WO2023210285A1

WO2023210285A1 - Joined body, and method for manufacturing joined body

Info

Publication number: WO2023210285A1
Application number: PCT/JP2023/014179
Authority: WO
Inventors: 基治芳我; 帥捷趙
Original assignee: 株式会社ダイセル; 国立大学法人大阪大学
Priority date: 2022-04-27
Filing date: 2023-04-06
Publication date: 2023-11-02

Abstract

The present disclosure provides a joined body in which copper and a cured product of a thermosetting composition are joined by a film, wherein: the film is formed from a thiol; the thiol is a prescribed compound having at least one first functional group selected from amino groups, carboxy groups, and hydroxyl groups; the thermosetting composition contains a thermosetting compound; and the thermosetting compound has a second functional group capable of reacting with the first functional group.

Description

Joined body and method for manufacturing the joined body

The present disclosure relates to a bonded body and a method for manufacturing the bonded body.

A multilayer printed circuit board is made by laminating an inner layer board on which a pattern is formed and a copper-clad laminate for the outer layer via a prepreg (a thermosetting composition in which fibers are impregnated with a thermosetting compound (e.g., epoxide)). The prepreg (thermosetting composition) can then be produced by thermosetting the prepreg (thermosetting composition).

Conventionally, in order to strengthen the bonding strength between the copper of the copper-clad laminate for the outer layer and the cured prepreg, the copper used for the copper-clad laminate for the outer layer has been immersed in an alkaline solution to form uneven surfaces. Copper with (convex and concave) formed therein is used.
Since the recesses are formed on the surface of the copper, when the prepreg is heated and thermosetted, a thermosetting compound flows into the recesses and the prepreg is thermosetted, and the anchor effect causes the prepreg to harden. The adhesive strength between the cured product and copper increases.

By the way, in a multilayer printed circuit board, when an alternating current flows through a conductor, the current density becomes high on the surface of the conductor due to the skin effect. Furthermore, the higher the frequency, the more the current concentrates on the surface of the conductor.
However, if uneven portions are formed on the surface of the copper, which is a conductor in the multilayer printed circuit board, transmission loss increases.
In addition, in recent years, there has been a demand for next-generation mobile communication systems (e.g., 6th generation mobile communication systems (6G) (radio waves: e.g., 100GHz to 3THz)) that use high-frequency radio waves (e.g., 100GHz or higher). In next-generation mobile communication systems, transmission loss due to unevenness on the copper surface becomes even greater.
For this reason, in addition to forming irregularities on the copper surface, there is a need for a further method to increase the bonding strength between the copper of the copper-clad laminate for the outer layer and the cured prepreg (thermosetting composition). ing.

In addition, other than the multilayer printed circuit boards (for example, power devices, power modules, etc.), a further method for increasing the bonding strength between copper and a cured product of a thermosetting composition may be required.

In recent years, a method of bonding copper and a cured product of a thermosetting composition using a silane coupling agent has attracted attention (for example, Non-Patent Document 1).

In the method described in Non-Patent Document 1, first, the surface of copper is subjected to UV/ozone treatment to oxidize the copper and form copper hydroxide (Cu(OH) ₂ ) on the surface of the copper.
Next, by applying a silane coupling agent to the surface on which copper hydroxide (Cu(OH) ₂ ) is formed, a bonding reaction between the copper hydroxide (Cu(OH) ₂ ) and the silane coupling agent is caused. .
Then, epoxide, which is a thermosetting compound, is applied to the surface coated with the silane coupling agent, and by heating the epoxide, the epoxide is cured while causing a bonding reaction between the silane coupling agent and the epoxide.
Thereby, a bonded body in which copper and the cured epoxide are bonded can be obtained.

However, in such bonding using a silane coupling agent, if the surface portion of the copper is not sufficiently oxidized, the bond between the copper and the silane coupling agent will be insufficient, and as a result, the bond between the copper and the cured product will be insufficient. may become insufficient.
On the other hand, if the surface of copper is excessively oxidized, problems may occur, such as the inability to fully exhibit the inherent properties of copper (such as a decrease in the strength of copper).
That is, there is a problem in that it is difficult to control the oxidation treatment of copper.

Therefore, it may be required to obtain a bonded body with high bonding strength between a cured product of a thermosetting composition and copper without controlling the oxidation treatment of copper.

Therefore, an object of the present disclosure is to provide a bonded body with high bonding strength between a cured product of a thermosetting composition and copper.

A first aspect of the present disclosure is a bonded body in which a cured product of a thermosetting composition and copper are bonded with a film,
The film is formed of thiol,
The thiol is a compound having at least one kind of first functional group selected from an amino group, a carboxy group, and a hydroxyl group, and is represented by the following formula (1),
The thermosetting composition contains a thermosetting compound,
The thermosetting compound relates to a conjugate having a second functional group capable of reacting with the first functional group.
Z-R-SH...(1)
(In the formula (1), Z is the first functional group, and R is an organic group having 1 to 20 carbon atoms.)

The second aspect of the present disclosure is a method for manufacturing a bonded body, which comprises fabricating a bonded body in which a cured product of a thermosetting composition and copper are bonded with a film,
The zygote is the zygote,
a step (A) of bonding the thiol and the copper to form the film by providing a bonding agent containing the thiol on the surface of the copper;
A step of providing the thermosetting composition on the film and heating the thermosetting composition to bond the thiol and the thermosetting composition and curing the thermosetting composition ( B).

According to the present disclosure, it is possible to provide a bonded body with high bonding strength between a cured product of a thermosetting composition and copper.

An embodiment of the present disclosure will be described below.

Note that the configurations and combinations thereof in each embodiment are merely examples, and additions, omissions, substitutions, and other changes to the configurations can be made as appropriate without departing from the gist of the present disclosure. This disclosure is not limited by the embodiments, but only by the scope of the claims.
Additionally, each aspect disclosed herein can be combined with any other feature disclosed herein.

The bonded body according to this embodiment is a bonded body in which a cured product of a thermosetting composition and copper are bonded with a film.
The membrane is made of thiol.
The thiol is a compound having at least one first functional group selected from an amino group, a carboxy group, and a hydroxyl group, and is represented by the following formula (1).
Z-R-SH...(1)
(In the formula (1), Z is the first functional group, and R is an organic group having 1 to 20 carbon atoms.)
The thermosetting composition contains a thermosetting compound.
The thermosetting compound has a second functional group that can react with the first functional group.

The thiol can be bonded to the copper through a thiol group contained in the thiol, and can be bonded to the thermosetting compound through the first functional group contained in the thiol.
Therefore, according to the present disclosure, a bonded body with high bonding strength between a cured product of a thermosetting composition and copper can be provided without controlling the oxidation treatment of copper.

Furthermore, even if the surface of the copper is not oxidized, the thiol can be bonded to the copper using a thiol group contained in the thiol.

Furthermore, the thiol group (-SH) contained in thiol has a smaller functional group size than the trialkoxysilyl group (-Si(OR) ₃ ) contained in the silane coupling agent, so thiol is attached to the copper surface. Many can be joined. As a result, the bonding strength between the cured product of the thermosetting composition and copper increases.

Furthermore, when a silane coupling agent is used, variations in bonding strength increase due to the oxidation state of the copper surface, but according to the present disclosure, variations in bonding strength can be easily suppressed. That is, according to the present disclosure, it is possible to provide a joined body with stable quality. In other words, it is possible to provide a bonded body that is highly mass-producible.

Examples of the shape of the copper include a plate shape and a rod shape.
Preferably, the surface of the copper that is to be joined to the cured product via the film is not oxidized.

Additionally, even if the copper surface has not been oxidized, the surface of the copper may be oxidized by acid or moisture in the air.In other words, the surface of the copper may contain an oxide film (copper oxide). Sometimes there are.
The surface portion of the copper may include an oxide film.
Preferably, the oxide film is removed from the surface of the copper.

The thiol is a compound having at least one first functional group selected from an amino group, a carboxy group, and a hydroxyl group, and is represented by the following formula (1).
Z-R-SH...(1)
(In the formula (1), Z is the first functional group, and R is an organic group having 1 to 20 carbon atoms.)

In the first functional group, the hydroxyl group may be an alcoholic hydroxyl group or a phenolic hydroxyl group.

The amino group in the first functional group may be "-NH ₂ ", "-NHR'", "-NR''R''', or "- It may be N ⁺ R''''R'''''R''''''.
R' is an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, and a propyl group.
R'' is an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. R''' is an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. R'' may be the same as R''' or different from R'''.
R'''' is an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. R''''' is an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. R'''''' is an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. R'''' may be the same as R''''' or different from R'''''. R'''' may be the same as R'''''' or different from R''''''. R''''' may be the same as R'''''' or different from R''''''.
The amino group in the first functional group is preferably "-NH ₂ " or "-NHR'", more preferably "-NH ₂ ".

A carboxy group is preferable as the first functional group from the viewpoint of increasing the bonding strength and reducing fluctuations in the bonding strength (from the viewpoint of stabilizing quality).

The carbon number of R in the formula (1) is preferably 1 to 15, more preferably 2 to 10.

R in the formula (1) preferably contains a carbon-carbon unsaturated bond.
The joined body according to this embodiment has excellent heat resistance because R in the above formula (1) includes a carbon-carbon unsaturated bond.
R in the formula (1) preferably contains a benzene ring, more preferably a benzene ring.
Examples of thiols in which R in the formula (1) is a benzene ring include 4-aminothiophenol (4-ATP) (formula (1-1) below), 4-mercaptobenzoic acid (MBA) (formula (1-2)), etc.

R in the above formula (1) also includes a linear hydrocarbon group (-(CH ₂ ) _n -).
Examples of thiols in which R in the formula (1) is a linear hydrocarbon group include 3-mercaptopropionic acid (3-MPA) (formula (1-3) below), 6-mercaptohexanoic acid ( MHA) (formula (1-4) below), 8-mercaptooctanoic acid (MOA) (formula (1-5) below), 11-mercaptoundecanoic acid (MUA) (formula (1-6) below), 6- Examples include mercapto-1-hexanol (MCH) (formula (1-7) below).

From the viewpoint of reducing fluctuations in bonding strength (from the viewpoint of stabilizing quality), the thiol is preferably 3-mercaptopropionic acid (3-MPA).

Thiols form a self-assembled molecular film on the copper surface. Due to this self-organization, the compounds contained in the thiol are arranged at high density and react with the thermosetting compound (second functional group) and copper, thereby providing high bonding strength. The self-organization of thiols is affected by steric hindrance due to the molecular structure of thiols. From the viewpoint of low steric hindrance, thiols in which R in the formula (1) is a linear hydrocarbon group are preferred.

Furthermore, the reactivity between a thiol and a thermosetting compound is considered to be influenced not only by the molecular structure of the thiol but also by the molecular structure of the thermosetting compound. According to the studies of the present disclosure, thiols with relatively short molecular chains are preferable for thermosetting compounds in which the second functional group is a glycidyl group, and thiols in which the second functional group is a cycloaliphatic epoxy group are preferable. For thermosetting compounds, thiols with relatively long molecular chains are preferred.
For example, the molecular length of thiol determined by molecular structure modeling software is preferably less than 0.9 nm for thermosetting compounds whose second functional group is a glycidyl group, and is preferably 0.5 to 0.8 nm. It may be 0.5 to 0.7 nm. Further, for a thermosetting compound in which the second functional group is an alicyclic epoxy group, the thickness is preferably 0.9 nm or more, may be 0.9 to 1.5 nm, and may be 0.9 to 1.4 nm. It may be between 0.9 and 1.3 nm.

The thickness of the film formed of the thiol is preferably 2.0 to 10 nm, more preferably 2.0 to 5.0 nm.
The film may contain dissolved matter (copper, copper oxide, etc.) from the surface portion of the copper.

The thermosetting composition contains a thermosetting compound.

The thermosetting compound has a second functional group that can react with the first functional group.
The second functional group more preferably has an epoxy group and/or a hydroxyl group, and particularly preferably has an epoxy group.
Moreover, it is preferable that the second functional group has the epoxy group by having a glycidyl group and/or an alicyclic epoxy group.

The thermosetting compound having an epoxy group has one or more epoxy groups, preferably two or more epoxy groups.
Examples of the thermosetting compound having an epoxy group include a compound represented by the following formula (2), a compound represented by the following formula (3), and the like.

In the formula (2), R ¹ represents a hydrogen atom or a monovalent hydrocarbon group. Moreover, R ² is the same as or different from R ¹ and represents a hydrogen atom or a monovalent hydrocarbon group. Furthermore, R ³ represents a divalent hydrocarbon group. Moreover, R ⁴ is the same as or different from R ³ and represents a divalent hydrocarbon group.

In the formula (3), X represents a single bond or a connecting group.

In the formula (2), the monovalent hydrocarbon group is preferably a monovalent aliphatic hydrocarbon group.
The monovalent hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, even more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
Examples of the carbon number of the monovalent hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, and decyl group. and dodecyl group.

Examples of the divalent hydrocarbon group include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group.

The divalent aliphatic hydrocarbon group may be linear or branched.
The divalent aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.
Examples of the divalent aliphatic hydrocarbon group include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group.

The divalent alicyclic hydrocarbon group preferably has 3 to 12 carbon atoms, more preferably 3 to 10 carbon atoms, and still more preferably 3 to 6 carbon atoms.
The divalent alicyclic hydrocarbon group is preferably a 3- to 10-membered alicyclic hydrocarbon group, more preferably a 3- to 6-membered alicyclic hydrocarbon group.
Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1 , 4-cyclohexylene group, etc.

The divalent aromatic hydrocarbon group preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms.
Examples of the divalent aromatic hydrocarbon group include a phenylene group (e.g., o-phenylene group, m-phenylene group, p-phenylene group), phenylenebis(methylene) group (e.g., 1,2-phenylenebis). (methylene) group, 1,3-phenylenebis(methylene) group, 1,4-phenylenebis(methylene) group), biphenylene group, naphthylene group, binaphthylene group, anthracenylene group, phenanthrylene group, etc.

Examples of the compound represented by the formula (2) include compounds represented by the following formulas (2-1) to (2-3).

In the formula (3), X represents a single bond or a connecting group.
Examples of the linking group include a divalent hydrocarbon group, an alkenylene group in which part or all of the carbon-carbon double bond is epoxidized, a carbonyl group (-CO-), an ether bond (-O-), Examples include an ester bond (-COO-), a carbonate group (-O-CO-O-), an amide group (-CONH-), and the like. Furthermore, examples of the connecting group include groups in which a plurality of these are connected.

Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the like.
Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group.
Examples of the divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms include 1,2-cyclopentylene group, 1,3-cyclopentylene group, 1,2-cyclohexylene group, and 1,3-cyclopentylene group. Examples include cycloalkylene groups such as cyclohexylene group and 1,4-cyclohexylene group.

Examples of alkenylene groups in which part or all of the carbon-carbon double bonds are epoxidized (hereinafter also referred to as "epoxidized alkenylene groups") include linear or Examples include branched alkenylene groups.
Examples of linear or branched alkenylene groups having 2 to 8 carbon atoms include vinylene group, propenylene group, 1-butenylene group, 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group. Examples include groups.
The above-mentioned epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, and more preferably an alkenylene group having 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized. .

A substituent (eg, an alkyl group having 1 to 10 carbon atoms, etc.) may be bonded to the cyclohexene oxide group in (3) above.

Typical examples of the compound represented by the formula (3) include compounds in which X in the formula (3) is a group containing an ester bond, (3,4,3',4'-diepoxy) Examples include cyclohexyl, 1,2-epoxy-1,2-bis(3,4-epoxycyclohexan-1-yl)ethane, and the like.
Examples of the compound in which X in the formula (3) is a group containing an ester bond include compounds represented by any of the following formulas (3-1) to (3-5).

The thermosetting compound preferably contains a saturated or unsaturated cyclic hydrocarbon group.
The cyclic hydrocarbon group may include a heteroatom (eg, nitrogen (N), sulfur (S), etc.).
The cyclic hydrocarbon group is a concept that also includes polycyclic aromatic groups (eg, naphthalene skeleton).
It is preferable that the thermosetting compound has at least one of a five-membered ring and a six-membered ring as the cyclic hydrocarbon group.
Moreover, it is more preferable that the thermosetting compound has a six-membered ring as the cyclic hydrocarbon group.
Furthermore, it is particularly preferable that the thermosetting compound has only a six-membered ring as the cyclic hydrocarbon group.
The six-membered ring is preferably a benzene skeleton or a cyclohexane skeleton.
Preferably, the cyclic hydrocarbon group does not contain a heteroatom.

In the second functional group, the hydroxyl group may be an alcoholic hydroxyl group or a phenolic hydroxyl group.
Thermosetting compounds having hydroxyl groups (hydroxyl group-containing compounds) include bisphenol, phenol novolak, cresol novolak, cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, dimethyldicyclohexylmethanediol, ethylene glycol, propylene glycol, butanediol. , pentanediol, hexanediol, polyester polyol, polyether polyol, and the like.
Examples of the bisphenols include bisphenol A, bisphenol AF, bisphenol AP, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, and bisphenol Z. can be mentioned.

The thermosetting composition preferably contains the thermosetting compound in an amount of 30 to 90% by weight, more preferably 50 to 95% by weight.

When the thermosetting compound is an epoxy compound, the thermosetting composition may further contain a curing agent for curing the epoxy compound.

Examples of the curing agent include acid anhydride curing agents, amine curing agents, phenol curing agents, and the like.

Examples of the acid anhydride curing agent include phthalic anhydride (formula (4) below), methyltetrahydrophthalic anhydride (for example, 4-methyltetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, etc.), and methylhexanhydride. Hydrophthalic anhydride (e.g. 4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, etc.), dodecenyl succinic anhydride, methylendomethylenetetrahydrophthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydro Phthalic anhydride, methylcyclohexenedicarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, nadic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, 4-(4- Methyl-3-pentenyl)tetrahydrophthalic anhydride, succinic anhydride, adipic anhydride, sebacic anhydride, dodecanedioic anhydride, methylcyclohexenetetracarboxylic anhydride, vinyl ether-maleic anhydride copolymer, alkylstyrene-maleic anhydride Examples include acid copolymers.

Examples of the amine curing agent include aliphatic polyamines, alicyclic polyamines, aromatic polyamines, and the like.
Examples of the aliphatic polyamine include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylene diamine, diethylaminopropylamine, and polypropylenetriamine.
Examples of the alicyclic polyamine include menzendiamine, isophoronediamine, bis(4-amino-3-methyldicyclohexyl)methane, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane, N-aminoethylpiperazine, 3,9 -bis(3-aminopropyl)-3,4,8,10-tetraoxaspiro[5,5]undecane and the like.
Examples of the aromatic polyamine include m-phenylene diamine, p-phenylene diamine, tolylene-2,4-diamine, tolylene-2,6-diamine, mesitylene-2,4-diamine, and 3,5-diethyltolylene. -2,4-diamine, 3,5-diethyltolylene-2,6-diamine, biphenylenediamine, 4,4-diaminodiphenylmethane, 2,5-naphthylenediamine, 2,6-naphthylenediamine, etc. .

Examples of the phenolic curing agent include novolac type phenol resin, novolac type cresol resin, p-xylylene modified phenol resin, p-xylylene/m-xylylene modified phenol resin, terpene modified phenol resin, dicyclopentadiene modified phenol resin, Examples include triphenolpropane.

The thermosetting composition preferably contains 1 to 10 parts by weight, more preferably 2 to 7 parts by weight of the curing agent based on 100 parts by weight of the thermosetting compound.

The thermosetting composition may be a prepreg, that is, may further contain fibers.
Examples of the fibers include carbon fibers, glass fibers, aramid fibers, boron fibers, polyparaphenylene benzobis oxazole (PBO) fibers, polyethylene fibers, alumina fibers, and silicon carbide fibers.
The fibers may be included in the thermosetting composition in the form of a woven fabric, or may be included in the thermosetting composition in the form of a nonwoven fabric, or the fibers may be heated in a loose state. It may be included in the curable composition.

The fibers may be monofilaments or multifilaments.
The fineness of the single fibers of the fibers is preferably 0.2 to 2.0 dtex, more preferably 0.4 to 1.8 dtex.

When the fiber is a multifilament, the number of filaments in the fiber is preferably 2,500 to 50,000.

From the viewpoint of adjusting curability, storage stability, etc., the thermosetting composition may contain a curing accelerator.
Examples of the curing accelerator include tetraphenylphosphonium tetraphenylborate, imidazoles, triphenylphosphate (TPP), and amine curing accelerators. Examples of the amine curing accelerator include boron trifluoride monoethylamine.

Moreover, from the viewpoint of adjusting molding shrinkage rate, coefficient of thermal expansion, thermal conductivity, mechanical strength, etc., the thermosetting composition may contain an inorganic filler.
Examples of the inorganic filler include silica filler, boron nitride filler, aluminum nitride filler, silicon nitride filler, gallium nitride filler, alumina filler, silicon carbide filler, magnesium oxide filler, and diamond filler.

Furthermore, the thermosetting composition may contain a mold release agent from the viewpoint of adjusting mold release properties, adhesion properties, imprintability, and the like.
Examples of the mold release agent include higher fatty acids, higher fatty acid esters, higher fatty acid calcium, and specific examples include carnauba wax and polyethylene wax.

Moreover, from the viewpoint of reducing the stress (lower elasticity) of the cured product, the thermosetting composition may contain a modifier (also referred to as a "stress reducing agent").
Examples of the modifier include butadiene rubber, silicone compounds, and the like.
Examples of the butadiene rubber include methyl acrylate-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, and the like.

Moreover, the thermosetting composition may contain other additives.
Examples of other additives include flame retardants, pigments, and ion trapping agents.
Examples of the flame retardant include organic phosphorus compounds, antimony oxide, aluminum hydroxide, magnesium hydroxide, and the like.
Examples of the pigment include carbon black and the like.
Examples of the ion trapping agent include hydrotalcites, bismuth hydroxide, and the like.

The joined body according to this embodiment is constructed as described above, and next, a method for manufacturing the joined body according to this embodiment will be explained.

The method for manufacturing a bonded body according to this embodiment is a method for producing the bonded body.
The method for manufacturing a bonded body according to the present embodiment includes a step (A) of forming the film by bonding the thiol and the copper by providing a bonding agent containing the thiol on the surface of copper; Step (B) of providing the thermosetting composition on a film and heating the thermosetting composition to bond the thiol and the thermosetting composition and curing the thermosetting composition ).
Further, the method for manufacturing a bonded body according to the present embodiment preferably includes a step (C) of removing an oxide film from the surface of copper before the step (A).

In step (C), the surface of the copper is brought into contact with acetone, the surface of the copper that has been brought into contact with the acetone is brought into contact with alcohol, and the copper that has been brought into contact with the alcohol is ultrasonically cleaned in pure water to remove the copper. Remove oil from surfaces.
Examples of the alcohol include isopropyl alcohol (IPA) and ethanol.
Then, in the step (C), the oxide film is removed from the surface of the copper by bringing the ultrasonically cleaned copper into contact with an acid aqueous solution.
Examples of the acid in the acid aqueous solution include sulfuric acid, nitric acid, and hydrochloric acid.

In the step (A), a thiol-containing alcohol solution is obtained by dissolving thiol in alcohol.
Examples of the alcohol include ethanol.
The thiol-containing alcohol solution contains thiol, preferably 0.2 to 5.0 mM, more preferably 1.0 to 2.0 mM.
Next, a film is formed on the surface of the copper by bringing the thiol-containing alcohol solution into contact with the surface of the copper.

In the step (B), the thermosetting composition is provided on the film, and the thermosetting composition is heated.
The heating temperature and heating time may be adjusted as appropriate depending on the thermosetting composition, and the heating temperature is, for example, 100 to 150° C., and the heating time is, for example, 2 to 5 hours.

[Disclosure items]
Each of the following items is a disclosure of a preferred embodiment.

[Item 1]
A bonded body in which a cured product of a thermosetting composition and copper are bonded with a film,
The film is formed of thiol,
The thiol is a compound having at least one kind of first functional group selected from an amino group, a carboxy group, and a hydroxyl group, and is represented by the following formula (1),
The thermosetting composition contains a thermosetting compound,
The thermosetting compound has a second functional group capable of reacting with the first functional group.
Z-R-SH...(1)
(In the formula (1), Z is the first functional group, and R is an organic group having 1 to 20 carbon atoms.)

[Item 2]
The conjugate according to item 1, wherein R in the formula (1) has 4 to 10 carbon atoms.

[Item 3]
The conjugate according to claim 1 or 2, wherein R in the formula (1) includes a carbon-carbon unsaturated bond.

[Item 4]
The conjugate according to item 3, wherein R in the formula (1) includes a benzene ring.

[Item 5]
The conjugate according to item 4, wherein R in the formula (1) is a benzene ring.

[Item 6]
The conjugate according to any one of items 1 to 5, wherein the second functional group has a hydroxyl group and/or an epoxy group.

[Item 7]
The conjugate according to item 6, wherein the second functional group has the epoxy group by having a glycidyl group and/or an alicyclic epoxy group.

[Item 8]
The conjugate according to any one of items 1 to 7, wherein the thermosetting compound contains a saturated or unsaturated cyclic hydrocarbon group.

[Item 9]
The joined body according to any one of items 1 to 8, wherein the copper is copper that has not been oxidized.

[Item 10]
The conjugate according to any one of items 1 to 9, wherein the film has a thickness of 2.0 to 5.0 nm.

[Item 11]
A method for producing a bonded body, the method comprising: producing a bonded body in which a cured product of a thermosetting composition and copper are bonded with a film,
The zygote is the zygote according to any one of items 1 to 10,
a step (A) of bonding the thiol and the copper to form the film by providing a bonding agent containing the thiol on the surface of the copper;
A step of providing the thermosetting composition on the film and heating the thermosetting composition to bond the thiol and the thermosetting composition and curing the thermosetting composition ( B) A method for manufacturing a joined body, comprising:

Next, the present disclosure will be described in more detail with reference to Examples and Comparative Examples. Note that the present disclosure is not limited to these examples in any way.

The following materials were prepared in order to produce the joined bodies of Examples and Comparative Examples. Note that the molecular length of thiol was determined using molecular structure modeling software.

(copper plate)
- A plate of oxygen-free copper (alloy number: C1020) specified in JIS H3100:2018, which has been buffed to a mirror finish (commercially available)
In addition, in this buffing, a particulate abrasive with a large particle size was used first, a particulate abrasive with a smaller particle size was gradually used, and finally a particulate abrasive of #800 was used. .

(thiol)
・4-aminothiophenol (4-ATP) (formula (1-1) below, molecular length 0.6399 nm)
・4-Mercaptobenzoic acid (MBA) (formula (1-2) below, molecular length 0.7300 nm)
・3-mercaptopropionic acid (3-MPA) (formula (1-3) below, molecular length 0.5325 nm)
・8-Mercaptooctanoic acid (MOA) (formula (1-4) below, molecular length 1.0368 nm)
・11-mercaptoundecanoic acid (MUA) (formula (1-5) below, molecular length 1.2836 nm)
・6-mercapto-1-hexanol (MCH) (formula (1-6) below, molecular length 0.9051 nm)

(thermosetting compound)
・Bisphenol A diglycidyl ether (YD-128 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) (formula (2-1) below)

・3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate (Celoxide 2021P (CEL2021P) manufactured by Daicel) (formula (3-1) below)

(hardening agent)
・Acid anhydride curing agent: Phthalic anhydride (formula (4) below)

(Silane coupling agent)
・(3-aminopropyl)trimethoxysilane (AMMO) (formula (5) below)

(Example 1-1)
The prepared copper plate is immersed in acetone for 5 minutes, the copper plate immersed in acetone is immersed in ethanol for 5 minutes, and the copper plate immersed in ethanol is immersed in pure water and ultrasonic cleaning is performed for 5 minutes. The surface of the copper plate was cleaned (oil was removed from the surface of the copper).
Next, the cleaned copper plate was immersed in a sulfuric acid aqueous solution (sulfuric acid concentration: 5% by weight) for 30 seconds to remove the oxide film from the surface of the copper plate.
Further, by dissolving 4-aminothiophenol (4-ATP), which is a thiol, in ethanol, a thiol-containing ethanol solution (thiol: 4-aminothiophenol (4-ATP), thiol concentration: 2 mM) was obtained.
Then, the copper plate from which the oxide film had been removed was immersed in the thiol-containing ethanol solution for 1 hour to form a film on the surface of the copper plate.
Next, the copper plate on which the film was formed was set in a mold.
Further, a thermosetting composition was obtained by mixing bisphenol A diglycidyl ether, which is a thermosetting compound, and the curing agent. The amount of curing agent was 80 parts by weight based on 100 parts by weight of the thermosetting compound.
Then, within the mold, the thermosetting composition was injected onto the surface of the copper plate on which the film was formed.
Next, the mold is heated in an oven at 120°C for 2 hours and further heated at 150°C for 3 hours to produce five cylindrical cured products of the thermosetting composition on the surface of the copper plate. A conjugate was obtained.
Note that the diameter of the cylindrical cured product was 4 mm, and the height of the cylindrical cured product was 5 mm. Further, the surface of the copper plate on which the film was formed was in contact with the circular surface of the cured product, and the copper plate and the cured product were joined.

(Example 1-2)
4-mercaptobenzoic acid (MBA) was used as the thiol, the concentration of thiol in the thiol-containing ethanol solution was 5mM, and the copper plate from which the oxide film was removed was immersed in the thiol-containing ethanol solution for 5 hours. A bonded body was obtained in the same manner as in Example 1-1 except for the following.

(Example 1-3)
A conjugate was obtained in the same manner as in Example 1-1 except that 3-mercaptopropionic acid (3-MPA) was used as the thiol.

(Example 1-4)
A conjugate was obtained in the same manner as in Example 1-1 except that 8-mercaptooctanoic acid (MOA) was used as the thiol.

(Example 1-5)
A conjugate was obtained in the same manner as in Example 1-1 except that 11-mercaptoundecanoic acid (MUA) was used as the thiol.

(Example 1-6)
A conjugate was obtained in the same manner as in Example 1-1 except that 6-mercapto-1-hexanol (MCH) was used as the thiol.

(Comparative example 1-1)
The prepared copper plate was immersed in ethanol and subjected to ultrasonic cleaning for 5 minutes to clean the surface of the copper plate.
Then, a bonded body was obtained in the same manner as in Example 1-1 except that a cleaned copper plate was set in the mold instead of the copper plate on which the film was formed.

(Comparative example 1-2)
The prepared copper plate was immersed in ethanol and subjected to ultrasonic cleaning for 5 minutes to clean the surface of the copper plate.
Further, by dissolving the silane coupling agent in pure water, a silane coupling agent-containing aqueous solution (silane coupling agent concentration: 1% by weight) was obtained.
Then, the washed copper plate was immersed in the silane coupling agent-containing aqueous solution for 20 minutes.
Next, the immersed copper plate was heated at 100° C. for 10 minutes (by dehydration condensation of the silane coupling agent and copper oxide) to form a film on the surface of the copper plate.
Then, a bonded body was obtained in the same manner as in Example 1-1 except that the copper plate on which a film was formed with a silane coupling agent was used.

(Reference example 1-1)
The prepared copper plate was immersed in ethanol and subjected to ultrasonic cleaning for 5 minutes to clean the surface of the copper plate.
The cleaned copper plate was then heated in an oven at 200° C. for 60 minutes in an atmospheric environment to oxidize the surface portion of the copper plate.
Next, a bonded body was obtained in the same manner as Comparative Example 1-2, except that instead of the washed copper plate, a copper plate whose surface portion was oxidized was immersed in the aqueous solution containing the silane coupling agent.

(Example 2-2)
As the thermosetting compound, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Celoxide 2021P (CEL2021P) manufactured by Daicel) was used, and the amount of curing agent was A bonded body was obtained in the same manner as in Example 1-2, except that the amount was 110 parts by weight based on 100 parts by weight of the compound.

(Example 2-3)
As the thermosetting compound, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Celoxide 2021P (CEL2021P) manufactured by Daicel) was used, and the amount of curing agent was A bonded body was obtained in the same manner as in Example 1-3, except that the amount was 110 parts by weight based on 100 parts by weight of the compound.

(Example 2-4)
As the thermosetting compound, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Celoxide 2021P (CEL2021P) manufactured by Daicel) was used, and the amount of curing agent was A bonded body was obtained in the same manner as in Example 1-4, except that the amount was 110 parts by weight based on 100 parts by weight of the compound.

(Example 2-5)
As the thermosetting compound, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Celoxide 2021P (CEL2021P) manufactured by Daicel) was used, and the amount of curing agent was A bonded body was obtained in the same manner as in Example 1-5, except that the amount was 110 parts by weight based on 100 parts by weight of the compound.

(Comparative example 2-1)
As the thermosetting compound, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Celoxide 2021P (CEL2021P) manufactured by Daicel) was used, and the amount of curing agent was A bonded body was obtained in the same manner as Comparative Example 1-1 except that the amount was 110 parts by weight based on 100 parts by weight of the compound.

(Comparative example 2-2)
As the thermosetting compound, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Celoxide 2021P (CEL2021P) manufactured by Daicel) was used, and the amount of curing agent was A bonded body was obtained in the same manner as in Comparative Example 1-2, except that the amount was 110 parts by weight based on 100 parts by weight of the compound.

(Measurement of joint strength)
By conducting a Shear test on the bonded bodies of Examples and Comparative Examples using a bond tester (Dage-4000 manufactured by Nordonson Dage) under the following conditions, the cured product of the thermosetting composition and copper were tested. The bonding strength of five samples was measured.
Distance between head and membrane: 200μm
Head speed: 50μm/s
The average value (arithmetic mean value), standard deviation, and coefficient of variation of bond strength are shown in Tables 1 and 2 below.
Note that the coefficient of variation was determined using the following formula.
Coefficient of variation (%) = (standard deviation/average value) x 100%

As shown in Table 1, in the joined bodies of Examples 1-1 to 1-6 within the scope of the present disclosure, Comparative Example 1-1 without a film and Comparative Example in which the film was formed with AMMO, which is a silane coupling agent. The average value of bonding strength was higher than that of Sample 1-2.
Furthermore, as shown in Table 2, in the joined bodies of Examples 2-2 to 2-5, which are within the scope of the present disclosure, in Comparative Example 2-1, which did not have a film, and in which the film was formed with AMMO, which is a silane coupling agent. The average value of bonding strength was higher than that of Comparative Example 2-2.
Therefore, according to the present disclosure, it is possible to provide a bonded body with high bonding strength between the cured product of the thermosetting composition and copper.

As shown in Table 1, from a comparison of Examples 1-1 and 1-2 in which the thiol contains an aromatic ring, in the conjugate of Example 1-2 in which the first functional group is a carboxyl group, the first The average value of bonding strength was higher than that of Example 1-1 in which the functional group of No. 1 was an amino group. Furthermore, from a comparison of Examples 1-3 to 1-6 in which the thiol does not contain an aromatic ring, in the conjugate of Example 1-6 in which the first functional group is a hydroxy group, the first functional group is a carboxyl group. The average value of bonding strength was higher than that of Examples 1-3 to 1-5.
Therefore, from the viewpoint of bonding strength, it can be seen that a carboxy group is preferable as the first functional group when it has an aromatic ring, and a hydroxy group is preferable as the first functional group when it does not contain an aromatic ring.

As shown in Table 1, in the joined bodies of Examples 1-1 to 1-6 within the scope of the present disclosure, Comparative Example 1-1 without a film and Comparative Example in which the film was formed with AMMO, which is a silane coupling agent. Compared to 1-2, the coefficient of variation of bonding strength was lower.
In addition, as shown in Table 2, in the joined bodies of Examples 2-2 to 2-5, which are within the scope of the present disclosure, in Comparative Example 2-1, which did not have a film, and in which the film was formed with AMMO, which is a silane coupling agent. Compared to Comparative Example 2-2, the coefficient of variation in bonding strength tended to be lower.
Therefore, it can be seen that according to the present disclosure, it is possible to provide a bonded body in which the bonding strength between the cured product of the thermosetting composition and copper has small fluctuations. That is, it can be seen that a bonded body with stable quality can be provided. In other words, it can be seen that a bonded body with excellent mass productivity can be provided.

As shown in Table 1, from a comparison of Examples 1-1 and 1-2 in which the thiol contains an aromatic ring, in the conjugate of Example 1-2 in which the first functional group is a carboxyl group, the first The coefficient of variation of bonding strength was lower than that of Example 1-1 in which the functional group 1 was an amino group. Furthermore, from a comparison of Examples 1-3 to 1-6 in which the thiol does not contain an aromatic ring, in the conjugate of Example 1-6 in which the first functional group is a hydroxy group, the first functional group is a carboxyl group. The coefficient of variation of bonding strength was lower than that of Examples 1-3 to 1-5.
Therefore, from the viewpoint of stabilizing quality, it can be seen that a carboxy group is preferable as the first functional group when an aromatic ring is present, and a hydroxy group is preferable as the first functional group when an aromatic ring is not included.

As shown in Table 1, when a thermosetting compound (YD128) having a glycidyl group as the second functional group is used, the bonding of Example 1-6 in which the thiol is 6-mercapto-1-hexanol (MCH) In comparison with Examples 1-1 to 1-5 in which other thiols were used, the coefficient of variation of bond strength was lower. Furthermore, for thiols whose first functional group is a carboxyl group, the coefficient of variation of bonding strength was low in Example 1-3, which was 3-mercaptopropionic acid (3-MPA) having 3 carbon atoms.
As shown in Table 2, when a thermosetting compound (CEL2021P) having an alicyclic epoxy group as the second functional group was used, Example 2-4 in which the thiol was 8-mercaptooctanoic acid (MOA) In the bonded body, the coefficient of variation in bond strength was lower than in Examples 2-2 and 2-3 in which other thiols were used.
Therefore, from the viewpoint of stabilizing quality, a thiol with a relatively short molecular chain is preferable for a thermosetting compound in which the second functional group is a glycidyl group, and a thiol in which the second functional group is an alicyclic epoxy group is preferable. It can be seen that thiols with relatively long molecular chains are preferable for certain thermosetting compounds.

Claims

A bonded body in which a cured product of a thermosetting composition and copper are bonded with a film,
The film is formed of thiol,
The thiol is a compound having at least one kind of first functional group selected from an amino group, a carboxy group, and a hydroxyl group, and is represented by the following formula (1),
The thermosetting composition contains a thermosetting compound,
The thermosetting compound has a second functional group capable of reacting with the first functional group.
Z-R-SH...(1)
(In the formula (1), Z is the first functional group, and R is an organic group having 1 to 20 carbon atoms.)
The zygote according to claim 1, wherein R in the formula (1) has 2 to 10 carbon atoms.
The conjugate according to claim 1 or 2, wherein R in the formula (1) includes a carbon-carbon unsaturated bond.
The conjugate according to claim 3, wherein R in the formula (1) includes a benzene ring.
The conjugate according to claim 4, wherein R in the formula (1) is a benzene ring.
The conjugate according to claim 1 or 2, wherein the second functional group has an epoxy group and/or a hydroxyl group.
The conjugate according to claim 6, wherein the second functional group has the epoxy group by having a glycidyl group and/or an alicyclic epoxy group.
The conjugate according to claim 1 or 2, wherein the thermosetting compound contains a saturated or unsaturated cyclic hydrocarbon group.
The joined body according to claim 1 or 2, wherein the copper is copper that has not been oxidized.
The joined body according to claim 1 or 2, wherein the thickness of the film is 2.0 to 5.0 nm.
A method for producing a bonded body, the method comprising: producing a bonded body in which a cured product of a thermosetting composition and copper are bonded with a film,
The zygote is the zygote according to claim 1 or 2,
a step (A) of bonding the thiol and the copper to form the film by providing a bonding agent containing the thiol on the surface of the copper;
A step of providing the thermosetting composition on the film and heating the thermosetting composition to bond the thiol and the thermosetting composition and curing the thermosetting composition ( B) A method for manufacturing a joined body, comprising: