improved resistance to resist solvents and heat resistance, and an adhesive capable of suitably removing residues derived from hydrogenated styrene-based elastomers by the stripping composition of this embodiment can be obtained. it can.

  The content ratio of the hydrogenated styrene-based elastomer in the adhesive is preferably in the range of 40 parts by mass to 99 parts by mass with respect to the total amount (100 parts by mass) of the polymer components contained in the adhesive, for example, 50 masses. Is more preferably in the range of 90 parts by mass or more and most preferably in the range of 60 parts by mass or more and 80 parts by mass or less. By making content of the hydrogenated styrene-type elastomer in an adhesive into the said range, a board | substrate and a support body can be bonded together suitably, maintaining heat resistance. Moreover, the adhesive agent which is easy to be removed with the peeling composition of this embodiment can be obtained.

(Other polymers)
The polymer that the adhesive can contain is not limited to the polymer (P1) and the polymer (P2). For example, the adhesive may contain a hydrocarbon resin, an acrylic-styrene resin, or the like in addition to one or both of the polymer (P1) and the polymer (P2). You may adjust the adhesiveness of an adhesive agent with these resin. Alternatively, instead of the polymer (P1) and the polymer (P2), a hydrocarbon resin, an acrylic-styrene resin, or the like may be contained.

[Hydrocarbon resin]
The adhesive to which the stripping composition of this embodiment is applied may contain a hydrocarbon resin. The hydrocarbon resin is a resin obtained by polymerizing a monomer composition having a hydrocarbon skeleton. As the hydrocarbon resin, cycloolefin polymer (hereinafter sometimes referred to as “resin (A)”), and at least one resin selected from the group consisting of terpene resin, rosin resin and petroleum resin (hereinafter referred to as “resin (A)”). Resin (B) ”), and the like, but is not limited thereto.

  Examples of the resin (A) include a resin obtained by polymerizing a monomer component containing a cycloolefin monomer. Specific examples include a ring-opening (co) polymer of a monomer component containing a cycloolefin monomer, a resin obtained by addition (co) polymerization of a monomer component containing a cycloolefin monomer, and the like.

  Examples of the cycloolefin monomer contained in the monomer component constituting the resin (A) include bicyclic compounds such as norbornene and norbornadiene, tricyclic compounds such as dicyclopentadiene and dihydroxypentadiene, tetracyclododecene, and the like. Tetracyclics, pentacyclics such as cyclopentadiene trimers, heptacyclics such as tetracyclopentadiene, or alkyl (methyl, ethyl, propyl, butyl, etc.) substitutions of these polycyclics, alkenyls (vinyl, etc.) Substitution, alkylidene (ethylidene, etc.) substitution, aryl (phenyl, tolyl, naphthyl, etc.) substitution, etc. are mentioned. Among these, norbornene-based monomers selected from the group consisting of norbornene, tetracyclododecene, and alkyl-substituted products thereof are particularly preferable.

  The monomer component constituting the resin (A) may contain another monomer copolymerizable with the above-described cycloolefin-based monomer, and preferably contains, for example, an alkene monomer. Examples of the alkene monomer include ethylene, propylene, 1-butene, isobutene, 1-hexene, α-olefin and the like. The alkene monomer may be linear or branched.

  Moreover, it is preferable from a viewpoint of high heat resistance (low thermal decomposition and thermal mass reduction | decrease property) to contain a cycloolefin monomer as a monomer component which comprises resin (A). The ratio of the cycloolefin monomer to the whole monomer component constituting the resin (A) is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 20 mol% or more. preferable. Further, the ratio of the cycloolefin monomer to the whole monomer component constituting the resin (A) is not particularly limited, but is preferably 80 mol% or less from the viewpoint of solubility and stability over time in a solution, More preferably, it is 70 mol% or less.

  Moreover, you may contain a linear or branched alkene monomer as a monomer component which comprises resin (A). The ratio of the alkene monomer to the whole monomer component constituting the resin (A) is preferably 10 to 90 mol%, more preferably 20 to 85 mol% from the viewpoint of solubility and flexibility. 30 to 80 mol% is more preferable.

  The resin (A) is a resin having no polar group, such as a resin obtained by polymerizing a monomer component composed of a cycloolefin monomer and an alkene monomer, at high temperatures. It is preferable for suppressing generation of gas.

  The polymerization method and polymerization conditions for polymerizing the monomer components are not particularly limited, and may be set as appropriate according to conventional methods.

  Examples of commercially available products that can be used as the resin (A) include “TOPAS” manufactured by Polyplastics Co., Ltd., “APEL” manufactured by Mitsui Chemicals, Inc., “ZEONOR” and “ZEONEX” manufactured by Zeon Corporation. And “ARTON” manufactured by JSR Corporation.

  Examples of the resin (A) include a cycloolefin copolymer which is a copolymer of a repeating unit represented by the following chemical formula (p3-1) and a repeating unit represented by the following chemical formula (p3-2).

［式中、ｎは０又は１〜３の整数である。］

[Wherein n is an integer of 0 or 1 to 3. ]

  Examples of the cycloolefin copolymer as described above include APL8008T, APL8009T, and APL6013T (all manufactured by Mitsui Chemicals, Inc.).

  The glass transition temperature (Tg) of the resin (A) is preferably 60 ° C. or higher, and particularly preferably 70 ° C. or higher. The high temperature tolerance of an adhesive agent can be improved as the glass transition temperature of resin (A) is 60 degreeC or more.

  The resin (B) is at least one resin selected from the group consisting of terpene resins, rosin resins and petroleum resins. Specifically, examples of the terpene resin include terpene resins, terpene phenol resins, modified terpene resins, hydrogenated terpene resins, hydrogenated terpene phenol resins, and the like. Examples of the rosin resin include rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, and modified rosin. Examples of petroleum resins include aliphatic or aromatic petroleum resins, hydrogenated petroleum resins, modified petroleum resins, alicyclic petroleum resins, coumarone-indene petroleum resins, and the like. Among these, hydrogenated terpene resins and hydrogenated petroleum resins are more preferable.

  Although the softening point of resin (B) is not specifically limited, It is preferable that it is 80-160 degreeC. When the softening point of the resin (B) is 80 ° C. or higher, an adhesive having high temperature resistance can be obtained. On the other hand, when the softening point of the resin (B) is 160 ° C. or lower, the peeling rate of the adhesive is good.

  Although the mass average molecular weight of resin (B) is not specifically limited, It is preferable that it is 300-3,000. When the mass average molecular weight of the resin (B) is 300 or more, the heat resistance is sufficient, and the degassing amount is reduced under a high temperature environment. On the other hand, when the mass average molecular weight of the resin (B) is 3,000 or less, the peeling rate of the adhesive is good. In addition, the mass average molecular weight of resin (B) means the molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC).

  As the hydrocarbon resin, a mixture of the resin (A) and the resin (B) may be used. By mixing, heat resistance and peeling speed are improved. For example, the mixing ratio of the resin (A) and the resin (B) can be (A) :( B) = 80: 20 to 55:45 (mass ratio).

[Acrylic-styrene resin]
The adhesive to which the peeling composition of this embodiment is applied may contain an acrylic-styrene resin. Examples of the acrylic-styrene resin include a resin obtained by polymerization using styrene or a styrene derivative and (meth) acrylic acid ester as monomers.

  Examples of the (meth) acrylic acid ester include a (meth) acrylic acid alkyl ester having a chain structure, a (meth) acrylic acid ester containing an aliphatic ring, and a (meth) acrylic acid ester containing an aromatic ring. It is done.

Examples of the (meth) acrylic acid alkyl ester having a chain structure include acrylic long-chain alkyl esters containing an alkyl group having 15 to 20 carbon atoms, acrylic alkyl esters containing an alkyl group having 1 to 14 carbon atoms, and the like. . The alkyl group may be linear or branched.
Examples of the acrylic long-chain alkyl ester include an alkyl acrylate or methacrylic acid whose alkyl group is n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, etc. Examples include acid alkyl esters.
Examples of the acrylic alkyl ester containing an alkyl group having 1 to 14 carbon atoms include known acrylic alkyl esters used in conventional (meth) acrylic adhesives. For example, acrylic acid alkyl ester or methacrylic acid whose alkyl group is methyl group, ethyl group, propyl group, butyl group, 2-ethylhexyl group, isooctyl group, isononyl group, isodecyl group, dodecyl group, lauryl group, tridecyl group, etc. Examples include alkyl esters.
Among these, acrylic long-chain alkyl esters are preferable, and eicosyl (meth) acrylate is more preferable.

  Examples of (meth) acrylic acid esters containing an aliphatic ring include cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, 1-adamantyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, and tricyclodecanyl. (Meth) acrylate, tetracyclododecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate and the like. Of these, isobornyl methacrylate, dicyclopentanyl (meth) acrylate, and 1-adamantyl (meth) acrylate are more preferable.

  The (meth) acrylic acid ester containing an aromatic ring is not particularly limited. For example, a phenyl group, a benzyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a phenoxymethyl group, An acrylic ester containing a phenoxyethyl group and the like can be mentioned. In addition, the aromatic ring may have a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, phenoxyethyl acrylate is preferable.

(Other ingredients)
The adhesive may contain other components in addition to the polymer component. Other components are not particularly limited, but for example, various commonly used additives such as mold release agents, plasticizers, adhesion assistants, stabilizers, colorants, thermal polymerization inhibitors and surfactants may be used. it can. The adhesive may contain a diluting solvent.

[Diluted solvent]
A dilution solvent is used to dilute the adhesive. Thereby, an adhesive agent can be adjusted to the viscosity suitable for the conditions for apply | coating.

  Examples of the diluent solvent include straight-chain hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, tridecane, etc .; branched hydrocarbons having 4 to 15 carbon atoms; cyclohexane, cyclohexane Cyclic hydrocarbons such as heptane, cyclooctane, naphthalene, decahydronaphthalene, tetrahydronaphthalene; p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpine, 1,8-terpine, bornane, norbornane, Pinang, Tujan, Karan, Longifolene, Geraniol, Nerol, Linalool, Citral, Citronellol, Menthol, Isomenthol, Neomenthol, α-Terpineol, β-Terpineol, γ-Terpineol, Terpinene-1-ol, Terpinene- Terpene solvents such as ol, dihydroterpinyl acetate, 1,4-cineol, 1,8-cineol, borneol, carvone, yonon, thuyon, camphor, d-limonene, l-limonene, dipentene; γ-butyrolactone, etc. Lactones; ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol A compound having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, the polyhydric alcohol Or derivatives of polyhydric alcohols such as monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, etc., or compounds having an ether bond such as monophenyl ether (among these, , Propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred); cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, Esters such as methoxybutyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate; anisole, ethyl benzyl ether, cresyl methyl ether, Phenyl ether, dibenzyl ether, phenetole, aromatic organic solvents such as butyl phenyl ether.

  According to the stripping composition of this embodiment, it can be applied to a wide range of adhesives containing a plurality of types of polymers by containing the first solvent and the second solvent. In particular, when the stripping composition of the present embodiment contains a non-hydrocarbon solvent as the second solvent, it is preferably used for stripping the adhesive containing the polymer (P1) and the polymer (P2) from the substrate. It is possible to more effectively prevent the generation of residues derived from the polymer component of the adhesive.

<Method of peeling adhesive>
The second aspect of the present invention is a method of peeling the adhesive from the substrate to which the adhesive has been attached. The method of this embodiment includes a dissolving step of bringing the peeling composition according to the first aspect into contact with the adhesive to dissolve the adhesive.

<< First Embodiment >>
FIG. 1 is a schematic process diagram illustrating one embodiment of a method for peeling an adhesive according to this embodiment. FIG. 1A is a diagram illustrating an example of a dissolution process. The laminated body 100 shown to Fig.1 (a) is comprised from the device layer 456 which consists of the board | substrate 4, the sealing material layer 5, and the wiring layer 6, and the contact bonding layer 3 which consists of an adhesive agent. The adhesive layer 3 is attached to the substrate 4 side that constitutes the device layer 456. In Fig.1 (a), the peeling composition 8 which concerns on the said 1st aspect is sprayed from the spray 7, the peeling composition 8 is made to contact the contact bonding layer 3, and the contact bonding layer 3 is melt | dissolved. .
FIG. 1B shows the device layer 456 from which the adhesive layer 3 has been removed.

[Dissolution process]
As shown to (a) of FIG. 1, in the melt | dissolution process, the peeling composition which concerns on the said 1st aspect is made to contact the contact bonding layer 3, and the said contact bonding layer 3 is dissolved. The adhesive layer 3 is preferably formed of the adhesive described in << Adhesive >> of <Peeling composition> above. More specifically, the adhesive preferably contains a polymer having a structural unit derived from a monomer containing a maleimide skeleton. Further, the adhesive more preferably contains a hydrogenated styrene elastomer in addition to a polymer having a structural unit derived from a monomer containing a maleimide skeleton.

  Since the peeling composition according to the first aspect is used in the dissolving step, the adhesive layer 3 can be quickly dissolved. Moreover, the residue derived from an adhesive agent can be suitably removed by the washing | cleaning property of a peeling composition in a melt | dissolution process. Therefore, it is possible to prevent the residue derived from the adhesive from being generated in the device layer 456 including the substrate 4.

  In the example of FIG. 1A, in the melting step, the peeling composition 8 according to the first embodiment is sprayed by the spray 7 to be brought into contact with the adhesive layer 3. The peeling composition 8 can be pressed against the adhesive layer 3 by spraying the peeling composition 8 with the spray 7. Thereby, the residue of the contact bonding layer 3 adhering to the board | substrate 4 can be washed away, and the board | substrate 4 can be wash | cleaned more suitably.

  A typical example of the spray 7 used for spraying the stripping composition 8 includes a two-fluid spray nozzle.

  In the method for peeling off the adhesive according to the present embodiment, since the adhesive attached to the substrate is dissolved using the peeling composition according to the first aspect, a residue derived from the adhesive is generated on the substrate. Can be prevented. Therefore, a substrate in a good state can be obtained.

[Optional process]
The method of this embodiment may include other steps in addition to the dissolution step. Examples of other steps include a separation step.

(Separation process)
The method of the present embodiment may include a separation step of separating the support from the laminate in which the support, the adhesive layer, and the substrate are laminated in this order before the melting step.

FIG. 2 is a schematic process diagram for explaining an example of the separation process.
The laminated body 200 in FIG. 2A includes a support body 12 including a support base 1 and a separation layer 2 in addition to the device layer 456 and the adhesive layer 3. In the laminated body 200, the support body 12, the adhesive layer 3, and the device layer 456 are laminated in this order. FIG. 2A is a diagram in which light is irradiated to the separation layer 2 through the support base 1. FIG. 2B shows a state in which the separation layer 2 has been altered by irradiation with light, resulting in a transformed separation layer 2 ′. FIG. 2C shows a state where the support base 1 is separated from the substrate 4.

  The separation layer 2 shown in FIG. 2A is made of a material that is altered by irradiation with light, and is disposed between the support base 1 and the adhesive layer 3. The support substrate 1 is made of a material that transmits light. Therefore, as shown in FIG. 2A, the separation layer 2 can be altered by irradiating the separation layer 2 with light through the support substrate 1.

  In this specification, the “deterioration” of the separation layer means a phenomenon in which the separation layer can be broken by receiving a slight external force, or a state in which the adhesive force with the layer in contact with the separation layer is reduced. Further, the alteration of the separation layer includes decomposition (exothermic or non-exothermic) due to absorbed light energy, cross-linking, configuration change or dissociation of functional groups (and curing of the separation layer accompanying these, degassing, Contraction or expansion) and the like.

  In this way, by altering the separation layer 2, it is possible to obtain a modified separation layer 2 'and to reduce the adhesive strength of the separation layer 2 ((b) of FIG. 1). Therefore, by applying a slight force to the laminate 200, the support 12 '(or the support substrate 1) can be separated from the laminate 200 ((d) in FIG. 1). In the present specification, the expression “separate the support from the laminate” includes separating the support substrate 1 from the laminate 200. In addition, the case where a residue of the altered separation layer 2 ′ remains in the laminate 200 is also included.

  For this reason, after separating support body 12 'from the laminated body 200, in the said melt | dissolution process, the adhesive composition 3 adhering to the board | substrate 4 (or device layer 456) is suitably used for the peeling composition which concerns on a 1st aspect. It is possible to make contact.

  The laser beam irradiation conditions in the separation step may be appropriately adjusted depending on the type of the separation layer, and are not particularly limited. For example, the average output value of laser light is preferably in the range of 1.0 W to 5.0 W, and more preferably in the range of 3.0 W to 4.0 W. The repetition frequency of the laser light is preferably in the range of 20 kHz to 60 kHz, and more preferably in the range of 30 kHz to 50 kHz. The wavelength of the laser light is preferably 300 nm or more and 700 nm or less, and more preferably 450 nm or more and 650 nm or less. According to such conditions, the energy of the pulsed light applied to the separation layer 2 can be set to an appropriate condition for altering the separation layer 2. For this reason, it is possible to prevent the substrate 4 from being damaged by the laser light.

  The beam spot diameter of the pulsed light and the irradiation pitch of the pulsed light may be any pitch as long as adjacent beam spots do not overlap and can change the separation layer 4.

[Each component of the laminate]
Next, each structure of the laminated body 100 of FIG. 1 and the laminated body 200 of FIG. 2 is demonstrated.

(Support)
The support is a member that supports the substrate, and the substrate is fixed on the support through an adhesive layer. In the example of FIG. 2, the support 12 includes a support base 1 and a separation layer 2 provided on the support base 1. In the case where the separation layer 2 is not provided, the support base 1 serves as a support.

[Support substrate]
The support substrate is a member that has a property of transmitting light and supports the substrate. In the case where a separation layer is provided as shown in FIG. 2, the support substrate is bonded to the substrate via the separation layer and the adhesive layer. When the separation layer is not provided, the support base is bonded to the substrate through the adhesive layer. Therefore, it is preferable that the supporting base has a strength necessary for preventing breakage or deformation of the substrate when the device is thinned, the substrate is transported, or mounted on the substrate. Further, the support substrate is preferably one that transmits light having a wavelength that can alter the separation layer.
For example, glass, silicon, acrylic resin, or the like is used as the material for the support base. Examples of the shape of the support base include, but are not limited to, a rectangle and a circle.
In addition, as the support base, a circular support base having a large size or a large panel having a square shape in plan view can be used for further high density integration and improvement of production efficiency.

(Separation layer)
The separation layer is a layer that is adjacent to the adhesive layer and is denatured by light irradiation so that the support substrate can be separated from the substrate bonded to the support.
This separation layer can be formed using a composition for forming a separation layer described later, for example, by firing components contained in the composition for forming a separation layer, or by chemical vapor deposition (CVD). It is formed. This separation layer is preferably altered by absorbing light irradiated through the support substrate.
The separation layer is preferably formed only from a material that absorbs light, but is a layer that is blended with a material that does not have a structure that absorbs light within a range that does not impair the essential characteristics of the present invention. There may be.

  The thickness of the separation layer is, for example, preferably in the range of 0.05 μm or more and 50 μm or less, and more preferably in the range of 0.3 μm or more and 1 μm or less. When the thickness of the separation layer is in the range of 0.05 μm or more and 50 μm or less, desired alteration can be caused in the separation layer by short-time light irradiation and low-energy light irradiation. The thickness of the separation layer is particularly preferably in the range of 1 μm or less from the viewpoint of productivity.

  The separation layer preferably has a flat surface on the side in contact with the adhesive layer (no irregularities are formed), whereby the adhesive layer can be easily formed, and the substrate or wiring layer, the supporting substrate, It becomes easy to affix evenly.

-Composition for forming separation layer The composition for forming a separation layer, which is a material for forming the separation layer, is, for example, a fluorocarbon, a polymer having a repeating unit containing a light-absorbing structure, an inorganic substance, an infrared ray Examples include compounds having an absorptive structure, infrared absorbing substances, reactive polysilsesquioxanes, or resin components having a phenol skeleton.
In addition, the composition for forming the separation layer improves the separation of the filler, plasticizer, thermal acid generator component, photoacid generator component, organic solvent component, surfactant, sensitizer, or supporting substrate as an optional component. May contain components that can be used.

..Fluorocarbon The separation layer may contain a fluorocarbon. The separation layer made of fluorocarbon is altered by absorbing light, and as a result, loses strength or adhesiveness before receiving light irradiation. Therefore, by applying a slight external force (for example, lifting the support), the separation layer is broken, and the support and the substrate or the wiring layer can be easily separated. The fluorocarbon constituting the separation layer can be suitably formed by a plasma CVD method.
The fluorocarbon absorbs light having a wavelength in a specific range depending on the type. By irradiating the separation layer with light having a wavelength within a range that is absorbed by the fluorocarbon used in the separation layer, the fluorocarbon can be suitably altered. The light absorption rate in the separation layer is preferably 80% or more.

As light to irradiate the separation layer, depending on the wavelength that can be absorbed by the fluorocarbon, for example, YAG laser, ruby laser, glass laser, YVO ₄ laser, LD laser, liquid laser such as fiber laser, liquid laser such as dye laser, etc. A gas laser such as a CO ₂ laser, an excimer laser, an Ar laser, or a He—Ne laser, a laser beam such as a semiconductor laser or a free electron laser, or a non-laser beam may be used as appropriate. As a wavelength that can alter the fluorocarbon, for example, a wavelength in the range of 600 nm or less can be used.

-The polymer which has a repeating unit containing the structure which has a light absorptivity The separation layer may contain the polymer which has a repeating unit containing the structure which has a light absorptivity. The polymer is altered by irradiation with light.
Examples of the structure having light absorption include an atomic group including a conjugated π electron system composed of a substituted or unsubstituted benzene ring, condensed ring, or heterocyclic ring. More specifically, the light-absorbing structure is a cardo structure, or a benzophenone structure, diphenyl sulfoxide structure, diphenyl sulfone structure (bisphenyl sulfone structure), diphenyl present in the side chain of the polymer. Structure or diphenylamine structure.
The light absorbing structure can absorb light having a wavelength in a desired range depending on the type of the structure. For example, the wavelength of light that can be absorbed by the light-absorbing structure is preferably in the range of 100 to 2000 nm, and more preferably in the range of 100 to 500 nm.

The light that can be absorbed by the light absorbing structure is, for example, a high-pressure mercury lamp (wavelength 254 nm or more and 436 nm or less), a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), or F _2. Light emitted from an excimer laser (wavelength 157 nm), XeCl laser (wavelength 308 nm), XeF laser (wavelength 351 nm) or solid-state UV laser (wavelength 355 nm), or g-line (wavelength 436 nm), h-line (wavelength 405 nm) or i-line (Wavelength 365 nm).

..Inorganic substance The separation layer may be made of an inorganic substance. The inorganic material may be any material that can be altered by absorbing light. For example, one or more types selected from the group consisting of metals, metal compounds, and carbon are preferable. A metal compound is a compound containing a metal atom, for example, a metal oxide and a metal nitride.
Examples of such an inorganic material include one or more selected from the group consisting of gold, silver, copper, iron, nickel, aluminum, titanium, chromium, SiO ₂ , SiN, Si ₃ N ₄ , TiN, and carbon.
Carbon is a concept that may include allotropes of carbon, and includes, for example, diamond, fullerene, diamond-like carbon, carbon nanotubes, and the like.
The inorganic material absorbs light having a wavelength in a specific range depending on the type.

The light applied to the separation layer made of an inorganic material may be, for example, a solid-state laser such as a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, or a fiber laser, or a dye laser, depending on the wavelength that the inorganic material can absorb. For example, a liquid laser such as a CO ₂ laser, an excimer laser, an Ar laser, a He—Ne laser, or a laser beam such as a semiconductor laser or a free electron laser, or a non-laser beam may be used as appropriate.
The separation layer made of an inorganic material can be formed on the support substrate by a known technique such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, spin coating, or the like.

.. Compound having infrared absorbing structure The separation layer may contain a compound having an infrared absorbing structure. The compound having an infrared absorbing structure is altered by absorbing infrared rays.
Examples of structures having infrared absorptivity or compounds having this structure include alkanes, alkenes (vinyl, trans, cis, vinylidene, trisubstituted, tetrasubstituted, conjugated, cumulene, cyclic), alkynes (one Substituted, disubstituted), monocyclic aromatics (benzene, monosubstituted, disubstituted, trisubstituted), alcohols or phenols (free OH, intramolecular hydrogen bonding, intermolecular hydrogen bonding, saturated secondary, saturated third Grade, unsaturated secondary, unsaturated tertiary), acetal, ketal, aliphatic ether, aromatic ether, vinyl ether, oxirane ether, peroxide ether, ketone, dialkylcarbonyl, aromatic carbonyl, 1,3 -Diketone enol, o-hydroxy aryl ketone, dialkyl aldehyde, aromatic aldehyde, carboxylic acid (dimer, carboxylic acid anion) ), Formic acid ester, acetic acid ester, conjugated ester, non-conjugated ester, aromatic ester, lactone (β-, γ-, δ-), aliphatic acid chloride, aromatic acid chloride, acid anhydride (conjugated, Non-conjugated, cyclic, acyclic), primary amide, secondary amide, lactam, primary amine (aliphatic, aromatic), secondary amine (aliphatic, aromatic), tertiary Amine (aliphatic, aromatic), primary amine salt, secondary amine salt, tertiary amine salt, ammonium ion, aliphatic nitrile, aromatic nitrile, carbodiimide, aliphatic isonitrile, aromatic isonitrile, isocyanic acid Ester, thiocyanate ester, aliphatic isothiocyanate ester, aromatic isothiocyanate ester, aliphatic nitro compound, aromatic nitro compound, nitroamine, nitrosamine, nitrate ester, Acid ester, nitroso bond (aliphatic, aromatic, monomer, dimer), sulfur compound such as mercaptan or thiophenol or thiolic acid, thiocarbonyl group, sulfoxide, sulfone, sulfonyl chloride, primary sulfonamide, Secondary sulfonamide, sulfate ester, carbon-halogen bond, Si-A ¹ bond (A ¹ is H, C, O or halogen), P-A ² bond (A ² is H, C or O) or Ti-O bond is mentioned.

As a structure containing halogen bond, for example _{-CH 2 Cl, -CH 2 Br,} -CH 2 I, -CF 2 - - Additional _{carbon, - CF 3, -CH = CF} 2, -CF = CF 2, fluoride Aryl chloride or aryl chloride.

Examples of the structure including the Si—A ¹ bond include SiH, SiH ₂ , SiH ₃ , Si—CH ₃ , Si—CH ₂ —, Si—C ₆ H ₅ , SiO—aliphatic, and Si—OCH _{3. , Si-OCH 2 CH 3,} Si-OC 6 H 5, Si-O-Si, Si-OH, SiF, etc. SiF ₂ or SiF ₃ and the like. As a structure including a Si—A ¹ bond, it is particularly preferable to form a siloxane skeleton or a silsesquioxane skeleton.

Examples of the structure including the P—A ² bond include PH, PH ₂ , P—CH ₃ , P—CH ₂ —, P—C ₆ H ₅ , A ³ ₃ —PO— (A ³ is a fatty acid). group or aromatic _{^{group), (A 4 O) 3}} -P-O (A 4 is an alkyl _{group), P-OCH 3, P} -OCH 2 CH 3, P-OC 6 H 5, P-O-P , P—OH or O═P—OH.

Examples of the compound containing the Ti—O bond include (i) tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, titanium-i-propoxyoctylene glycolate, and the like. (Ii) chelating titanium such as di-i-propoxy bis (acetylacetonato) titanium or propanedioxytitanium bis (ethylacetoacetate); (iii) i-C ₃ H ₇ O — [— Ti ( _{O-i-C 3 H 7} ) 2 -O-] n -i-C 3 H 7 or _{n-C 4 H 9 O -} [- Ti (O-n-C 4 H 9) 2 -O-] n _-n-C 4 titanium polymers such as _{H 9;} (iv) tri -n- butoxy titanium monostearate, titanium stearate, di -i- propoxytitanium diisopropyl Sos Areto or (2-n-butoxycarbonyl benzoyloxy) tributoxy acylate titanium such as titanium; (v) di -n- butoxy bis (triethanolaminato) a water-soluble titanium compound such as titanium, and the like.
Among these, as a compound containing a Ti—O bond, di-n-butoxy bis (triethanolaminato) titanium (Ti (OC ₄ H ₉ ) ₂ [OC ₂ H ₄ N (C ₂ H ₄ OH)] ₂ ] ₂ ) is preferred.

The above infrared-absorbing structure can absorb infrared rays having a wavelength in a desired range by selecting the type. Specifically, the wavelength of infrared rays that can be absorbed by the above infrared-absorbing structure is, for example, in the range of 1 to 20 μm, and more preferably in the range of 2 to 15 μm.
Furthermore, when the said structure is a Si-O bond, a Si-C bond, or a Ti-O bond, the inside of the range of 9-11 micrometers is preferable.

  In addition, those skilled in the art can easily understand the wavelength of infrared rays that can be absorbed by each of the above structures. For example, as an absorption band in each structure, Non-Patent Document: SILVERSTEIN / BASSLER / MORRILL, “Identification method by spectrum of organic compound (5th edition) —Combination of MS, IR, NMR and UV” (published in 1992) The description on pages 146 to 151 can be referred to.

  As a compound having an infrared-absorbing structure used for forming the separation layer, among the compounds having the structure as described above, it can be dissolved in a solvent for coating and solidified into a solid layer. If it can form, it will not be specifically limited. However, in order to effectively alter the compound in the separation layer and facilitate separation of the support substrate and the substrate, the absorption of infrared rays in the separation layer is large, that is, the infrared rays when the separation layer is irradiated with infrared rays. It is preferable that the transmittance is low. Specifically, the infrared transmittance in the separation layer is preferably lower than 90%, and the infrared transmittance is more preferably lower than 80%.

..Infrared absorbing substance The separation layer may contain an infrared absorbing substance. The infrared absorbing material only needs to be altered by absorbing light. For example, carbon black, iron particles, or aluminum particles can be suitably used.
The infrared absorbing material absorbs light having a wavelength in a specific range depending on the type. By irradiating the separation layer with light having a wavelength within a range that is absorbed by the infrared absorbing material used in the separation layer, the infrared absorbing material can be suitably altered.

.. Reactive polysilsesquioxane The separation layer can be formed by polymerizing reactive polysilsesquioxane. The separation layer formed thereby has high chemical resistance and high heat resistance.

  “Reactive polysilsesquioxane” refers to a polysilsesquioxane having a silanol group at the end of a polysilsesquioxane skeleton or a functional group capable of forming a silanol group by hydrolysis. . By condensing the silanol groups or functional groups capable of forming silanol groups, they can be polymerized with each other. The reactive polysilsesquioxane has a silsesquioxane skeleton such as a random structure, a cage structure, and a ladder structure as long as it has a silanol group or a functional group capable of forming a silanol group. The reactive polysilsesquioxane provided can be employed.

The siloxane content of the reactive polysilsesquioxane is preferably 70 to 99 mol%, and more preferably 80 to 99 mol%.
If the siloxane content of the reactive polysilsesquioxane is within the above preferred range, it can be suitably altered by irradiating with infrared rays (preferably far infrared rays, more preferably light with a wavelength of 9 to 11 μm). Possible separation layers can be formed.

The weight average molecular weight (Mw) of the reactive polysilsesquioxane is preferably 500 to 50,000, and more preferably 1000 to 10,000.
When the weight average molecular weight (Mw) of the reactive polysilsesquioxane is within the above preferred range, it can be suitably dissolved in a solvent and can be suitably applied on a support plate.

  Examples of commercially available products that can be used as reactive polysilsesquioxane include SR-13, SR-21, SR-23, or SR-33 (trade name) manufactured by Konishi Chemical Co., Ltd.

.. Resin component having phenol skeleton The separation layer may contain a resin component having a phenol skeleton. By having a phenol skeleton, it is easily altered (oxidized or the like) by heating or the like, and the photoreactivity is increased.
As used herein, “having a phenol skeleton” means containing a hydroxybenzene structure.
The resin component having a phenol skeleton has a film forming ability, and preferably has a molecular weight of 1000 or more. When the molecular weight of the resin component is 1000 or more, the film forming ability is improved. The molecular weight of the resin component is more preferably 1000 to 30000, further preferably 1500 to 20000, and particularly preferably 2000 to 15000. When the molecular weight of the resin component is not more than the upper limit of the above preferred range, the solubility of the composition for forming a separation layer in a solvent is enhanced.
In addition, as a molecular weight of a resin component, the weight average molecular weight (Mw) of polystyrene conversion by GPC (gel permeation chromatography) shall be used.

  Examples of the resin component having a phenol skeleton include novolak type phenol resin, resol type phenol resin, hydroxystyrene resin, hydroxyphenylsilsesquioxane resin, hydroxybenzylsilsesquioxane resin, phenol skeleton-containing acrylic resin, and a general formula described later. Examples thereof include a resin having a repeating unit represented by (P2). Among these, novolac type phenol resins and resol type phenol resins are more preferable.

(Adhesive layer)
The adhesive layer 3 in the laminate 100 in FIG. 1 and the laminate 200 in FIG. 2 is preferably a dry product of the adhesive described in the “Adhesive” of the above <Peeling composition>. More specifically, the adhesive preferably contains a polymer having a structural unit derived from a monomer containing a maleimide skeleton, and more preferably contains a hydrogenated styrene elastomer. The thickness of the adhesive layer 3 is, for example, preferably in the range of 1 μm to 200 μm, and more preferably in the range of 5 μm to 150 μm.

(Device layer)
The device layer is a composite of a member made of metal or semiconductor and a resin that seals or insulates the member. Specifically, the device layer includes at least one of a sealing material layer and a wiring layer, and can further include a substrate.
In the stacked body 100 illustrated in FIG. 1 and the stacked body 200 illustrated in FIG. 2, the device layer 456 includes the substrate 4, the sealing material layer 5, and the wiring layer 6.

〔substrate〕
The substrate (bare chip) is subjected to processes such as thinning and mounting while being supported by the support. For example, a structure such as an integrated circuit or a metal bump is mounted on the substrate.
As the substrate, a silicon wafer substrate is typically used, but is not limited thereto, and a ceramic substrate, a thin film substrate, a flexible substrate, or the like may be used.

  The substrate may be a semiconductor element or other element, and may have a single-layer or multi-layer structure. When the substrate is a semiconductor element, the electronic component obtained by dicing the device layer is a semiconductor device. Preferably, the substrate is a semiconductor element.

(Encapsulant layer)
The sealing material layer is provided to seal the substrate and is formed using a sealing material. As the sealing material, a member that can insulate or seal a member made of metal or semiconductor is used. A resin may be used for the sealing material. Although resin used for a sealing material will not be specifically limited if a metal or a semiconductor can be sealed and / or insulated, For example, an epoxy resin, a polyimide, etc. are mentioned.
The sealing material may contain other components such as a filler in addition to the resin. Examples of the filler include spherical silica particles.

(Wiring layer)
The wiring layer is also referred to as RDL (Redistribution Layer) and is a thin-film wiring body that forms a wiring connected to the substrate, and may have a single-layer or multi-layer structure. The wiring layer is made of a conductive material (for example, aluminum, copper, titanium, nickel, gold and silver, and silver) between patterned resin materials (such as photosensitive polyimide and photosensitive acrylic resin). The wiring may be formed by an alloy such as a tin alloy), but is not limited thereto.

  In the laminate 200 of FIG. 2, 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 is further formed between the support base 1 and the separation layer 2. May be. In this case, the other layer should just be comprised from the material which permeate | transmits light. According to this, it is possible to appropriately add a layer that imparts preferable properties and the like to the laminate 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 materials constituting the other layers do not need to transmit light of all wavelengths, and can be appropriately selected from materials that transmit light of wavelengths that can alter the material constituting the separation layer 2.

<< Second Embodiment >>
The method of peeling the adhesive of this embodiment is not limited to said embodiment. For example, the support may not be provided with a separation layer but may be composed only of a support base.

  In this case, the dissolution step is performed, for example, by bringing the peeling composition according to the first aspect into contact with the adhesive layer in the laminate in which the support base, the adhesive layer, and the substrate (device layer) are laminated in this order. Do. Thus, the adhesive layer can be suitably dissolved and removed by the peeling composition according to the first aspect. Therefore, even if the laminate does not include a separation layer, the supporting substrate can be separated from the laminate and the residue derived from the adhesive can be removed from the substrate by performing the dissolving step.

  Further, for example, a support base provided with a plurality of through holes penetrating in the thickness direction may be used as the support base. In this case, the adhesive layer is dissolved by performing a step (dissolution step) of bringing the peeling composition according to the first aspect into contact with the adhesive layer of the laminate through a plurality of through holes provided in the support base. The support substrate can be separated from the laminate. Then, the residue derived from the adhesive agent can be removed from the substrate by further bringing the peeling composition according to the first aspect into contact with the adhesive layer remaining on the substrate and dissolving the adhesive layer.

<< Third Embodiment >>
Another embodiment may be sufficient as the method of peeling the adhesive agent of this embodiment. For example, a part of the outer peripheral portion of the adhesive layer in the laminate is removed with a blade or the like, and then an organic solvent such as ethanol is supplied to the portion where the adhesive layer 3 is removed with the blade. Thereafter, for example, the support base may be separated from the laminate by fixing the substrate in the laminate, holding the support base with a gripping means such as a clamp, and applying force to the stack.

  In the above method, since the organic solvent such as ethanol is supplied to the portion where the adhesive layer is removed by the blade, the adhesiveness of the portion where the adhesive layer is partially removed in the laminate can be lowered. For this reason, force can be suitably concentrated on the part from which a part of the adhesive layer has been removed.

  Moreover, the adhesiveness of an adhesive layer can also be adjusted by forming an adhesive layer using an adhesive containing a release agent. Accordingly, the support base can be easily separated from the substrate without applying excessive force to the laminate.

  After separating the supporting base from the laminate as described above, the adhesive layer is dissolved by performing a step (dissolution step) of bringing the peeling composition according to the first aspect into contact with the adhesive layer remaining on the substrate, Residues derived from the adhesive can be removed from the substrate.

  As described above, the method of peeling the adhesive according to the present embodiment can be performed by bringing the peeling composition according to the first aspect into contact with the adhesive layer formed using the adhesive in the dissolving step. The method for separating the support (support substrate) from the substrate is not particularly limited.

<Method for manufacturing electronic parts>
A third aspect of the present invention is a method for manufacturing an electronic component. In the method of this embodiment, the support, the adhesive layer, and the substrate are separated from the laminate laminated in this order, and the adhesive that adheres to the substrate after the separation step, A dissolving step of bringing the peeling composition according to the first aspect into contact with and dissolving the adhesive.

The separation step and the dissolution step in the method for manufacturing an electronic component of the present embodiment can be performed in the same manner as described in the above <Method for peeling adhesive>.
Below, the manufacturing method of the laminated body 200 of FIG. 2 is demonstrated.

FIG. 3 is a schematic process diagram for explaining a part of one embodiment of a method for producing a laminate. FIG. 3A is a diagram for explaining a process for producing a support, and FIG. 3B is a diagram for explaining an adhesive layer forming process.
FIG. 4 is a schematic process diagram illustrating one embodiment of a method for producing the laminate 40 from the support 123 with an adhesive layer. 4A is a view showing the support 123 with an adhesive layer, FIG. 4B is a view showing a substrate fixing step, and FIG. 4C is a view for explaining a sealing step. is there.
FIG. 5 is a schematic process diagram for explaining an embodiment of a method for producing the laminate 200 from the laminate 40. FIG. 5A is a diagram illustrating the laminated body 40, FIG. 5B is a diagram illustrating a grinding process, and FIG. 5C is a diagram illustrating a rewiring forming process.

  In the manufacturing method of the laminated body of this embodiment, what contains a fluorocarbon is used as a composition for separated layer formation. Moreover, it is preferable that the adhesive agent demonstrated by << adhesive >> of the above-mentioned <peeling composition> is used as an adhesive agent.

[Process for producing support]
The step of producing the support is a step of obtaining a support by forming a separation layer on one side of the support substrate using the composition for forming a separation layer.
In FIG. 3A, the separation layer 2 is formed on the support substrate 1 by using the composition for forming a separation layer (containing a fluorocarbon) (that is, the support substrate with the separation layer is produced). )

The method for forming the separation layer 2 on the support substrate 1 is not particularly limited, and examples thereof include spin coating, dipping, roller blade, spray coating, slit coating, and chemical vapor deposition (CVD).
For example, in the step of producing the support, a film is formed by removing the solvent component from the coating layer of the composition for forming a separation layer applied on the support substrate 1 in a heating environment or a reduced pressure environment (separation layer 2). Or a film is formed on the support substrate 1 by vapor deposition (the separation layer 2 is formed) to obtain the support 12.

[Adhesive layer forming step]
The adhesive layer forming step in the embodiment is a step of forming an adhesive layer on one side of the support using the adhesive layer forming composition of the above-described embodiment.
In FIG.3 (b), the contact bonding layer 3 is formed in the surface at the side of the separation layer 2 of the support body 12 using an adhesive agent (namely, the support body 123 with an adhesive layer is produced).

  The method for forming the adhesive layer 3 on the support 12 is not particularly limited, and examples thereof include spin coating, dipping, roller blades, spray coating, and slit coating. Then, an adhesive is applied on the support 12 and heated, or the solvent component contained in the adhesive composition is removed under a reduced pressure environment.

  Thereafter, when the adhesive layer 3 contains a curable monomer and a thermal polymerization initiator, the curable monomer may be polymerized by heating. What is necessary is just to set suitably the conditions which heat the contact bonding layer 3 based on the half hour temperature for 1 minute in a thermal-polymerization initiator, and the half hour temperature for one hour, for example, in the temperature within the range of 50-300 degreeC, under vacuum, or nitrogen It is preferable to carry out in inert gas atmosphere, such as gas, and it is more preferable to carry out in inert gas atmosphere.

  Moreover, when the contact bonding layer 3 contains a curable monomer and a photoinitiator, it is good to polymerize a curable monomer by exposing in inert gas atmosphere, such as nitrogen gas. What is necessary is just to set the conditions to expose suitably according to the kind etc. of photoinitiator.

[Device layer formation process]
In the device layer forming step, a device layer that is a composite of a member made of metal or semiconductor and a resin that seals or insulates the member is formed. The device layer forming step can include any of a substrate fixing step, a sealing step, a grinding step, and a wiring layer forming step.
In the embodiment, the device layer forming step includes a substrate fixing step and a sealing step. In this case, the device layer forming step may further include a grinding step and a wiring layer forming step.
In another embodiment, the device layer forming step includes a wiring layer forming step. In this case, the device layer forming step may further include a substrate fixing step, a sealing step, and a grinding step.

-About board | substrate fixing process A board | substrate fixing process is a process of fixing a board | substrate (bare chip | tip) on a support body through an adhesive layer.
In FIG. 4B, the support base 1 (support 12) on which the separation layer 2 is formed and the substrate 4 are laminated via the adhesive layer 3, and the support 12, the adhesive layer 3, and the substrate 4 are in this order. A stacked structure 30 is obtained.

  The method of fixing the substrate 4 on the support 12 via the adhesive layer 3 is to place the substrate 4 at a predetermined position on the adhesive layer 3 and support it by a die bonder or the like while heating under vacuum (for example, about 100 ° C.). This can be done by pressure bonding the body 12 and the substrate 4.

-About a sealing process A sealing process is a process of sealing the board | substrate fixed on the support body using a sealing material.
In FIG. 4C, a laminate 40 is obtained in which the entire substrate 4 fixed to the support 12 via the adhesive layer 3 is sealed with the sealing material layer 5. In the stacked body 40, the substrate 4 and the sealing material layer 5 constitute a device layer 45.

In the sealing step, for example, a sealing material heated to 130 to 170 ° C. is supplied onto the adhesive layer 3 and compression-molded so as to cover the substrate 4 while maintaining a high viscosity state. Thus, a laminate 40 in which the sealing material layer 5 is provided on the adhesive layer 3 is produced.
In that case, temperature conditions are 130-170 degreeC, for example.
The pressure applied to the substrate 4 is, for example, 50 to 500 N / cm ² .

  The sealing material layer 5 is not provided for each individual substrate 4, but is preferably provided so as to cover the entire substrate 4 on the adhesive layer 3.

-About a grinding process A grinding process is a process of grinding the sealing material part (sealing material layer 5) in a sealing body after the said sealing process so that a part of board | substrate may be exposed.
For example, as shown in FIG. 5B, the sealing material portion is ground by scraping the sealing material layer 5 until the thickness becomes substantially equal to that of the substrate 4.

-Wiring layer formation process A wiring layer formation process is a process of forming a wiring layer on the said exposed substrate after the said grinding process.
In FIG. 5C, the wiring layer 6 is formed on the substrate 4 and the sealing material layer 5. Thereby, the laminated body 200 can be obtained. In the stacked body 200, the substrate 4, the sealing material layer 5, and the wiring layer 6 constitute a device layer 456.

Examples of the method for forming the wiring layer 6 include the following methods.
First, a dielectric layer such as silicon oxide (SiO _x ) or photosensitive resin is formed on the sealing material layer 5. The dielectric layer made of silicon oxide can be formed by, for example, a sputtering method, a vacuum deposition method, or the like. The dielectric layer made of the photosensitive resin can be formed by applying the photosensitive resin on the sealing material layer 5 by a method such as spin coating, dipping, roller blade, spray coating, slit coating or the like. .

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

The laminated body 200 is a laminated body manufactured in the process based on the fan-out type technique in which the terminals provided on the substrate 4 are mounted on the wiring layer 6 extending outside the chip area.
After obtaining the laminate 200, bumps may be formed on the wiring layer 6 or elements may be mounted. The element can be mounted on the wiring layer 6 using, for example, a chip mounter.

  After obtaining the laminated body 200 as described above, the electronic component 50 can be obtained by performing the separation step and the dissolution step described in <Adhesive peeling method> (FIG. 1B).

  In the method for manufacturing an electronic component according to this embodiment, after the melting step, the electronic component 50 may be further subjected to processing such as solder ball formation, dicing, or oxide film formation.

  According to the method for manufacturing an electronic component of this embodiment, since the melting step is performed using the peeling composition according to the first aspect, it is possible to prevent the residue derived from the adhesive from being generated in the electronic component 50. can do. Therefore, an electronic component in a good state can be obtained.

  The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments. Is also included in the technical scope of the present invention.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these examples.

<Preparation of adhesive>
Adhesive compositions A and B used for evaluating the detergency of the peeling composition were prepared according to the compositions and blending amounts shown in Table 1.
First, a resin composition was obtained by mixing 25 parts by mass of (P1) -1, 65 parts by mass of (P2) -1, and 10 parts by mass of (P3) -1. Subsequently, 100 parts by mass of the resin composition was dissolved in a mixed solvent of 208 parts by mass of decahydronaphthalene and 20 parts by mass of butyl acetate. Subsequently, 1 part by weight of IRGANOX (trade name) 1010 (manufactured by BASF) was added to 100 parts by mass of the resin mixture to obtain an adhesive (A).
Then, according to the composition and compounding quantity shown in Table 1, the adhesive agent (B) was prepared according to the procedure similar to an adhesive agent (A).

In Table 1, each abbreviation has the following meaning. The numerical value in [] is a compounding amount (part by mass).
In addition, the mass average molecular weight about the resin component shown below was calculated | required using the value of polystyrene conversion by GPC (gel permeation chromatography).

  (P1) -1: Maleimide copolymer. Weight average molecular weight 10,000; copolymer of cyclohexylmaleimide, methyl methacrylate and isobornyl methacrylate (cyclohexylmaleimide / methyl methacrylate / isobonyl methacrylate = 40/20/40).

  (P2) -1: Tuftec 1051 (trade name), manufactured by Asahi Kasei Corporation. A hydrogenated styrene-based elastomer having a plurality of structural units represented by the following chemical formula (P2) -1.

  (P3) -1: TU-311DL-M10 (trade name), manufactured by Harima Kasei Co., Ltd. A polymer having a plurality of structural units represented by the following chemical formula (P3) -1 (l / m / n = 60/20/20).

(A) -1: IRGANOX (trade name) 1010 (manufactured by BASF)
(S1) -1: Decahydronaphthalene (S1) -2: Butyl acetate

<Preparation of test piece>
In order to produce a test piece for evaluating the cleaning performance, a laminate was formed using the adhesive group (A) and the adhesive (B), and the glass support substrate was separated from the wafer substrate after the laminate was processed. . Thus, a wafer substrate in which the residue of the separation layer and the adhesive layer remained was produced as a test piece.

  First, the adhesive composition A was spin-coated on a semiconductor wafer substrate (12-inch silicon), and baked at 100 ° C., 160 ° C., and 220 ° C. for 4 minutes to form an adhesive layer (film thickness 50 μm).

Next, a bare glass support (12 inches, thickness 700 μm) was used as a support base, and a separation layer was formed on the support plate by a plasma CVD method using fluorocarbon. The support plate is a fluorocarbon film (thickness 1 μm) as a separation layer by performing a CVD method using C ₄ F ₈ as a reaction gas, a flow rate of 400 sccm, a pressure of 700 mTorr, a high frequency power of 2500 W, and a film forming temperature of 240 ° C. Formed on top.

  Thereafter, the glass support substrate, the separation layer, the adhesive layer, and the wafer substrate were superposed in this order, and a laminate was produced by pressing at 215 ° C. under vacuum with a pressure of 4000 kgf.

Subsequently, as a process for the laminated body, the wafer substrate was thinned to a thickness of 50 μm using a back grinder manufactured by DISCO, and then a plasma CVD process using N ₂ was performed at 220 ° C.

Thereafter, the glass support was separated from the wafer substrate by irradiation with a laser beam having a wavelength of 532 nm, and a wafer substrate in which the residue of the adhesive layer formed using the adhesive (A) remained was obtained as a test piece (A).
Moreover, the test piece (B) was produced also about the adhesive agent (B) according to the procedure similar to the case where an adhesive agent (A) is used.

<Preparation of peeling composition>
According to the composition shown in Table 2, the peeling composition of Examples 1-10 and Comparative Examples 1-2 was prepared. The numerical value of each solvent shown to Tables 2-4 is a compounding quantity (mass part).
In addition, the value of logPow of each solvent is as shown below.
-P-menthan: 5.56
Decahydronaphthalene (decalin): 4.20
・ Ethylcyclohexane: 4.56
D-limonene: 4:57
・ Butyl acetate: 1.82
PGMEA (propylene glycol monomethyl ether acetate): 0.36
2-Heptanone: 1.98

<Evaluation of detergency>
The test pieces (A) and (B) prepared using the adhesives (A) and (B) were spray-washed using the stripping compositions of Examples 1 to 10 and Comparative Examples 1 and 2, and were washed. Was evaluated.

  In the evaluation of cleaning properties, foreign matter inspection was performed using LS6600 (manufactured by Hitachi High-Tech) in order to examine the presence or absence of residues on the cleaned semiconductor wafer surface.

The number of foreign matters was evaluated for cleaning performance according to the following evaluation criteria. The evaluation results are shown in Tables 2-4.
Evaluation criteria ○: Number of foreign matter less than 100 Δ: Number of foreign matter 100 or more and 3000 or less ×: Number of foreign matter 3000

From the results shown in Tables 2 to 3, it was confirmed that the stripping compositions of Examples 1 to 10 have good cleaning performance and can prevent generation of residues derived from the adhesive.
On the other hand, in Comparative Example 1, many residual particles were observed, and the cleaning performance was insufficient. In Comparative Example 2, dissolution of the adhesive remaining on the substrate was not observed.

1 support substrate,
2 separation layer,
3 Adhesive layer,
4 substrates,
5 sealing material layer,
6 Wiring layer,
7 Spray 8 Stripping composition 10 Intermediate layer,
12 support,
30 laminates,
40 laminates,
45 device layer 50 electronic component,
100 laminates,
200 laminates,
123 Support 456 with adhesive layer Device layer 645 Device layer.

Claims (15)

A stripping composition for stripping an adhesive,
Containing a first solvent and a second solvent;
The first solvent is a hydrocarbon solvent,
The second solvent is a solvent satisfying logP _ow2 / logP _ow1 <1 where octanol / water partition coefficient (logP _ow ) of the first solvent is logP _ow1 and logP _{ow of} the second solvent is logP _ow2. A peeling composition.   The stripping composition according to claim 1, wherein the second solvent contains at least one non-hydrocarbon solvent. The stripping composition according to claim 2, wherein the non-hydrocarbon solvent has a log _Pow of 3.0 or less.   The stripping composition according to claim 3, wherein the non-hydrocarbon solvent is a solvent containing at least one structure selected from the group consisting of an ester bond, an ether bond, a ketone group, an amide bond, and a hydroxy group. object.   The ratio for the non-hydrocarbon solvent to the entire solvent (100% by mass) contained in the stripping composition is 1 to 20% by mass, for exfoliation according to any one of claims 2 to 4. Composition.   The stripping composition according to any one of claims 1 to 5, wherein the second solvent contains at least one hydrocarbon solvent.   The peeling composition according to any one of claims 1 to 6, wherein the adhesive contains a polymer having a structural unit derived from a monomer containing a maleimide skeleton.   The stripping composition according to claim 7, wherein the adhesive further contains a hydrogenated styrene-based elastomer. A method of peeling the adhesive from the substrate to which the adhesive is attached,
Including a dissolving step of bringing the peeling composition according to any one of claims 1 to 8 into contact with the adhesive to dissolve the adhesive.
A method of peeling the adhesive.   The method according to claim 9, wherein the adhesive contains a polymer having a structural unit derived from a monomer containing a maleimide skeleton.   The method for peeling an adhesive according to claim 10, wherein the adhesive further contains a hydrogenated styrene elastomer. Prior to the dissolving step, further includes a separation step of separating the support from the laminate in which the support, the adhesive layer, and the substrate are laminated in this order.
The method of peeling the adhesive agent as described in any one of Claims 9-11. The support is composed of a support base made of a material that transmits light and a separation layer that is altered by light irradiation, and the separation layer is disposed between the support base and the adhesive layer,
The separation step is a step of altering the separation layer by irradiating the separation layer with light through the support substrate to separate the support from the laminate.
The method of peeling the adhesive agent of Claim 12. A separation step of separating the support from the laminate in which the support, the adhesive layer, and the substrate are laminated in this order;
After the separation step, a dissolving step of bringing the adhesive composition attached to the substrate into contact with the peeling composition according to any one of claims 1 to 8 and dissolving the adhesive agent;
A method for manufacturing an electronic component, comprising: The support is composed of a support base made of a material that transmits light and a separation layer that is altered by light irradiation, and the separation layer is disposed between the support base and the adhesive layer,
The separation step is a step of altering the separation layer by irradiating the separation layer with light through the support substrate to separate the support from the laminate.
The method for manufacturing an electronic component according to claim 14.

Images