Curable composition, laminate, and method for producing laminate

Abstract

Provided is a curable composition which, when a conductive layer is formed on the surface thereof, can form an insulating layer having excellent adhesion to the conductive layer and excellent smoothness of the conductive layer. A curable composition for forming an insulating layer adjacent to a conductive layer, the curable composition containing a cyclization polymerizable monomer, a thermally crosslinkable group-containing monomer, a polyfunctional monomer, a photopolymerization initiator, and a surface conditioning agent that does not contain either a fluorine atom or a silicon atom.

Description

Technical Field

[0001] The present invention relates to a curable composition, a laminate, and a method for manufacturing a laminate. Background Art

[0002] Semiconductor devices and the like are disturbed by electromagnetic waves and may malfunction, preventing normal operation. Also, when electromagnetic waves are generated by semiconductor devices and the like, these electromagnetic waves can interfere with other semiconductor devices and the like or electronic components, also preventing normal operation.

[0003] To prevent interference caused by electromagnetic waves between such electronic components, an electromagnetic wave shielding member that shields electromagnetic waves from the outside and electromagnetic waves generated by semiconductor devices and the like can be used. As a technique for forming such an electromagnetic wave shielding member, for example, a method of forming an electromagnetic wave shielding member by laminating an insulating layer and a conductive layer on a printed wiring board on which a semiconductor device is mounted is known.

[0004] When forming the laminate as described above, in view of manufacturing advantages such as being able to reduce the amount of ink used and being able to easily correspond to various shapes, a method of forming the laminate using an inkjet recording method has been explored.

[0005] As a curable composition capable of forming an insulating layer by such an inkjet recording method, for example, Patent Document 1 discloses a curable composition containing: (A) a photocurable component containing a (meth)acrylic monomer having no hydroxyl group and a (meth)acrylic monomer having a hydroxyl group; (B) a thermocurable component containing an adduct type blocked isocyanate compound; and (C) a photopolymerization initiator.

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2022 - 007466 Summary of the Invention

[0009] Technical Problem to be Solved by the Invention

[0010] The present inventors investigated the curable composition disclosed in Patent Document 1, and as a result, found that it is difficult to achieve both the adhesion between the conductive layer and the insulating layer and the smoothness of the conductive layer when forming a conductive layer on the insulating layer formed using the above curable composition.

[0011] In view of the above actual situation, an object of the present invention is to provide a curable composition capable of forming an insulating layer having excellent adhesion to a conductive layer and excellent smoothness of the conductive layer when forming a conductive layer on the surface.

[0012] Further, an object of the present invention is to provide a laminate including a conductive layer and an insulating layer formed using the above curable composition, and a method for manufacturing the above laminate.

[0013] Means for Solving the Technical Problem

[0014] As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by the following structure.

[0015] 〔1〕A curable composition for forming an insulating layer adjacent to a conductive layer,

[0016] The above curable composition contains a cyclopolymerizable monomer, a monomer having a thermally crosslinkable group, a polyfunctional monomer, a photoinitiator, and a surface conditioner containing neither a fluorine atom nor a silicon atom.

[0017] 〔2〕The curable composition according to 〔1〕, wherein

[0018] The mass ratio of the content of the above cyclopolymerizable monomer to the content of the above monomer having a thermally crosslinkable group is 5.0 to 40.0,

[0019] The mass ratio of the content of the above cyclopolymerizable monomer to the content of the above polyfunctional monomer is 1.0 to 7.0.

[0020] 〔3〕The curable composition according to 〔1〕 or 〔2〕, wherein

[0021] The above cyclopolymerizable monomer is α-allyloxymethyl methacrylate.

[0022] 〔4〕The curable composition according to any one of 〔1〕 to 〔3〕, wherein

[0023] The content of the above monomer having a thermally crosslinkable group is 0.5% by mass or more and less than 5.0% by mass with respect to the total mass of the above curable composition.

[0024] 〔5〕The curable composition according to any one of 〔1〕 to 〔4〕, wherein

[0025] The above monomer having a thermally crosslinkable group is a compound represented by the following formula (B2).

[0026] 〔6〕The curable composition according to any one of 〔1〕 to 〔5〕, wherein

[0027] The above conductive layer contains silver or copper.

[0028] 〔7〕A laminate including a conductive layer and an insulating layer formed using the curable composition according to any one of 〔1〕 to 〔6〕.

[0029] (8) The laminate according to (7), which is used as an electromagnetic wave shielding member disposed on a printed wiring board.

[0030] (9) A method for manufacturing a laminate, comprising:

[0031] Step 1 of forming an insulating layer by an inkjet recording method using the curable composition according to any one of (1) to (6); and

[0032] Step 2 of forming a conductive layer on the insulating layer using a conductive ink.

[0033] (10) The method for manufacturing a laminate according to (9), wherein

[0034] the above Step 1 includes a step of heating after irradiating an active energy ray to a coating film of the curable composition.

[0035] Advantageous Effects of the Invention

[0036] According to the present invention, it is possible to provide a curable composition capable of forming an insulating layer having excellent adhesion to a conductive layer and excellent smoothness of the conductive layer when forming the conductive layer on the surface.

[0037] Moreover, according to the present invention, it is also possible to provide a laminate including a conductive layer and an insulating layer formed using the above curable composition, and a method for manufacturing the laminate. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 is a schematic plan view of an electronic substrate used in the examples.

[0039] Figure 2 is Figure 1 a schematic cross-sectional view taken along line A-A of

[0040] Figure 3 is a view showing a state in which an insulating layer is formed on an electronic substrate in the schematic cross-sectional view taken along line A-A of Figure 1

[0041] Figure 4 is a view showing a state in which an insulating layer and a conductive layer are formed on an electronic substrate in the schematic cross-sectional view taken along line A-A of Figure 1 DETAILED DESCRIPTION OF THE INVENTION

[0042] Hereinafter, the present invention will be described in detail.

[0043] The following description is completed based on a representative embodiment of the present invention, and the present invention is not limited to such an embodiment.

[0044] ​​In this specification, the numerical range indicated by "~" means a range that includes the numerical values described before and after "~" as the lower limit value and the upper limit value. In the numerical ranges described in stages in this specification, the upper limit value or the lower limit value described in a certain numerical range can be replaced with the upper limit value or the lower limit value of another numerically described range in stages. Moreover, within the numerical ranges described in this specification, the upper limit value or the lower limit value described in a certain numerical range can be replaced with the value shown in the examples.

[0045] In this specification, "(meth)acrylic acid" is a general term for acrylic acid and methacrylic acid, and means "one or more of acrylic acid and methacrylic acid". Similarly, "(meth)acrylate" means "one or more of acrylate and methacrylate", "(meth)acryloyl" means "one or more of acryloyl and methacryloyl", and "acrylic resin" means "a polymer having one or more repeating units derived from acrylate monomers and / or methacrylate monomers".

[0046] In this specification, "electric conductivity" means a property in which the volume resistivity is less than 10 8 Ω·cm.

[0047] In this specification, unless otherwise specified, "monomer" means a compound having at least one polymerizable group.

[0048] In this specification, each component can be a single substance corresponding to each component, or two or more substances can be used. Here, when two or more substances are used for each component, unless otherwise specified, the content of the component means the total content of two or more substances.

[0049] In this specification, the combination of two or more preferred modes is a more preferred mode.

[0050] In this specification, "process" includes not only an independent process, but also includes this term even when it cannot be clearly distinguished from other processes as long as the desired purpose of the process is achieved.

[0051] In this specification, unless otherwise specifically stated, the bonding direction of the divalent group (for example, -CO-O-, etc.) described is not limited. For example, when Y in the compound represented by the formula composed of "X - Y - Z" is -CO - O-, the above compound can be any one of "X - O - CO - Z" and "X - CO - O - Z".

[0052] [Curable Composition]

[0053] Hereinafter, the curable composition of the present invention (hereinafter, also simply referred to as "curable composition") will be described in detail.

[0054] The curable composition of the present invention contains a cyclopolymerizable monomer, a monomer having a thermally crosslinkable group, a polyfunctional monomer, a photopolymerization initiator, and a surface conditioner containing neither a fluorine atom nor a silicon atom.

[0055] According to the curable composition having the above structure, when forming a conductive layer on the surface, an insulating layer having excellent adhesion to the conductive layer and excellent smoothness of the conductive layer can be formed. Although the detailed reasons for this are not clear, the present inventors speculate as follows.

[0056] In addition, there is no limitation on the mechanism of the effects that can be obtained through the following speculation. In other words, even in the case where effects are obtained through mechanisms other than the following, it is included within the scope of the present invention.

[0057] A curable composition containing a cyclopolymerizable monomer, a monomer having a thermally crosslinkable group, a polyfunctional monomer, and a photopolymerization initiator can form an insulating layer through a photopolymerization reaction, and since it contains a cyclopolymerizable monomer and a monomer having a thermally crosslinkable group, the adhesion of the above insulating layer to other layers is excellent. However, when forming a conductive layer on the above insulating layer, there may be a case where at least one of the smoothness of the conductive layer and the adhesion between the conductive layer and the insulating layer does not reach the desired level. The reason for this is considered to be that when the curable composition contains a surface conditioner containing at least one of a silicon atom and a fluorine atom, the wettability of the insulating layer with respect to the conductive ink used to form the above conductive layer is low, and the conductive ink is repelled and a uniform coating film cannot be formed.

[0058] Regarding the insulating layer formed using the curable composition of the present invention containing a surface conditioner containing neither silicon nor fluorine, its surface state and wettability with respect to the conductive ink are excellent. Therefore, it is speculated that when forming a conductive layer using a conductive ink on the surface of the insulating layer formed using the curable composition of the present invention, the adhesion between the conductive layer and the insulating layer is excellent and the smoothness of the conductive layer is excellent.

[0059] Hereinafter, the case where at least one of the adhesion between the conductive layer and the insulating layer and the smoothness of the conductive layer is more excellent is also referred to as "the effects of the present invention are more excellent".

[0060] 〔Cyclopolymerizable monomer〕

[0061] The curable composition contains a cyclopolymerizable monomer.

[0062] By containing a cyclopolymerizable monomer in the curable composition, the adhesion between the conductive layer and the insulating layer and the smoothness of the conductive layer are excellent, and the ejectability of the curable composition based on an inkjet recording method or the like is also excellent.

[0063] The cyclopolymerizable monomer is a monomer that forms a ring structure in the molecule through a polymerization reaction.

[0064] The polymerizable group possessed by the cyclization polymerizable monomer is not particularly limited, and may be either a cationic polymerizable group or a radical polymerizable group. Preferably, it is a radical polymerizable group, and more preferably an ethylenically unsaturated group.

[0065] As the ring structure formed by the cyclization polymerizable monomer through a polymerization reaction, an aliphatic hydrocarbon ring and an aliphatic heterocycle can be mentioned. Preferably, it is an aliphatic heterocycle, and more preferably a cyclic ether. When the ring structure formed by the cyclization polymerizable monomer through a polymerization reaction is a cyclic ether, an ether bond as a polar group is present in the main chain, whereby the adhesion is more excellent.

[0066] The number of ring members of the above ring structure is preferably 3 to 8, more preferably 5 or 6, and further preferably 5.

[0067] The cyclization polymerizable monomer is preferably a monomer having two or more ethylenically unsaturated groups in one molecule, and the two ethylenically unsaturated groups are bonded to each other by radical polymerization and form a ring structure in the molecule.

[0068] As the cyclization polymerizable monomer as described above, for example, d-(allyloxymethyl) acrylate, α-(allyloxymethyl) acrylic acid, and acrylic ether dimers can be mentioned. Preferably, it is α-(allyloxymethyl) acrylate.

[0069] As α-(allyloxymethyl) acrylate, a compound represented by the formula (A1) can be mentioned.

[0070] The compound represented by the formula (A1) forms a repeating unit represented by the formula (PA1) through a polymerization reaction. The repeating unit represented by the formula (PA1) is a repeating unit having a tetrahydrofuran ring in the main chain.

[0071] [Chemical formula 1]

[0072]

[0073] In the formula (A1), R A1 represents a monovalent organic group.

[0074] As the above monovalent organic group, for example, a hydrocarbon group which may have a divalent linking group selected from an ether bond and an amide bond and may have a substituent can be mentioned.

[0075] As the above hydrocarbon group, an aliphatic hydrocarbon group and an aromatic hydrocarbon group can be mentioned.

[0076] The above aliphatic hydrocarbon group can be any of linear, branched, and cyclic.

[0077] The number of carbon atoms of the above-mentioned aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 12, still more preferably 1 to 6, and particularly preferably 1 to 3.

[0078] The above-mentioned aromatic hydrocarbon group may be either a monocyclic or polycyclic group.

[0079] The number of carbon atoms of the above-mentioned aromatic hydrocarbon group is preferably 3 to 30, more preferably 6 to 20, still more preferably 6 to 12.

[0080] That the hydrocarbon group may have an ether bond means that a divalent linking group represented by -O- may be present between carbon-carbon bonds in the hydrocarbon group. And that the hydrocarbon group may have an amide bond means that a divalent linking group represented by -NRCO- may be present. R represents a hydrogen atom or a monovalent hydrocarbon group.

[0081] The substituents that the above-mentioned hydrocarbon group may have are not particularly limited, and are preferably a hydroxyl group, an amino group (which may be any of a primary amino group, a secondary amino group, and a tertiary amino group), or a halogen atom.

[0082] As for R A1 , it is preferably an aliphatic hydrocarbon group, more preferably a linear aliphatic hydrocarbon group having 1 to 6 carbon atoms, and still more preferably a methyl group or an ethyl group.

[0083] Examples of the compound represented by formula (A1) include methyl α-allyloxymethacrylate (AOMA), ethyl α-allyloxymethacrylate, n-propyl α-allyloxymethacrylate, isopropyl α-allyloxymethacrylate, n-butyl α-allyloxymethacrylate, sec-butyl α-allyloxymethacrylate, tert-butyl α-allyloxymethacrylate, n-hexyl α-allyloxymethacrylate, 2-ethylhexyl α-allyloxymethacrylate, methoxyethyl α-allyloxymethacrylate, methoxyethoxyethyl α-allyloxymethacrylate, methoxyethoxyethoxyethyl α-allyloxymethacrylate, 3-methoxybutyl α-allyloxymethacrylate, ethoxyethyl α-allyloxymethacrylate, ethoxyethoxyethyl α-allyloxymethacrylate, phenoxyethyl α-allyloxymethacrylate, phenoxyethoxyethyl α-allyloxymethacrylate, 2-hydroxyethyl α-allyloxymethacrylate, 2-hydroxypropyl α-allyloxymethacrylate, 2-hydroxybutyl α-allyloxymethacrylate, 2,3-dihydroxypropyl α-allyloxymethacrylate, dimethylaminoethyl α-allyloxymethacrylate, diethylaminoethyl α-allyloxymethacrylate, acetamideethyl α-allyloxymethacrylate, N-methacetamideethyl α-allyloxymethacrylate, propionamideethyl α-allyloxymethacrylate, pyrrolidinoethyl α-allyloxymethacrylate, cyclohexyl α-allyloxymethacrylate, isobornyl α-allyloxymethacrylate, tetrahydrofurfuryl α-allyloxymethacrylate, tetrahydrofurfuryloxyethyl α-allyloxymethacrylate, tetrahydrofurfuryloxyethoxyethyl α-allyloxymethacrylate, tetrahydropyranyl α-allyloxymethacrylate, (5-methyl-5-m-dioxacyclohexyl)methyl α-allyloxymethacrylate, phenyl α-allyloxymethacrylate, benzyl α-allyloxymethacrylate, and naphthyl α-allyloxymethacrylate.

[0084] Among them, as the cyclopolymerizable monomer, AOMA is preferably used in view of more excellent effects of the present invention.

[0085] As the acrylic ether dimer, an ether dimer of (α-hydroxymethyl)acrylate is preferred.

[0086] Examples of the ether dimer of (α-hydroxymethyl)acrylate include the compound represented by formula (A2).

[0087] The compound represented by formula (A2) forms a repeating unit represented by formula (PA2) through a polymerization reaction. The repeating unit represented by formula (PA2) is a repeating unit having a tetrahydropyran ring in the main chain.

[0088] [Chemical formula 2]

[0089]

[0090] In formula (A2), R A2 and R A3 each independently represent a monovalent organic group.

[0091] The definitions and preferred forms of the monovalent organic groups represented by the above R A2 and R A3 are the same as those of the monovalent organic group represented by R A1 in formula (A1).

[0092] Examples of the compound represented by formula (A2) include dimethyl 2,2'-[oxybis(methylene)] bisacrylate, diethyl 2,2'-[oxybis(methylene)] bisacrylate, di(n-propyl) 2,2'-[oxybis(methylene)] bisacrylate, di(isopropyl) 2,2'-[oxybis(methylene)] bisacrylate, di(n-butyl) 2,2'-[oxybis(methylene)] bisacrylate, di(isobutyl) 2,2'-[oxybis(methylene)] bisacrylate, di(tert-butyl) 2,2'-[oxybis(methylene)] bisacrylate, di(tert-pentyl) 2,2'-[oxybis(methylene)] bisacrylate, di(stearyl) 2,2'-[oxybis(methylene)] bisacrylate, di(lauryl) 2,2'-[oxybis(methylene)] bisacrylate, di(2-ethylhexyl) 2,2'-[oxybis(methylene)] bisacrylate, di(1-methoxyethyl) 2,2'-[oxybis(methylene)] bisacrylate, di(1-ethoxyethyl) 2,2'-[oxybis(methylene)] bisacrylate, bibenzyl 2,2'-[oxybis(methylene)] bisacrylate, diphenyl 2,2'-[oxybis(methylene)] bisacrylate, dicyclohexyl 2,2'-[oxybis(methylene)] bisacrylate, di(tert-butylcyclohexyl) 2,2'-[oxybis(methylene)] bisacrylate, di(dicyclopentadiene) 2,2'-[oxybis(methylene)] bisacrylate, di(tricyclodecyl) 2,2'-[oxybis(methylene)] bisacrylate, di(isobornyl) 2,2'-[oxybis(methylene)] bisacrylate, diadamantyl 2,2'-[oxybis(methylene)] bisacrylate, and di(2-methyl-2-adamantyl) 2,2'-[oxybis(methylene)] bisacrylate, etc., dialkyl 2,2'-(oxydimethylene) diacrylate.

[0093] Among them, as the cyclopolymerizable monomer, dimethyl 2,2'-[oxybis(methylene)] bisacrylate is preferred.

[0094] As the cyclization polymerizable monomer, it is preferably at least one compound selected from the group consisting of the compound represented by formula (A1) and the compound represented by formula (A2), more preferably contains the compound represented by formula (A1), and further preferably contains AOMA.

[0095] Moreover, the cyclization polymerizable monomer is preferably the compound represented by formula (A1), and more preferably AOMA.

[0096] The cyclization polymerizable monomer may be used alone or in combination of two or more.

[0097] From the aspect of more excellent effects of the present invention, the content of the cyclization polymerizable monomer is preferably 1.0 to 90.0% by mass, more preferably 5.0 to 80.0% by mass, and further preferably 20.0 to 70.0% by mass based on the total mass of the curable composition.

[0098] (Monomer containing a thermally crosslinkable group)

[0099] The curable composition contains a monomer containing a thermally crosslinkable group. The monomer containing a thermally crosslinkable group is a compound different from the above-mentioned cyclization polymerizable monomer.

[0100] By the curable composition containing a monomer containing a thermally crosslinkable group, the adhesion between the conductive layer and the insulating layer, the crack inhibition property, and the peelability are excellent.

[0101] In addition, the above-mentioned crack inhibition property refers to the property of being able to inhibit the generation of cracks in the insulating layer when using the curable composition to form the insulating layer. When using the laminate composed of the insulating layer and the conductive layer as an electromagnetic wave shielding member, from the aspect of being able to prevent short circuits between the conductive layer and wiring and having excellent electromagnetic wave shielding properties of the laminate, excellent crack inhibition property is preferred.

[0102] Moreover, the above-mentioned peelability refers to the ease of peeling of the insulating layer from the substrate when using the curable composition to form the insulating layer on a substrate such as a module. From the aspect of manufacturing and being able to reuse the module by peeling off the insulating layer, excellent peelability is preferred.

[0103] The monomer containing a thermally crosslinkable group is a compound having a photopolymerizable group and a thermally crosslinkable group in the molecule. In addition, the photopolymerizable group and the thermally crosslinkable group are different groups.

[0104] The photopolymerizable group possessed by the monomer containing a thermally crosslinkable group is not particularly limited, and preferably an ethylenically unsaturated group such as vinyl, styryl, (meth)acryloxy group, and (meth)acrylamide group.

[0105] As described above, the thermal crosslinkable group of the monomer containing a thermal crosslinkable group is a group different from the above photopolymerizable group, and is not particularly limited as long as it is a group that undergoes a crosslinking reaction by heat. Examples thereof include an epoxy group, an oxetanyl group, an isocyanate group, a blocked isocyanate group, a hydroxyl group, and a leaving group (e.g., a halogenated alkyl group). Among them, as the thermal crosslinkable group, from the viewpoint of more excellent effects of the present invention, an epoxy group or an oxetanyl group is preferred, and an epoxy group is more preferred.

[0106] As the monomer containing a thermal crosslinkable group having an epoxy group as the thermal crosslinkable group, a compound represented by the formula (B1) is preferred.

[0107] [Chemical formula 3]

[0108]

[0109] In the formula (B1), R 1 and R 2 each independently represent a hydrogen atom or an alkyl group.

[0110] The above alkyl group may be any of linear, branched, and cyclic.

[0111] The number of carbon atoms of the above alkyl group is preferably 1 to 12, more preferably 1 to 6, and further preferably 1 to 3.

[0112] As R 1 and R 2 , a hydrogen atom, a methyl group, or an ethyl group is preferred.

[0113] In the formula (B1), X represents a single bond, a phenylene group, -COO-, or -CONH-.

[0114] As X, -COO- is preferred.

[0115] In the formula (B1), L represents a divalent linking group.

[0116] As the above divalent linking group, for example, a divalent hydrocarbon group which may have a substituent and may have a divalent linking group selected from -O-, -COO-, and -CONH- can be exemplified.

[0117] As the above divalent hydrocarbon group, an alkylene group, a divalent aromatic hydrocarbon group, and a group combining these can be exemplified.

[0118] The above alkylene group may be any of linear, branched, and cyclic, is preferably linear or branched, and more preferably linear.

[0119] The number of carbon atoms of the above alkylene group is preferably 1 to 30, more preferably 1 to 10, further preferably 2 to 8, and particularly preferably 3 to 6.

[0120] The divalent aromatic hydrocarbon group described above can be either monocyclic or polycyclic.

[0121] The number of carbon atoms of the divalent aromatic hydrocarbon group described above is preferably 4 to 12, more preferably 6 to 10.

[0122] As the divalent aromatic hydrocarbon group described above, a phenylene group is preferred.

[0123] There are no particular restrictions on the substituents that the divalent hydrocarbon group described above can have, and halogen atoms, hydroxyl groups, alkoxy groups, or acyl groups are preferred.

[0124] There are no particular restrictions on the number of divalent linking groups selected from -O-, -COO-, and -CONH- in the divalent hydrocarbon group described above, and it is preferably 1 to 4, more preferably 1 or 2, and further preferably 1.

[0125] The compound represented by formula (B1) is preferably the compound represented by formula (B2).

[0126] [Chemical formula 4]

[0127]

[0128] In formula (B2), R 1 and R 2 each independently represent a hydrogen atom or an alkyl group.

[0129] In formula (B2), R 1 and R 2 The meanings of the groups represented are the same as those of R 1 and R 2 in formula (B1).

[0130] In formula (B2), R 3 represents an alkylene group that may have an ether bond.

[0131] May have an ether bond means that a divalent linking group represented by -O- can be present between the carbon-carbon bonds in the above divalent alkylene group.

[0132] The above alkylene group can be any of linear, branched, and cyclic, preferably linear or branched, and more preferably linear.

[0133] From the aspect of more excellent adhesion between the conductive layer and the insulating layer, crack suppression, and peelability, the number of carbon atoms of the above alkylene group is preferably 1 to 10, more preferably 2 to 8, and further preferably 3 to 6.

[0134] When the above alkylene group has an ether bond, the number thereof is not particularly limited, and is preferably 1 to 3, and more preferably 1.

[0135] As R 3 , preferably an alkylene group, or * 0 -alkylene-O-methylidene-* E the group represented. * 0 In the formula (B2), the bonding position of the oxygen atom adjacent to R 3 and * E represents the bonding position to another epoxy group. R 3 is * 0 -alkylene-O-methylidene-* E the compound represented by the group represents a compound having a glycidyl ether group as an epoxy group. * 0 -alkylene-O-methylidene-* E In the group represented by, the number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 2 to 8. And, * 0 -alkylene-O-methylidene-* E the alkylene group in the group represented is preferably linear.

[0136] As the monomer containing a thermally crosslinkable group having an epoxy group as a thermally crosslinkable group, for example, epoxy (meth) acrylic acid alkyl ester, mono-glycidyl ether mono (meth) acrylate of diol, reaction product of glycidyl and isocyanate containing (meth) acrylate, vinylbenzyl glycidyl ether, (meth) acrylamide containing an epoxy group, 1:1 addition reaction product of diglycidyl ether and (meth) acrylic acid, and mono-glycidyl ester mono (meth) acryloyloxyethyl ester of dicarboxylic acid can be mentioned. Preferably, epoxy (meth) acrylic acid alkyl ester or mono-glycidyl ether mono (meth) acrylate of diol is used, and more preferably mono-glycidyl ether mono (meth) acrylate of diol is used.

[0137] As the above-mentioned epoxy (meth) acrylic acid alkyl ester, specifically, for example, glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 4,5-epoxypentyl (meth) acrylate, 5,6-epoxyhexyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, 10,11-epoxyundecyl (meth) acrylate, 4-epoxypropylcyclohexyl (meth) acrylate, etc. can be mentioned.

[0138] As the diol in the above-mentioned mono-glycidyl ether mono (meth) acrylate of diol, for example, ethylene glycol, propylene glycol, tetramethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, ditetramethylene glycol, bisphenol A, etc. can be mentioned.

[0139] As the mono-glycidyl ether mono(meth)acrylate of the above diol, specifically, for example, glycidyl ether of 4-hydroxybutyl (meth)acrylate, glycidyl ether of 2-hydroxyethyl (meth)acrylate, glycidyl ether of 3-hydroxypropyl (meth)acrylate, glycidyl ether of 6-hydroxyhexyl (meth)acrylate, glycidyl ether of 8-hydroxyoctyl (meth)acrylate, etc. can be cited.

[0140] As the (meth)acrylate group-containing isocyanate in the reaction product of the above glycidyl and the (meth)acrylate group-containing isocyanate, for example, 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, (isocyanatoethyloxy)ethyl methacrylate, etc. can be cited.

[0141] As the above vinylbenzyl glycidyl ether, for example, the compounds described in Japanese Patent Laid-Open No. 09-227540 can be cited.

[0142] As the above epoxy group-containing (meth)acrylamide, for example, the compounds described in Japanese Patent Laid-Open No. 2015-229633 can be cited.

[0143] As the diglycidyl ether in the 1:1 addition reaction product of the above diglycidyl ether and (meth)acrylic acid, for example, bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, etc. can be cited.

[0144] As the dicarboxylic acid in the mono-glycidyl ester mono(meth)acryloyloxyethyl ester of the above dicarboxylic acid, for example, phthalic acid, cyclohexene dicarboxylic acid, cyclohexane dicarboxylic acid, maleic acid, malonic acid, succinic acid, etc. can be cited.

[0145] As the monomers having an epoxy group as a thermally crosslinkable group other than the above, for example, 1-chloro-2,3-epoxypropyl acrylate, 1-chloro-2,3-epoxypropyl methacrylate, 2-bromo-3,4-epoxybutyl acrylate, 2-bromo-3,4-epoxybutyl methacrylate, 2-(3,4-epoxybutyloxy)-ethyl acrylate, 2-(3,4-epoxybutyloxy)-ethyl methacrylate, etc. can be cited.

[0146] As the monomers containing a thermally crosslinkable group, among them, glycidyl (meth)acrylate, glycidyl ether of 4-hydroxybutyl (meth)acrylate, or 3,4-epoxycyclohexylmethyl (meth)acrylate is preferred, and glycidyl ether of 4-hydroxybutyl acrylate is more preferred.

[0147] As a monomer having an oxetanyl group as a thermally crosslinkable group, for example, (3-ethyl-oxetan-3-yl) methacrylate and the like can be mentioned.

[0148] As a monomer having an isocyanate group as a thermally crosslinkable group, for example, 2-(meth)acryloyloxyethyl isocyanate, 3-(meth)acryloyloxypropyl isocyanate, 4-(meth)acryloyloxybutyl isocyanate, 6-(meth)acryloyloxyhexyl isocyanate, 8-(meth)acryloyloxyoctyl isocyanate, 10-(meth)acryloyloxydecyl isocyanate and other (meth)acrylic acid derivatives; 1,1-(bisacryloyloxymethyl)ethyl isocyanate, (isocyanatoethyloxy)ethyl methacrylate and the like.

[0149] As a leaving group in a monomer having a leaving group as a thermally crosslinkable group, for example, a halogen atom and a toluenesulfonyl group can be mentioned.

[0150] As a monomer having a leaving group as a thermally crosslinkable group, specifically, for example, 2-iodoethyl (meth)acrylate, 2-bromoethyl (meth)acrylate, 2-chloroethyl (meth)acrylate, 2-tosylethyl (meth)acrylate, 4-iodobutyl (meth)acrylate, 4-bromobutyl (meth)acrylate, 4-chlorobutyl (meth)acrylate, 4-tosylbutyl (meth)acrylate and the like can be mentioned.

[0151] As a monomer having a hydroxyl group as a thermally crosslinkable group, for example, a mono(meth)acrylate of a diol can be mentioned. As the above diol, for example, bisphenol A, ethylene glycol, propylene glycol, tetramethylene glycol, diethylene glycol, dipropylene glycol, ditetramethylene glycol, polyethylene glycol and the like can be mentioned.

[0152] In addition to the above, unsaturated fatty acid hydroxyalkyl esters modified ε-caprolactone can also be used. As commercially available products, PLACCEL FA1, PLACCEL FM1, PLACCEL FA2D, PLACCEL FM2D, PLACCEL FA5, PLACCEL FM5, PLACCEL FA10L (all manufactured by Daicel Corporation) and the like can be mentioned.

[0153] As a monomer having a hydroxyl group as a thermally crosslinkable group, specifically, for example, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate and the like can be used.

[0154] The monomers containing thermally crosslinkable groups may be used alone or in combination of two or more kinds.

[0155] When the curable composition contains a monomer having a hydroxyl group, an isocyanate group, a blocked isocyanate group or a thermally crosslinkable group having a leaving group as a thermally crosslinkable group, it is preferable to further contain a compound having two or more groups reactive with the above-mentioned thermally crosslinkable groups (for example, a thermally crosslinking agent described later).

[0156] From the viewpoint of more excellent adhesion between the conductive layer and the insulating layer and crack suppression property, the content of the monomer containing a thermally crosslinkable group is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more, based on the total mass of the curable composition. From the viewpoint of more excellent adhesion between the conductive layer and the insulating layer, the upper limit is preferably 30.0% by mass or less, more preferably 20.0% by mass or less, further preferably less than 5.0% by mass, and particularly preferably 3.0% by mass or less.

[0157] From the viewpoint of more excellent adhesion between the conductive layer and the insulating layer, the mass ratio of the content of the cyclopolymerizable monomer to the content of the monomer containing a thermally crosslinkable group is preferably 1.0 or more, more preferably 2.0 or more, and further preferably 5.0 or more. From the viewpoints of more excellent adhesion between the conductive layer and the insulating layer, crack suppression property and smoothness of peelability, the upper limit is preferably 100.0 or less, more preferably 80.0 or less, and further preferably 40.0 or less.

[0158] [Polyfunctional monomer]

[0159] The curable composition of the present invention contains a polyfunctional monomer. The polyfunctional monomer is a compound different from the above-mentioned cyclopolymerizable monomer and the monomer containing a thermally crosslinkable group.

[0160] By containing a polyfunctional monomer in the curable composition, the curability is excellent, and the smoothness, crack suppression property and peelability of the conductive layer are also excellent.

[0161] The polyfunctional monomer is a monomer having two or more polymerizable groups in one molecule.

[0162] From the viewpoint of more excellent curability, the polyfunctional monomer is preferably a polyfunctional radical polymerizable monomer, and more preferably a polyfunctional ethylenically unsaturated monomer.

[0163] Examples of the polyfunctional ethylenically unsaturated monomer include polyfunctional (meth)acrylates and polyfunctional vinyl ethers, and polyfunctional (meth)acrylates are preferred.

[0164] As polyfunctional (meth)acrylates, examples thereof include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, heptanediol di(meth)acrylate, EO-modified neopentyl glycol di(meth)acrylate, PO-modified neopentyl glycol di(meth)acrylate, EO-modified hexanediol di(meth)acrylate, PO-modified hexanediol di(meth)acrylate, octanediol di(meth)acrylate, nonanediol di(meth)acrylate, decanediol di(meth)acrylate, dodecanediol di(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane EO adduct tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(meth)acryloyloxyethoxytrimethylolpropane, glycerol polyglycidyl ether poly(meth)acrylate, and tris(2-acryloyloxyethyl)isocyanurate.

[0165] As polyfunctional vinyl ethers, examples thereof include 1,4-butanediol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, EO adduct trimethylolpropane trivinyl ether, PO adduct trimethylolpropane trivinyl ether, EO adduct ditrimethylolpropane tetravinyl ether, PO adduct ditrimethylolpropane tetravinyl ether, EO adduct pentaerythritol tetravinyl ether, PO adduct pentaerythritol tetravinyl ether, EO adduct dipentaerythritol hexavinyl ether, and PO adduct dipentaerythritol hexavinyl ether.

[0166] Among them, as the polyfunctional monomer, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, or 1,4-butanediol di(meth)acrylate is preferred, and polyethylene glycol di(meth)acrylate (EO chain n = 4 to 14) or 1,6-hexanediol di(meth)acrylate is more preferred.

[0167] The polyfunctional monomer can be used alone or in combination of two or more.

[0168] In terms of more excellent smoothness and peelability of the conductive layer, the content of the polyfunctional monomer is preferably 1.0 to 90.0% by mass, more preferably 5.0 to 80.0% by mass, and further preferably 10.0 to 60.0% by mass based on the total mass of the curable composition.

[0169] In terms of more excellent adhesion between the conductive layer and the insulating layer, the mass ratio of the content of the cyclopolymerizable monomer to the content of the polyfunctional monomer is preferably 0.05 or more, more preferably 0.2 or more, and further preferably 1.0 or more. In terms of more excellent crack inhibition and peelability, the upper limit is preferably 15.0 or less, more preferably 12.0 or less, and further preferably 7.0 or less.

[0170] In terms of more excellent effects of the present invention, the mass ratio of the content of the polyfunctional monomer to the content of the monomer containing a thermally crosslinkable group is preferably 0.1 to 100.0, more preferably 1.0 to 80.0, further preferably 5.0 to 50.0, and particularly preferably 10.0 to 35.0.

[0171] 〔Photoinitiator〕

[0172] The curable composition contains a photoinitiator.

[0173] Due to the curable composition containing a photoinitiator, the curability based on the photopolymerization reaction is excellent.

[0174] As the photoinitiator, there is no particular limitation as long as it is a compound capable of polymerizing monomers (such as the above-mentioned cyclopolymerizable monomer, polyfunctional monomer, and monomer containing a thermally crosslinkable group) by irradiation with actinic rays such as ultraviolet rays, electron beams, and chemical rays, and known photoinitiators can be used.

[0175] As the photoinitiator, for example, a photo radical polymerization initiator and a photo cationic polymerization initiator can be mentioned, and a photo radical polymerization initiator is preferred.

[0176] As a photoinitiator, for example, alkylbenzophenone compounds, thioxanthone compounds, oxime compounds, aromatic onium salt compounds, organic peroxides, hexaarylbiimidazole compounds, borate compounds, azinium compounds, titanocene compounds, active ester compounds, compounds having a carbon-halogen bond, and alkylamines can be cited.

[0177] Among them, from the aspect of electromagnetic wave shielding property, it is preferable that the photoinitiator contains at least one selected from alkylbenzophenone compounds and thioxanthone compounds, and more preferably contains alkylbenzophenone compounds and thioxanthone compounds.

[0178] As the alkylbenzophenone compound, for example, α-hydroxyalkylbenzophenone compounds, α-aminoalkylbenzophenone compounds, and benzyl ketal alkylbenzophenone compounds can be cited.

[0179] As the α-hydroxyalkylbenzophenone compound, for example, 2,2'-dihydroxy-2,2'-dimethyl-1,1'-[methylenebis(4,1-phenylene)]bis(propane-1-one), 1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-2-hydroxy-1-propanone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and 1-hydroxycyclohexyl phenyl ketone can be cited.

[0180] As the d-aminoalkylbenzophenone compound, for example, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl-1-[4-(hexyl)phenyl]-2-morpholinopropan-1-one, 2-ethyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butan-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-butan-1-one can be cited.

[0181] As the benzyl ketal alkylbenzophenone compound, for example, 2,2-dimethoxy-2-phenylacetophenone can be cited.

[0182] As commercially available products of the alkylbenzophenone compound, for example, Omnirad 379, Omnitad651, Omnitad184, Omnitad 1173, Omnitad 2959, Omnitad 127, Omnitad907, Omnitad 369, and Omnitad369E (all manufactured by IGM Resins B.V.) can be cited.

[0183] As thioxanthone compounds, thioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-dodecylthioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 1-methoxycarbonylthioxanthone, 2-ethoxycarbonylthioxanthone, 3-(2-methoxyethoxycarbonyl)thioxanthone, 4-butoxycarbonylthioxanthone, 3-butoxycarbonyl-7-methylthioxanthone, 1-cyano-3-chlorothioxanthone, 1-ethoxycarbonyl-3-chlorothioxanthone, 1-ethoxycarbonyl-3-ethoxythioxanthone, 1-ethoxycarbonyl-3-aminothioxanthone, 1-ethoxycarbonyl-3-phenylsulfurylthioxanthone, 3,4-bis[2-(2-methoxyethoxy)ethoxycarbonyl]thioxanthone, 1-ethoxycarbonyl-3-(1-methyl-1-morpholinoethyl)thioxanthone, 2-methyl-6-dimethoxymethylthioxanthone, 2-methyl-6-(1,1-dimethoxybenzyl)thioxanthone, 2-morpholinomethylthioxanthone, 2-methyl-6-morpholinomethylthioxanthone, n-allylthioxanthone-3,4-dicarboximide, n-octylthioxanthone-3,4-dicarboximide, N-(1,1,3,3-tetramethylbutyl)thioxanthone-3,4-dicarboximide, 1-phenoxythioxanthone, 6-ethoxycarbonyl-2-methoxythioxanthone, 6-ethoxycarbonyl-2-methylthioxanthone, thioxanthone-2-polyethylene glycol ester, and 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthone-2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride can be cited.

[0184] As commercially available products of thioxanthone compounds, the SPEEDCURE series manufactured by Lambson Co., Ltd. (such as SPEEDCURE ITX, SPEEDCURE 7010, and SPEEDCURE CPTX, etc.) can be cited.

[0185] The photoinitiator can be used alone or in combination of two or more. Preferably, it is used in combination of two or more.

[0186] When the photoinitiator contains an alkyl phenyl ketone compound and a thioxanthone compound, from the aspect of more excellent effects of the present invention, the mass ratio of the content of the alkyl phenyl ketone compound to the content of the thioxanthone compound is preferably 0.1 to 3.0, more preferably 0.1 to 2.0, and further preferably 0.3 to 1.5.

[0187] The content of the photoinitiator is preferably 0.5 to 20.0% by mass, more preferably 5.0 to 15.0% by mass, based on the total mass of the curable composition.

[0188] [Surface conditioner that does not contain any of fluorine atoms and silicon atoms]

[0189] The curable composition contains a surface conditioner that does not contain any of fluorine atoms and silicon atoms.

[0190] By the curable composition containing a surface conditioner that does not contain any of fluorine atoms and silicon atoms, the adhesion between the conductive layer and the insulating layer and the smoothness of the conductive layer are excellent.

[0191] The above surface conditioner is a compound that exists on the surface of the coating film of the curable composition and has the function of controlling the wettability and leveling property of the curable composition and the insulating layer formed using the curable composition, but it can also be a compound having the function of an antifoaming agent, a defoaming agent, an antifoaming agent and / or an adhesion promoter.

[0192] The surface conditioner that does not contain any of fluorine atoms and silicon atoms is also preferably composed of atoms selected from the group consisting of carbon atoms, oxygen atoms, hydrogen atoms and nitrogen atoms, and more preferably composed of atoms selected from the group consisting of carbon atoms, oxygen atoms and hydrogen atoms.

[0193] The curable composition also preferably substantially does not contain a surface conditioner that contains any of silicon atoms and fluorine atoms. That the curable composition substantially does not contain a surface conditioner that contains any of silicon atoms and fluorine atoms means that the content of the surface conditioner containing silicon atoms or fluorine atoms is 1% by mass or less, preferably 0.1% by mass or less, more preferably 0.01% by mass or less, relative to the total mass of the surface conditioner contained in the curable composition. The lower limit is preferably 0% by mass.

[0194] As the surface conditioner that does not contain any of fluorine atoms and silicon atoms, there is no limitation as long as it does not contain fluorine atoms and silicon atoms, and known surface conditioners can be used.

[0195] The surface conditioner can be a compound having a hydrophobic part and a hydrophilic part.

[0196] As the above hydrophobic part, for example, an aliphatic hydrocarbon group and an aromatic hydrocarbon group can be cited.

[0197] As the above hydrophilic part, for example, a hydroxyl group, a carboxyl group, a sulfo group, a phosphonic acid group, an amino group and a quaternary ammonium salt group can be cited.

[0198] As the surface conditioner that does not contain any of fluorine atoms and silicon atoms, nonionic surface conditioners, anionic surface conditioners and cationic surface conditioners can be cited, and nonionic surface conditioners are preferred.

[0199] As a nonionic surface conditioner that does not contain either fluorine atoms or silicon atoms, examples include acrylic surface conditioners, polyether surface conditioners, and vinyl surface conditioners, with acrylic surface conditioners or polyether surface conditioners being preferred.

[0200] As the above-mentioned acrylic surface conditioner, an acrylic resin can be cited. The acrylic resin is a polymer containing structural units derived from (meth)acrylic acid-based monomers, and the above polymer can be either a homopolymer or a copolymer.

[0201] As the above-mentioned polyether surface conditioner, examples include polyalkylene glycols such as polyethylene glycol and polypropylene glycol, polyalkylene ether such as polyoxyethylene alkyl ether, polyalkylene allyl ether such as polyoxyethylene alkyl allyl ether, polyoxyethylene alkyl phenyl ether, alkyl polyglucoside, and polyoxyethylene-polyoxypropylene block copolymer, etc.

[0202] As the above-mentioned vinyl surface conditioner, a surface conditioner containing vinyl polymers such as polyacetylene, polybutadiene, polyvinyl ether, and vinyl ester polymer can be cited.

[0203] As nonionic surface conditioners other than the above, for example, polyalkylene oxide fatty acid esters, acetylene diols, mineral oils, vegetable oils, fatty alcohols, and fatty acid amides can also be used.

[0204] As an anionic surface conditioner, examples include surface conditioners having a carboxyl group, surface conditioners having a phosphate group, surface conditioners having a phosphonic acid group, surface conditioners having a sulfo group, and surface conditioners having a sulfate group.

[0205] As a cationic surface conditioner, examples include surface conditioners having a quaternary ammonium salt group.

[0206] The surface conditioner that does not contain either fluorine atoms or silicon atoms can be modified as long as it does not contain either fluorine atoms or silicon atoms. For example, the above surface conditioner can introduce functional groups such as epoxy groups and / or (meth)acrylic groups into the side chain, and can also be crosslinked through the above functional groups. Specifically, for example, the above polyether surface conditioner can be a modified polyether such as polyether-modified (meth)acrylate.

[0207] As a surface modifier containing neither fluorine atoms nor silicon atoms, there is no particular limitation as long as it contains neither fluorine atoms nor silicon atoms. Specifically, for example, BYK-UV-3535, BYK-350, BYK-354, BYK-355 / 356, BYK-358N / 361N, BYK-381, BYK-391, BYK-394, BYK-3441, BYK-399, BYK-3440, BYK-3560, BYK-4500, BYK-4509, BYK-4510, BYK-4512, BYK-4513, BYKETOL-OK, BYK-051N, BYK-052N, BYK-054, BYK-055, BYK-057, BYK-354, BYK-392, BYK-1752, BYK-1759, BYK-1788, BYK-1790, BYK-1791, BYK-1794, BYK-1795, BYK-1797, BYK-1799 and BYK-361N (all manufactured by BYK-CHEMIE), TEGO Flow 300, TEGO Flow 370, TEGO Flow ZFS 460, TEGO Airex 910, TEGO Airex920, TEGO Airex 936 and TEGO Airex 966 (all manufactured by Evonik), FLOWLEN AC-202, FLOWLENAC-230, FLOWLEN AC-247, FLOWLEN AC-253, FLOWLEN AC-262H, FLOWLEN AC-265, FLOWLENAC-300, FLOWLEN AC-300VF, FLOWLEN AC-324, FLOWLEN AC-326F, FLOWLEN AC-380, FLOWLENAC-1190, FLOWLEN AC-1190HF and FLOWLEN AC-2300C (all manufactured by KYOEISHA CHEMICAL CO., LTD.), and SURFYNOL104E, SURFYNOL104H, SURFYNOL104A, SURFYNOL104PA, SURFYNOL420, SURFYNOL440, SURFYNOL465, SURFYNOL485, SURFYNOLDF110D, SURFYNOLAD01 and SURFYNOLMD-20 (all manufactured by Nissin Chemical Co., Ltd.).

[0208] The surface modifier containing neither fluorine atoms nor silicon atoms can be used alone as one kind, or two or more kinds can be used in combination.

[0209] The content of the surface conditioner containing neither a fluorine atom nor a silicon atom is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 1.0% by mass, and still more preferably 0.05 to 0.5% by mass relative to the total mass of the curable composition.

[0210] 〔Other components〕

[0211] The curable composition may contain other components other than those described above.

[0212] Examples of the other components other than those described above include monofunctional monomers, polymerization inhibitors, thermal crosslinking agents, thermal curing catalysts, chain transfer agents, sensitizers, and organic solvents.

[0213] <Monofunctional monomer>

[0214] The curable composition may contain a monofunctional monomer different from the above-mentioned respective monomers (cyclopolymerizable monomers, polyfunctional monomers, and monomers containing a thermally crosslinkable group) within the range that does not impair the effects of the present invention.

[0215] A monofunctional monomer is a monomer having only one polymerizable group.

[0216] From the viewpoint of curability, as the monofunctional monomer, a monofunctional radical polymerizable monomer is preferred, and a monofunctional ethylenically unsaturated monomer is more preferred.

[0217] Examples of the monofunctional ethylenically unsaturated monomer include monofunctional (meth)acrylate, monofunctional (meth)acrylamide, monofunctional aromatic vinyl compound, monofunctional vinyl ether, and monofunctional N-vinyl compound, and monofunctional (meth)acrylate or monofunctional N-vinyl compound is preferred.

[0218] As monofunctional (meth)acrylates, examples include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, tert-octyl (meth)acrylate, isoamyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, cyclohexyl (meth)acrylate, tert-butylcyclohexyl acrylate, 4-n-butylcyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-ethylhexyl diglycol (meth)acrylate, butoxyethyl (meth)acrylate, 2-chloroethyl (meth)acrylate, 4-bromobutyl (meth)acrylate, cyanoethyl (meth)acrylate, benzyl (meth)acrylate, butoxymethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-(2-methoxyethoxy)ethyl (meth)acrylate, 2-(2-butoxyethoxy)ethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 1H,1H,2H,2H-perfluorodecyl (meth)acrylate, 4-butylphenyl (meth)acrylate, phenyl (meth)acrylate, 2,4,5-tetramethylphenyl ester, 4-chlorophenyl (meth)acrylate, 2-phenoxymethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, glycidyl (meth)acrylate, glycidyloxybutyl (meth)acrylate, glycidyloxyethyl (meth)acrylate, glycidyloxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, phenyl glycidyl ether (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminopropyl (meth)acrylate, trimethoxyallylpropyl (meth)acrylate, trimethylsilylpropyl (meth)acrylate, polyethylene oxide monomethyl ether (meth)acrylate, polyethylene oxide (meth)acrylate, polyethylene oxide monoalkyl ether (meth)acrylate, dipropylene glycol (meth)acrylate, polypropylene oxide monoalkyl ether (meth)acrylate, 2-methacryloyloxyethyl succinate, 2-methacryloyloxyhexahydrophthalate, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, ethoxydiethylene glycol (meth)acrylate, butoxydiethylene glycol (meth)acrylate, trifluoroethyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, ethylene oxide (EO) modified phenol (meth)acrylate, EO modified cresol (meth)acrylate, EO modified nonylphenol (meth)acrylate, propylene oxide (PO) modified nonylphenol (meth)acrylate, EO modified-2-ethylhexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, dicyclopentyl (meth)acrylate, (3-ethyl-3-oxetanylmethyl) (meth)acrylate, phenoxyethylene glycol (meth)acrylate, 2-carboxyethyl (meth)acrylate and 2-(meth)acryloyloxyethyl succinate.,

[0219] From the aspect of improving heat resistance, as the monofunctional (meth)acrylate, the monofunctional (meth)acrylate having an aromatic ring or an aliphatic ring is preferred, and isobornyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate or dicyclopentyl (meth)acrylate is more preferred.

[0220] As monofunctional (meth)acrylamide, examples thereof include (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-n-butyl(meth)acrylamide, N-tert-butyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, and (meth)acryloylmorpholine.

[0221] As monofunctional aromatic vinyl compounds, examples thereof include styrene, dimethylstyrene, trimethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, methyl vinyl benzoate, 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3-hexylstyrene, 4-hexylstyrene, 3-octylstyrene, 4-octylstyrene, 3-(2-ethylhexyl)styrene, 4-(2-ethylhexyl)styrene, allylstyrene, isopropenylstyrene, butenylstyrene, octenylstyrene, 4-tert-butoxycarbonylstyrene, and 4-tert-butoxystyrene.

[0222] As monofunctional vinyl ethers, examples thereof include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexylmethyl vinyl ether, 4-methylcyclohexylmethyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentylethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexylmethyl vinyl ether, diethylene glycol mono vinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloroethoxyethyl vinyl ether, phenylethyl vinyl ether, and phenoxypolyethylene glycol vinyl ether.

[0223] As monofunctional N-vinyl compounds, examples thereof include N-vinyl-ε-caprolactam and N-vinylpyrrolidone.

[0224] The monofunctional monomers can be used alone or in combination of two or more.

[0225] When the curable composition contains a monofunctional monomer, its content is preferably 1.0 to 40.0% by mass, more preferably 5.0 to 25.0% by mass, based on the total mass of the curable composition.

[0226] <Polymerization inhibitor>

[0227] The curable composition preferably contains a polymerization inhibitor.

[0228] Examples of the polymerization inhibitor include p-methoxyphenol, quinones (e.g., hydroquinone, benzoquinone, and methoxybenzoquinone), phenothiazine, catechols, alkylphenols (e.g., dibutylhydroxytoluene (BHT)), alkylbisphenols, zinc dimethyldithiocarbamate, copper dimethyldithiocarbamate, copper dibutyldithiocarbamate, copper salicylate, thiodipropionates, mercaptobenzimidazole, phosphites, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl (TEMPOL), and aluminum tris(N-nitroso-N-phenylhydroxylamine) (alias: CupferronAl).

[0229] The polymerization inhibitor is preferably at least one selected from the group consisting of p-methoxyphenol, catechols, quinones, alkylphenols, TEMPO, TEMPOL, and aluminum tris(N-nitroso-N-phenylhydroxylamine), and more preferably at least one selected from the group consisting of p-methoxyphenol, hydroquinone, benzoquinone, BHT, TEMPO, TEMPOL, and aluminum tris(N-nitroso-N-phenylhydroxylamine).

[0230] The content of the polymerization inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.02 to 3.0% by mass, based on the total mass of the curable composition.

[0231] <Thermal crosslinking agent>

[0232] The curable composition may contain a thermal crosslinking agent. The thermal crosslinking agent is a compound different from the above-mentioned compounds (e.g., cyclopolymerizable monomers, monomers containing a thermally crosslinkable group, polyfunctional monomers, and monofunctional monomers) that can be contained in the curable composition.

[0233] The thermal crosslinking agent is a compound having two or more thermally crosslinkable groups in the molecule.

[0234] Examples of the thermally crosslinkable group include an epoxy group, an oxetanyl group, an isocyanate group, a blocked isocyanate group, and a hydroxyl group, as long as it is a group that undergoes a crosslinking reaction by heating.

[0235] As the thermal crosslinking agent, known thermal crosslinking agents can be used. For example, there can be mentioned epoxy compounds having at least two epoxy groups in the molecule, oxetane compounds having at least two oxetanyl groups in the molecule, polyisocyanate compounds having at least two isocyanate groups in the molecule, blocked isocyanate compounds, and melamine derivatives.

[0236] The above-mentioned epoxy compound is a compound having at least two epoxy groups in the molecule, and the β-position of the above-mentioned epoxy group can be substituted by an alkyl group.

[0237] As the above-mentioned epoxy compound, specifically, for example, bisphenol F type epoxy resin (as a commercial product, "Epotohto YDF-170, manufactured by TOHTO Chemical Industry Co., Ltd." etc.), xylenol type or bisphenol type epoxy resin or a mixture thereof (as a commercial product, "YX4000, manufactured by Japan Epoxy Resins Co., Ltd." etc.), heterocyclic epoxy resin having an isocyanurate skeleton etc. (as a commercial product, "TEPIC, manufactured by Nissan Chemical Industries, LTD." and "Araldite PT810, manufactured by Ciba Specialty Chemicals Co., Ltd." etc.), bisphenol A type epoxy resin, novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, halogenated epoxy resin (for example, low brominated epoxy resin, highly halogenated epoxy resin and brominated phenol novolac type epoxy resin etc.), allyl-containing bisphenol A type epoxy resin, triphenol methane type epoxy resin, diphenyldimethylol type epoxy resin, phenol biphenylene type epoxy resin, dicyclopentadiene type epoxy resin (as a commercial product "HP-720, HP-7200H, manufactured by Dainippon Ink and Chemicals, Inc." etc.), glycidylamine type epoxy resin (for example, diaminodiphenylmethane type epoxy resin, diglycidylaniline and triglycidylaminophenol etc.), glycidyl ester type epoxy resin (for example, diglycidyl phthalate, diglycidyl adipate, diglycidyl hexahydrophthalate and diglycidyl dimer acid), hydantoin type epoxy resin, alicyclic epoxy resin (for example, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate and dicyclopentadiene diepoxide etc. As a commercial product "GT-300, GT-400, ZEHPE3150, manufactured by DAICEL CHEMICAL INDUSTRIES, LTD." etc.), imide type alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolac type epoxy resin, tetraphenylol ethane type epoxy resin, glycidyl phthalate resin, tetraepoxypropylxylene acyl ethane resin, naphthalene-containing epoxy resin (naphthol biphenylaralkyl type epoxy resin, naphthol novolac type epoxy resin and 4-functional naphthalene type epoxy resin etc.).As commercial products such as "ESN-190, ESN-360, manufactured by NIPPON STEEL&SUMIKIN CHEMICAL Co., Ltd." and "HP-4032, EXA-4750, EXA-4700, manufactured by Dainippon Ink and Chemicals, Inc.", reaction products of polyphenol compounds obtained by the addition reaction of phenolic compounds and diene compounds (such as divinylbenzene and dicyclopentadiene, etc.) and epichlorohydrin, compounds obtained by epoxidizing the ring-opening polymer of 4-vinylcyclohexene-1-peroxide, epoxy resins having a linear phosphorus-containing structure, epoxy resins having a cyclic phosphorus-containing structure, α-methylstilbene-type liquid crystal epoxy resins, dibenzoyloxybenzene-type liquid crystal epoxy resins, azobenzene-type liquid crystal epoxy resins, azomethinebenzene-type liquid crystal epoxy resins, binaphthyl-type liquid crystal epoxy resins, oxazine-type epoxy resins, glycidyl methacrylate copolymer-based epoxy resins (as commercial products, such as "CP-50S, CP-50M, manufactured by Nippon Oil&Fats GmbH", etc.), copolymer epoxy resins of cyclohexyl maleimide and glycidyl methacrylate, bis(epoxypropoxyphenyl)fluorene-type epoxy resins, bis(epoxypropoxyphenyl)adamantane-type epoxy resins, etc.

[0238] The above oxetane compound is a compound having at least two oxetanyl groups in the molecule. Specifically, for example, bis[(3-methyl-3-oxetanylmethoxy)methyl] ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl] ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl] benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl] benzene, etc. can be cited.

[0239] The above polyisocyanate compound is a compound having at least two isocyanate groups in the molecule. For example, the polyisocyanate compound described in Japanese Patent Laid-Open No. 5-009407 can be used.

[0240] And as the above polyisocyanate compound, for example, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, bis(4-isocyanate-phenyl)methane, bis(4-isocyanate cyclohexyl)methane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate and other bifunctional isocyanates can also be cited; the addition reaction products of the above bifunctional isocyanates and polyfunctional alcohols (for example, trimethylolpropane, neopentyl glycol and glycerol) or alkylene oxide adducts of the above polyfunctional alcohols; cyclic trimers of hexamethylene diisocyanate, hexamethylene-1,6-diisocyanate and their derivatives, etc.

[0241] The above blocked isocyanate compound is a compound obtained by reacting a blocking agent with the above polyisocyanate compound.

[0242] As the above blocking agent, for example, alcohols such as isopropyl alcohol and tert-butyl alcohol can be cited; lactams such as ε-caprolactam; phenols such as phenol, cresol, p-tert-butylphenol, p-sec-butylphenol, p-sec-amylphenol, p-octylphenol and p-nonylphenol; heterocyclic hydroxy compounds such as 3-hydroxypyridine and 8-hydroxyquinoline; active methylene compounds such as dialkyl malonate, methyl ethyl ketoxime, acetylacetone, alkyl acetyloxyacetate oxime, acetone oxime and cyclohexanone oxime, etc.

[0243] As the blocked isocyanate compound, the compounds described in Japanese Patent Laid-Open No. 6-295060 can also be used.

[0244] As the above melamine derivative, for example, alkylated hydroxymethyl melamines such as hydroxymethyl melamine and hexamethylated hydroxymethyl melamine can be cited.

[0245] The content of the thermosetting crosslinking agent is preferably 0.1 to 20.0% by mass, more preferably 1.0 to 15.0% by mass, based on the total mass of the curable composition.

[0246] <Thermosetting catalyst>

[0247] The curable composition may contain a thermosetting catalyst.

[0248] The thermosetting catalyst is a compound having a function of promoting the crosslinking reaction of the thermosetting groups contained in the above monomers containing thermosetting groups.

[0249] As the above thermosetting catalyst, for example, the compounds described in paragraph

[0093] of Japanese Patent Laid-Open No. 2008-250074 can be used.

[0250] <Chain transfer agent>

[0251] The curable composition may contain a chain transfer agent.

[0252] The chain transfer agent is preferably a polyfunctional thiol from the viewpoint of being able to improve the reactivity of the photopolymerization reaction.

[0253] Examples of the polyfunctional thiol include aliphatic thiols, aromatic thiols, polyol poly(thioglycolate), polyol poly(3-mercaptopropionate), and poly(mercaptobutyrate).

[0254] The content of the chain transfer agent is preferably 0.01 to 20.0% by mass, more preferably 0.02 to 5.0% by mass, based on the total mass of the curable composition.

[0255] <Sensitizer>

[0256] The curable composition may contain a sensitizer.

[0257] Examples of the sensitizer include polynuclear aromatic compounds (e.g., pyrene, perylene, triphenylene, and 2-ethyl-9,10-dimethoxyanthracene), xanthene compounds (e.g., fluorescent yellow, eosin, erythrosine, rose red B, and rose bengal), cyanine compounds (e.g., thiacarbocyanine and oxacarbocyanine), merocyanine compounds (e.g., merocyanine and carbomerocyanine), thiazine compounds (e.g., thionine, methylene blue, and toluidine blue), acridine compounds (e.g., acridine orange, chloroflavin, and acriflavin), anthraquinones (e.g., anthraquinone), squarylium compounds (e.g., squarylium), coumarin compounds (e.g., 7-diethylamino-4-methylcoumarin), and dihydrochromanone compounds (e.g., dihydrochromanone).

[0258] The content of the sensitizer is preferably 1.0 to 15.0% by mass, more preferably 1.5 to 5.0% by mass, based on the total mass of the curable composition.

[0259] <Organic Solvents>

[0260] The curable composition may contain an organic solvent.

[0261] Examples of the organic solvent include (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether (PGME), dipropylene glycol monomethyl ether, and tripropylene glycol monomethyl ether; (poly)alkylene glycol dialkyl ethers such as ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol diethyl ether, and tetraethylene glycol dimethyl ether; (poly)alkylene glycol acetates such as diethylene glycol acetate; (poly)alkylene glycol diacetates such as ethylene glycol diacetate and propylene glycol diacetate; (poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monobutyl ether acetate and propylene glycol monomethyl ether acetate; ketones such as methyl ethyl ketone and cyclohexanone; lactones such as γ-butyrolactone; esters such as ethyl acetate, propyl acetate, butyl acetate, 3-methoxybutyl acetate (MBA), methyl propionate, and ethyl propionate; cyclic ethers such as tetrahydrofuran and dioxane; and amides such as dimethylformamide and dimethylacetamide.

[0262] The content of the organic solvent is preferably 70.0% by mass or less, more preferably 50.0% by mass or less, relative to the total mass of the curable composition. The lower limit can be 0% by mass relative to the total mass of the curable composition.

[0263] In addition to the above, the curable composition may contain additives such as a thermal polymerization initiator, a co-sensitizer, an ultraviolet absorber, an antioxidant, a fading inhibitor, and a basic compound.

[0264] 〔Physical properties〕

[0265] From the viewpoint of ejection stability when forming a coating film by the inkjet recording method described below, the pH (hydrogen ion concentration) of the curable composition is preferably 7 to 10, more preferably 7.5 to 9.5.

[0266] The above pH is a value measured for the object to be measured at 25°C using a pH meter (for example, pH meter model "HM-31", manufactured by DKK-TOA CORPORATION).

[0267] The viscosity of the curable composition is preferably 0.5 to 60 mPa·s, more preferably 2 to 40 mPa·s. The above viscosity is a value at 25°C.

[0268] The above viscosity is a value measured for the object to be measured at 25°C using a viscometer (for example, TV-22 type viscometer, manufactured by TOKI SANGYO CO., LTD.).

[0269] The surface tension of the curable composition is preferably 60 mN / m or less, more preferably 10 to 50 mN / m, and further preferably 15 to 45 mN / m.

[0270] The above surface tension is the value measured for the object to be measured at 25°C by the plate method using a surface tensiometer (automatic surface tensiometer, product name "CBVP-Z", manufactured by Kyowa Interface Science Co., Ltd.).

[0271] 〔Preparation method〕

[0272] As a preparation method of the curable composition, a known method can be used.

[0273] Specifically, for example, a method of separately adding or adding together various components contained in the curable composition and stirring using a stirrer (for example, a mixer, etc.) can be cited.

[0274] 〔Use〕

[0275] The curable composition is used to form an insulating layer adjacent to the conductive layer described later.

[0276] In other words, the curable composition is used to manufacture a laminate having a conductive layer and an insulating layer adjacent to the conductive layer. The use of the above laminate will be described later.

[0277] [Laminate]

[0278] The laminate of the present invention has a conductive layer and an insulating layer adjacent to the conductive layer.

[0279] 〔Insulating layer〕

[0280] The above insulating layer is a layer formed by the above curable composition.

[0281] Preferably, the above insulating layer contains a cured product of the above curable composition and / or decomposition products thereof.

[0282] The method for forming the insulating layer will be described later.

[0283] The thickness of the insulating layer is not particularly limited and can be appropriately adjusted according to the use and / or the shape of the object on which the insulating layer is formed. Among them, the thickness of the insulating layer is preferably 0.1 to 1000 μm, more preferably 10 to 500 μm.

[0284] The thickness of the above insulating layer is the arithmetic average of the thicknesses of 10 measured points obtained by measuring the height difference between the substrate and the insulating layer using a probe type step gauge.

[0285] The volume resistivity of the insulating layer is preferably 10 10 Ω·cm or more, more preferably 10 12 Ω·cm or more. The upper limit is not particularly limited, but can be 10 16 Ω·cm or less.

[0286] The volume resistivity of the insulating layer can be measured using a high-resistance resistivity meter.

[0287] The glass transition temperature (Tg) of the insulating layer is not particularly limited. However, in the case where the insulating layer is formed on a substrate having irregularities (for example, a printed wiring board on which an electronic component described later is mounted), it is preferably 0 to 100°C, more preferably 5 to 80°C, and still more preferably 10 to 60°C.

[0288] By satisfying the above necessary conditions for the glass transition temperature of the insulating layer, the internal stress generated in the insulating layer can be alleviated, and the crack inhibitory property is excellent and more preferable.

[0289] The glass transition temperature can be measured using a differential scanning calorimeter (for example, differential scanning calorimeter Q2000, manufactured by TA Instruments).

[0290] 〔Conductive layer〕

[0291] The conductive layer is a layer adjacent to the above insulating layer and having conductivity. Having conductivity means that the volume resistivity of the conductive layer is less than 10 8 Ω cm.

[0292] The method for forming the conductive layer will be described later.

[0293] The conductive layer is preferably a layer containing a metal. Examples of the above metal include gold, silver, platinum, palladium, iridium, osmium, ruthenium, rhodium, rhenium, nickel, titanium, cobalt, copper, chromium, manganese, iron, zirconium, tin, tungsten, molybdenum, vanadium, aluminum, magnesium, zinc, and lead.

[0294] Among them, from the viewpoint of conductivity, it is preferable that the conductive layer contains at least one metal selected from the group consisting of gold, silver, copper, platinum, nickel, and palladium, and more preferably contains at least one metal selected from the group consisting of silver and copper.

[0295] The conductive layer preferably contains the components contained in the conductive ink described later and / or these decomposition products and does not contain the solvent contained in the conductive ink.

[0296] The thickness of the conductive layer is not particularly limited and can be appropriately adjusted according to the use and / or the shape of the object on which the insulating layer is formed. Among them, the thickness of the conductive layer is preferably 0.1 to 100 μm, and more preferably 1 to 50 μm.

[0297] The thickness of the above conductive layer can be measured by the same method as the thickness of the insulating layer.

[0298] The volume resistivity of the conductive layer is preferably less than 10 8 Ω cm, 10 0 Ω cm or less. The lower limit is not particularly limited, but can be 10 -8 Ω cm or more.

[0299] The volume resistivity of the above conductive layer can be measured using a low-resistance resistivity meter.

[0300] The ratio of the film thickness of the insulating layer to the film thickness of the conductive layer in the laminate is preferably from 1 to 10,000, more preferably from 10 to 5,000, and still more preferably from 50 to 2,000.

[0301] 〔Use〕

[0302] The use of the laminate is not particularly limited, but examples thereof include an electromagnetic wave shielding member.

[0303] Among them, it is preferable that the laminate is used as an electromagnetic wave shielding member disposed on a printed wiring board. The printed wiring board refers to a board in which wiring is formed on at least one of the board and inside the board.

[0304] Examples of the printed wiring board include a flexible printed board, a rigid printed board, and a rigid-flexible board.

[0305] Examples of the board constituting the printed wiring board include a glass epoxy board, a ceramic board, a polyimide board, and a polyethylene terephthalate board. The board may have a single-layer structure or a multilayer structure.

[0306] The wiring provided on the printed wiring board is preferably copper wiring. For example, one end of the wiring is connected to an external power source, and the other end is connected to a terminal of an electronic component.

[0307] The above printed wiring board may be mounted with electronic components. There is no particular limitation on the electronic components, and examples thereof include a semiconductor chip, a capacitor, and a transistor.

[0308] When the laminate is used as an electromagnetic wave shielding member disposed on a printed wiring board, it is preferable to dispose the laminate so as to cover the electronic components that can be mounted on the printed wiring board.

[0309] [Manufacturing method of laminate]

[0310] The manufacturing method of the laminate of the present invention includes: Step 1 of forming an insulating layer by an inkjet recording method using a curable composition; and Step 2 of forming a conductive layer on the insulating layer using a conductive ink.

[0311] 〔Step 1〕

[0312] Step 1 is a step of forming an insulating layer by an inkjet recording method using a curable composition.

[0313] The details of the curable composition are as described above.

[0314] Hereinafter, each step that Step 1 can include will be described in detail.

[0315] <Inkjet recording method>

[0316] The inkjet recording method may be any one of a charge control method of ejecting ink using electrostatic attraction, an on-demand inkjet method (pressure pulse method) of applying vibration pressure of a piezoelectric element, an acoustic inkjet method of converting an electric signal into a sound beam and irradiating the ink and ejecting the ink using radiation pressure, and a thermal inkjet (Bubble Jet (registered trademark)) method of heating the ink to form bubbles and ejecting the ink using the generated pressure.

[0317] As the inkjet recording method, the method described in Japanese Patent Laid-Open No. 54-059936 is preferred, and more preferably an inkjet recording method in which the ink under the action of heat energy undergoes a sharp volume change and is ejected from the nozzle by the acting force based on this state change.

[0318] And, as the inkjet recording method, for example, the method described in paragraphs

[0093] to

[0105] of Japanese Patent Laid-Open No. 2003-306623 can also be cited.

[0319] As the inkjet head used in the inkjet recording method, for example, a shuttle method of using a short-size serial head to scan the head in the width direction of the substrate and perform recording and a line type method of using a line head in which recording elements are arranged corresponding to the entire area of at least one side of the substrate can be cited.

[0320] In the above line type method, by scanning the substrate in a direction crossing the arrangement direction of the recording elements, a pattern can be formed on the entire surface of the substrate, so a conveying system such as a carriage for scanning a short-size head is not required.

[0321] And, the movement of the carriage and the complex scanning control of the substrate are not required, and only the substrate is moved, so the forming speed can be increased compared with the shuttle method.

[0322] As an inkjet recording device for applying a curable composition using an inkjet recording method, for example, DMP-2850 (manufactured by FUJIFILM DIMATIX) can be cited.

[0323] The droplet ejection amount of the curable composition ejected from the nozzle of the inkjet head is preferably 1 to 100 pL (picoliters) per dot, more preferably 3 to 80 pL, and further preferably 3 to 20 pL.

[0324] (Substrate)

[0325] Preferably, the curable composition is applied to the substrate by an inkjet recording method.

[0326] The material of the base material is not particularly limited and can be selected according to the purpose. As the material of the base material, for example, synthetic resins such as polyimide, polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycarbonate, polyurethane, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, acrylic resin, AS resin (acrylonitrile-styrene resin), ABS resin (acrylonitrile-butadiene-styrene copolymer), triacetyl cellulose, polyamide, polyacetal, polyphenylene sulfide, polysulfone, epoxy resin, glass epoxy resin (an impregnated resin obtained by impregnating glass fiber with epoxy resin), melamine resin, phenolic resin, urea resin, alkyd resin, fluororesin, and polylactic acid; inorganic materials such as copper, steel, aluminum, silicon, soda glass, non-alkali glass, and indium tin oxide (ITO); and papers such as base paper, coated paper, coated paper, cast coated paper, resin coated paper, and synthetic paper can be cited.

[0327] From the aspects of insulation and the adhesion between the insulating layer and the base material, the base material is preferably a synthetic resin base material such as glass epoxy resin or polyimide.

[0328] The base material can be one layer or two or more layers. When the base material is two or more layers, the materials of the multiple layers can be the same or different.

[0329] The base material can be a printed wiring board. The details of the printed wiring board are as described above.

[0330] As the form of the base material, a sheet form or a film form is preferred.

[0331] The thickness of the base material is preferably 20 to 2000 μm.

[0332] The base material can have an ink receiving layer. The ink receiving layer refers to a coating formed on the base material to absorb the ink and fix the ink.

[0333] From the aspect of improving the homogeneity of the wetting and diffusion of the curable composition, the thickness of the ink receiving layer is preferably 1 to 20 μm.

[0334] Before applying the curable composition to the base material, the base material can be pretreated. As the pretreatment, for example, known methods such as ozone treatment, plasma treatment, corona treatment, primer treatment, and roughening treatment can be used.

[0335] The temperature of the base material when applying the curable composition is preferably 20 to 80 °C, more preferably 40 to 80 °C. When the temperature of the above-mentioned base material is 20 to 80 °C, while suppressing deformation of the base material caused by heat, etc., the drying of the curable composition can be promoted.

[0336] <Activating energy ray irradiation step>

[0337] Step 1 is preferably an active energy ray irradiation step of irradiating a coating film of the curable composition formed by the above inkjet recording method with active energy rays.

[0338] In the active energy ray irradiation step, examples of the active energy rays include ultraviolet rays (hereinafter also referred to as "UV"), visible light, and electron beams, and ultraviolet rays are preferred.

[0339] Examples of the light source of the active energy rays include mercury lamps, gas lasers, solid lasers, mercury lamps, metal halide lamps, ultraviolet fluorescent lamps, UV-LEDs (ultraviolet light-emitting diodes), and UV-LDs (ultraviolet lasers), and metal halide lamps, high-pressure mercury lamps, medium-pressure mercury lamps, low-pressure mercury lamps, or UV-LEDs are preferred.

[0340] The peak wavelength of the active energy rays is preferably 200 to 405 nm, more preferably 250 to 400 nm, and still more preferably 300 to 400 nm.

[0341] The illuminance of the active energy rays is preferably 4 W / cm 2 or more, more preferably 8 W / cm 2 or more, and still more preferably 10 cm 2 or more. There is no particular limitation on the upper limit. For example, it is 20 W / cm 2 .

[0342] The exposure of the active energy rays is preferably 0.1 to 10 J / cm 2 , more preferably 0.5 to 7.5 J / cm 2 .

[0343] <Heating step>

[0344] Step 1 is preferably a heating step including further performing a heat treatment after the above active energy ray irradiation step.

[0345] There is no particular limitation on the heating method, and known methods can be used.

[0346] The heating temperature is preferably 80 to 200 °C, more preferably 80 to 180 °C, and still more preferably 80 to 160 °C.

[0347] The heating time is preferably 1 to 180 minutes, more preferably 1 to 120 minutes.

[0348] In the manufacturing process of the laminate, Step 1 can be carried out only once or more than twice. When Step 1 is carried out more than twice, the conditions for each time can be the same or different.

[0349] Moreover, each process that can be included in Process 1 can be implemented only once or implemented two or more times. For example, the active energy ray irradiation process can be implemented two or more times.

[0350] Among them, from the aspect of easily forming an insulating layer with a desired thickness, it is preferable to use the application of the curable composition based on the inkjet recording method and the active energy ray irradiation process as one cycle, and repeat the above cycle. In addition, it is more preferable to implement a heating process after obtaining a coating film with a desired thickness by repeating the above cycle.

[0351] 〔Process 2〕

[0352] Process 2 is a process of forming a conductive layer on the insulating layer formed by Process 1 using a conductive ink.

[0353] Hereinafter, each process that can be included in Process 2 will be described in detail.

[0354] <Application of Conductive Ink>

[0355] Process 2 includes a process of applying a conductive ink onto the insulating layer formed by Process 1.

[0356] The conductive ink will be described later.

[0357] There is no particular limitation on the method of applying the conductive ink, and known methods can be used. For example, methods of coating the conductive ink and the inkjet recording method can be cited.

[0358] Among them, from the aspect that ejecting a small amount of droplets can make the thickness of the conductive layer formed by one application thinner, the inkjet recording method is preferable.

[0359] As the inkjet recording method for applying the conductive ink, for example, the inkjet recording method in the above Process 1 can be cited.

[0360] The temperature of the substrate with the insulating layer when applying the conductive ink is preferably 20 to 120 °C, and more preferably 40 to 100 °C.

[0361] <Curing Treatment Process>

[0362] Process 2 preferably further includes a curing treatment process of curing the conductive ink by performing at least one of a calcination treatment and a light irradiation treatment on the conductive ink applied to the insulating layer.

[0363] The curing treatment process can perform only one of the calcination treatment and the light irradiation treatment, or can perform both.

[0364] The calcination temperature in the calcination treatment is preferably 80 °C or higher, more preferably 100 °C or higher. Considering the aspect of being able to reduce damage to the substrate and the like, the upper limit is preferably 250 °C or lower, more preferably 200 °C or lower.

[0365] The calcination time in the calcination treatment is preferably 1 minute or longer. Considering the aspect of being able to reduce damage to the substrate and the like, the upper limit is preferably 120 minutes or shorter, more preferably 60 minutes or shorter.

[0366] As the light in the light irradiation treatment, for example, ultraviolet rays and infrared rays can be cited.

[0367] The peak wavelength of the above light is preferably 200 to 405 nm, more preferably 250 to 400 nm, and further preferably 300 to 400 nm.

[0368] The exposure amount during the light irradiation treatment is preferably 0.1 to 10000 J / cm 2 and more preferably 1 to 500 J / cm 2 .

[0369] Considering the aspect that the conductivity of the conductive layer is more excellent, the time from the end point of the application of the conductive ink to the start of the calcination treatment or the light irradiation treatment is preferably 60 seconds or shorter. In addition, the "end point of the application of the conductive ink" means the point in time when all the ink droplets of the conductive ink have landed on the insulating layer.

[0370] In the manufacturing process of the laminate, Process 2 can be carried out only once or can be carried out two or more times. In the case of carrying out Process 1 two or more times, the conditions for each time can be the same or different.

[0371] Moreover, each process that can be included in Process 2 can be carried out only once or can be carried out two or more times. For example, the light irradiation treatment can be carried out two or more times.

[0372] Among them, considering the aspect of easily forming a conductive layer with a desired thickness, it is preferable to take the application and curing treatment process of the conductive ink (preferably a heat treatment) as one cycle and repeat the above cycle.

[0373] 〔Conductive Ink〕

[0374] The conductive ink used in Process 2 will be described in detail.

[0375] The conductive ink refers to the ink used for forming the conductive layer.

[0376] As the conductive ink, for example, inks containing metal particles (hereinafter, also referred to as "metal particle inks"), inks containing metal complexes (hereinafter, also referred to as "metal complex inks"), and inks containing metal salts (hereinafter, also referred to as "metal salt inks") can be cited. Metal complex inks or metal salt inks are preferred.

[0377] From the aspect of ejection stability, the pH (hydrogen ion concentration) of the conductive ink is preferably 7 to 10, more preferably 7.5 to 9.5.

[0378] The above pH can be measured by the same method as the pH of the curable composition.

[0379] The viscosity of the conductive ink is preferably 1 to 100 mPa·s, more preferably 2 to 50 mPa·s, and further preferably 3 to 30 mPa·s. The above viscosity is the value at 25°C.

[0380] The above viscosity can be measured by the same method as the viscosity of the curable composition.

[0381] The surface tension of the conductive ink is preferably 20 to 45 mN / m, more preferably 25 to 40 mN / m.

[0382] The above surface tension can be measured by the same method as the surface tension of the curable composition.

[0383] <Metal particle ink>

[0384] The metal particle ink is, for example, a conductive ink in which metal particles are dispersed in a dispersion medium.

[0385] (Metal particles)

[0386] The metal particle ink contains metal particles.

[0387] As the metal constituting the metal particles, for example, nickel, titanium, cobalt, copper, chromium, manganese, iron, zirconium, tin, tungsten, molybdenum, vanadium, gold, silver, platinum, palladium, iridium, osmium, ruthenium, rhodium, rhenium, and alloys containing these metals can be cited.

[0388] From the aspect of conductivity, it is preferred that the metal constituting the metal particles contains at least one selected from the group consisting of silver, gold, platinum, nickel, palladium, and copper. More preferably, it contains at least one of silver and copper, and further preferably, it contains silver.

[0389] In the present invention, "metal particles" do not contain metal oxide particles such as titanium oxide.

[0390] In terms of the process suitability of the conductive layer, pattern formability, and thickness uniformity of the conductive layer, the average primary particle diameter of the metal particles is preferably 10 to 500 nm, more preferably 10 to 200 nm.

[0391] The average primary particle diameter of the metal particles is measured by the laser diffraction / scattering method.

[0392] Moreover, the metal particle ink may contain, as needed, metal particles having an average primary particle diameter of 500 nm or more.

[0393] In the metal particle ink, the content of the metal particles is preferably 10 to 90% by mass, more preferably 20 to 50% by mass, based on the total mass of the metal particle ink.

[0394] (Dispersant)

[0395] The metal particle ink may contain a dispersant that adheres to at least a part of the surface of the metal particles. The dispersant substantially forms metal colloid particles together with the metal particles. The dispersant has the function of coating the metal particles to improve the dispersibility of the metal particles and prevent aggregation.

[0396] The dispersant is preferably an organic compound capable of forming metal colloid particles. From the aspects of conductivity and dispersion stability, the dispersant is preferably an amine, carboxylic acid or its salt, alcohol, or resin dispersant.

[0397] In the metal particle ink, the content of the dispersant is preferably 0.5 to 50% by mass, more preferably 1 to 30% by mass, based on the total mass of the metal particle ink.

[0398] (Solvent)

[0399] The metal particle ink preferably contains a solvent.

[0400] Preferably, the solvent functions as a dispersion medium, and is also preferably a component different from the above-mentioned dispersant.

[0401] The type of the solvent is not particularly limited, and examples thereof include organic solvents such as hydrocarbons and alcohols, and water.

[0402] The solvent contained in the metal particle ink is preferably volatile. In addition, in this specification, unless otherwise specified, the boiling point refers to the standard boiling point.

[0403] From the aspects of the stability and calcination property of the metal particle ink, the boiling point of the solvent is preferably 50 to 250 °C, more preferably 70 to 220 °C, and further preferably 80 to 200 °C.

[0404] In the metal particle ink, the content of the solvent is preferably 1 to 50% by mass, more preferably 10 to 45% by mass, and still more preferably 20 to 40% by mass relative to the total mass of the metal particle ink.

[0405] (Resin)

[0406] The metal particle ink may contain a resin.

[0407] Examples of the resin include polyester, polyurethane, melamine resin, acrylic resin, styrene resin, polyether, and terpene resin.

[0408] (Thickener)

[0409] The metal particle ink may contain a thickener.

[0410] Examples of the thickener include clay minerals such as clay, bentonite, and lithium montmorillonite; cellulose derivatives such as methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and hydroxypropyl methyl cellulose; and polysaccharides such as xanthan gum and guar gum.

[0411] (Surfactant)

[0412] From the viewpoint of easily forming a uniform coating film, the metal particle ink may contain a surfactant.

[0413] (Method for manufacturing metal particle ink)

[0414] The metal particles may be commercially available products or particles manufactured by known methods.

[0415] Examples of the method for manufacturing the metal particles include a wet reduction method, a vapor phase method, and a plasma method, and preferably the wet reduction method capable of manufacturing metal particles having an average particle diameter of 200 nm or less with a narrowed particle size distribution.

[0416] In the manufacture of the metal particle ink, in order to adjust the contents of various components contained in the metal particle ink within a specified range, heat treatment may be performed. The heat treatment may be performed under reduced pressure or under normal pressure. And, when performed under normal pressure, it may be performed in the air or in an inert gas atmosphere.

[0417] (Metal complex ink)

[0418] The metal complex ink is, for example, a conductive ink in which a metal complex is dissolved in a solvent.

[0419] (Metal complex)

[0420] The metal complex ink contains a metal complex.

[0421] Examples of the metal constituting the metal complex include silver, copper, gold, aluminum, magnesium, tungsten, molybdenum, zinc, nickel, iron, platinum, tin, copper, and lead. From the perspective of conductivity, it is preferably at least one selected from the group consisting of silver, gold, platinum, nickel, palladium, and copper, more preferably at least one of silver and copper, and further preferably silver.

[0422] In the metal complex ink, the content of the metal is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, and further preferably 7 to 20% by mass in terms of metal element conversion relative to the total mass of the metal complex ink.

[0423] The metal complex is obtained, for example, by reacting a metal salt with a complexing agent. Examples of the method for producing the metal complex include a method of adding a metal salt and a complexing agent to an organic solvent and stirring for a specified time. The stirring method is not particularly limited, and can be appropriately selected from known methods such as a method of stirring using a stirrer, stirring blades, or a mixer, and a method of applying ultrasonic waves.

[0424] Examples of the metal salt include metal oxides, thio-citrates, sulfides, chlorides, cyanides, cyanates, carbonates, acetates, nitrates, nitrites, sulfates, phosphates, perchlorates, tetrafluoroborates, acetylacetonate complexes, and carboxylates. In addition, two or more salts can be combined.

[0425] Examples of the complexing agent include amines, ammonium carbamate-based compounds, ammonium carbonate-based compounds, ammonium bicarbonate compounds, and carboxylic acids. From the perspectives of conductivity and the stability of the metal complex, it is preferably at least one selected from the group consisting of ammonium carbamate-based compounds, ammonium carbonate-based compounds, amines, and carboxylic acids having 8 to 20 carbon atoms.

[0426] Preferably, the metal complex has a structure derived from the complexing agent and a structure derived from at least one selected from the group consisting of ammonium carbamate-based compounds, ammonium carbonate-based compounds, amines, and carboxylic acids having 8 to 20 carbon atoms.

[0427] In the metal complex ink, the content of the metal complex is preferably 10 to 90% by mass, more preferably 10 to 40% by mass relative to the total mass of the metal complex ink.

[0428] (Solvent)

[0429] The metal complex ink preferably contains a solvent.

[0430] The solvent is not particularly limited as long as it can dissolve various components such as the metal complex contained in the metal complex ink.

[0431] From the aspect of ease of manufacture, the boiling point of the solvent is preferably 30 to 300 °C, more preferably 50 to 200 °C, and still more preferably 50 to 150 °C.

[0432] The solvent is preferably contained in the metal complex ink such that the concentration of the metal ion relative to the metal complex (the amount of metal present as free ions relative to 1 g of the metal complex) is 0.01 to 3.6 mmol / g, and more preferably is contained such that it becomes 0.05 to 2 mmol / g. When the concentration of the metal ion is within the above range, the metal complex ink has excellent fluidity and exhibits excellent conductivity.

[0433] Examples of the solvent include hydrocarbons, cyclic hydrocarbons, aromatic hydrocarbons, urethanes, olefins, amides, ethers, esters, alcohols, thiols, thioethers, phosphines, and water, and aromatic hydrocarbons are preferred.

[0434] (Reducing agent)

[0435] The metal complex ink may contain a reducing agent.

[0436] When the metal complex ink contains a reducing agent, the reduction from the metal complex to the metal is promoted.

[0437] Examples of the reducing agent include metal borohydride salts, aluminum hydride salts, amines, alcohols, organic acids, reducing sugars, sugar alcohols, sodium sulfite, hydrazine compounds, dextrin, hydroquinone, hydroxylamine, ethylene glycol, glutathione, and oxime compounds.

[0438] In the metal complex ink, the content of the reducing agent is preferably 0.1 to 20% by mass, more preferably 0.3 to 10% by mass, and still more preferably 1 to 5% by mass relative to the total mass of the metal complex ink.

[0439] (Resin)

[0440] The metal complex ink may contain a resin.

[0441] When the metal complex ink contains a resin, the adhesion to the substrate and the insulating layer of the metal complex ink is improved.

[0442] Examples of the resin include polyesters, polyethylenes, polypropylenes, polyacetals, polyolefins, polycarbonates, polyamides, fluororesins, silicone resins, ethyl cellulose, hydroxyethyl cellulose, rosin, acrylic resins, polyvinyl chlorides, polysulfones, polyvinylpyrrolidones, polyvinyl alcohols, polyvinyl-based resins, polyacrylonitriles, polysulfides, polyamideimides, polyethers, polyarylesters, polyetheretherketones, polyurethanes, epoxy resins, vinyl ester resins, phenolic resins, melamine resins, and urea resins.

[0443] In the metal complex ink, the content of the resin is preferably 0.1 to 5% by mass relative to the total mass of the metal complex ink.

[0444] (Additive)

[0445] The metal complex ink may also contain additives within a range that does not impair the coating property or electromagnetic wave shielding property.

[0446] Examples of the additive include inorganic salts, organic salts, inorganic oxides such as silica, surface modifiers, wetting agents, crosslinking agents, antioxidants, rust inhibitors, heat stabilizers, surfactants, plasticizers, curing agents, thickeners, and silane coupling agents.

[0447] <Metal salt ink>

[0448] The metal salt ink is, for example, a conductive ink in which a metal salt is dissolved in a solvent.

[0449] The metal salt ink preferably does not contain the above-mentioned complexing agent.

[0450] (Metal salt)

[0451] The metal salt ink contains a metal salt.

[0452] Examples of the metal constituting the metal salt include silver, copper, gold, aluminum, magnesium, tungsten, molybdenum, zinc, nickel, iron, platinum, tin, copper, and lead. From the viewpoint of conductivity, it is preferred that the metal constituting the metal salt contains at least one selected from the group consisting of silver, gold, platinum, nickel, palladium, and copper, more preferably contains at least one of silver and copper, and still more preferably contains silver.

[0453] In the metal salt ink, the content of the metal is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 7 to 20% by mass in terms of metal element conversion relative to the total mass of the metal salt ink.

[0454] In the metal salt ink, from the viewpoints of surface resistivity and ejection stability, the content of the metal salt is preferably 10 to 90% by mass, more preferably 10 to 40% by mass relative to the total mass of the metal salt ink.

[0455] Examples of the metal salt include benzoates, halides, carbonates, citrates, iodates, nitrites, nitrates, acetates, phosphates, sulfates, sulfides, trifluoroacetates, and carboxylates of metals. In addition, two or more salts can be combined.

[0456] From the viewpoints of conductivity and storage stability, the metal salt is preferably a metal carboxylate.

[0457] The carboxylic acid for forming the metal carboxylate is preferably at least one selected from the group consisting of formic acid and carboxylic acids having 1 to 30 carbon atoms, more preferably carboxylic acids having 8 to 20 carbon atoms, and still more preferably fatty acids having 8 to 20 carbon atoms. The fatty acid may be either straight-chain or branched-chain, and may also have substituents.

[0458] The metal salt may be a commercially available product or a salt produced by a known method. The silver salt is produced, for example, by the following method.

[0459] A silver compound (such as silver acetate) serving as a source of silver and formic acid or a fatty acid having 1 to 30 carbon atoms in an amount equivalent to the molar equivalent of the silver compound are added to an organic solvent such as ethanol. Stirring is carried out for a specified time using an ultrasonic stirrer, and the resulting precipitate is washed with ethanol and decanted. All of these steps can be carried out at room temperature (25 °C). The mixing ratio of the silver compound to formic acid or the fatty acid having 1 to 30 carbon atoms is preferably 1:2 to 2:1, more preferably 1:1, in terms of molar ratio.

[0460] (Additive)

[0461] The metal salt ink may contain additives such as a solvent, a reducing agent, and a resin.

[0462] The preferred modes of the solvent, the reducing agent, and the resin are the same as those of the various components that can be contained in the metal complex ink, respectively.

[0463] Examples

[0464] Hereinafter, the present invention will be described in further detail based on examples.

[0465] The materials, amounts used, ratios, treatment contents, treatment steps, etc. shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0466] [Curable Composition]

[0467] Each component contained in the curable composition of the present invention and the preparation method of the curable composition will be described.

[0468] Mixtures of the various components and contents shown in Table 1 below were prepared, and using a mixer (product name "L4R", manufactured by Silverson Nippon Limited), stirring was carried out at 25 °C and 5000 revolutions per minute for 20 minutes to obtain the curable compositions of the respective examples and comparative examples.

[0469] In addition, the contents of the various components in the table are in parts by mass.

[0470] [Cyclopolymerizable Monomer]

[0471] ·AOMA: Methyl α-(allyloxymethyl)acrylate (manufactured by NIPPON SHOKUBAI CO., LTD.)

[0472] ·RHMA-D: Dimethyl 2,2'-[oxybis(methylene)]bisacrylate

[0473] RHMA-D was synthesized according to the procedure described in Japanese Patent Laid-Open No. 2015-172120.

[0474] [Monomer containing a thermally crosslinkable group]

[0475] ·4HBAGE: 4-Hydroxybutyl acrylate glycidyl ether (manufactured by Shinryo Corporation)

[0476] ·GMA: Glycidyl methacrylate

[0477] ·4HBA: 4-Hydroxybutyl acrylate

[0478] [Polyfunctional monomer]

[0479] ·HDDA: 1,6-Hexanediol diacrylate (product name "SR238", manufactured by Sartomer Company, Inc.)

[0480] ·PEGDA: Polyethylene glycol (400) diacrylate (manufactured by Sartomer Company, Inc.)

[0481] [Photoinitiator]

[0482] ·Omnirad379: 2-(Dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-1-butanone (manufactured by IGM Resins B.V.)

[0483] ·ITX: 2-Isopropylthioxanthone (product name "SPEEDCURE ITX", manufactured by LAMBSON)

[0484] ·SC7010: Product name "SpeedCure7010" (manufactured by LAMBSON)

[0485] [Surface modifier]

[0486] ·BYK-UV-3535: Modified polyether-based surface modifier (manufactured by BYK Chemie, does not contain either fluorine atoms or silicon atoms)

[0487] · BYK-381: Acrylic surface modifier (manufactured by BYK Chemie, containing neither fluorine atoms nor silicon atoms)

[0488] · F-554: Fluorine-containing and lipophilic oligomer (product name "MEGAFACE F-554", manufactured by DIC CORPORATION)

[0489] · BYK-307: Silicone surface modifier (manufactured by BYK Chemie)

[0490] 〔Polymerization inhibitor〕

[0491] · MEHQ: p-Methoxyphenol (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0492] 〔Thermal crosslinking agent〕

[0493] · E402-B80: Blocked isocyanate (manufactured by Asahi Kasei Corporation)

[0494] 〔Other components (monofunctional monomers)〕

[0495] · NVC: N-Vinyl-ε-caprolactam (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0496] · IBOA: Isobornyl acrylate (product name "SR506D", manufactured by Sartomer Company, Inc)

[0497] [Conductive ink]

[0498] Silver neodecanoate (30 g) was added to a 200 mL three-necked flask. Then, terpineol (30 g) and xylene (40 g) were added and stirred to obtain a solution containing a silver salt. The obtained solution was filtered using a PTFE (polytetrafluoroethylene) membrane filter with a pore size of 0.45 μm to obtain a conductive ink.

[0499] [Fabrication of laminate]

[0500] 〔Preparation of electronic substrate〕

[0501] An electronic substrate as shown in Figure 1 and Figure 2 was prepared as the electronic substrate 10. Hereinafter, the dimensions of the electronic substrate 10 are shown.

[0502] Width of the ground electrode 13: 900 μm

[0503] Height of the grounding electrode 13 (height of the portion protruding from the wiring substrate 11): 25 μm

[0504] Area surrounded by the grounding electrode 13: 20 mm × 18 mm

[0505] Height of the electronic component 12A: 200 μm

[0506] Height of the electronic component 12B: 500 μm

[0507] Distance between the electronic component 12B and the grounding electrode: 200 μm

[0508] 〔Formation of the insulating layer〕

[0509] The curable composition prepared by the above method was filled into the ink core (for 10 picoliters) of an inkjet recording apparatus (product name “DMP-2850”, manufactured by FUJIFILM DIMATIX). Regarding the image recording conditions, the resolution was set to 1270 dpi (dots per inch), and the droplet ejection amount was set to 10 picoliters per dot.

[0510] Hereinafter, the step of applying the curable composition using the inkjet recording apparatus within the target range and irradiating ultraviolet rays was defined as one cycle. The above ultraviolet ray irradiation was performed using an ultraviolet ray irradiation apparatus (product name “UVSpot Cure 0mniCure S2000”, manufactured by LumenDynamics) provided laterally to the inkjet head. The illuminance of the ultraviolet rays was set to 12 W / cm 2 , and the resolution and frequency of the inkjet recording apparatus were adjusted so that the exposure amount per one cycle was 1.8 J / cm 2 . Also, the time from the point of applying the curable composition to the start of ultraviolet ray irradiation was set to 0.2 seconds.

[0511] In the region A where the electronic component 12A and the electronic component 12B in Figure 1 were not arranged, the above cycle was repeated twice. Next, in the region B where the above region A and the electronic component 12A in Figure 1 were arranged, the above cycle was repeated three times. Further, in the above region A and region B and the region C where the electronic component 12B in Figure 1 was arranged, the above cycle was repeated twice.

[0512] The maximum value of the thickness of the exposed curable composition based on the surface of the wiring substrate 11 of the laminate obtained as above was 700 μm. Also, the thickness of the exposed curable composition based on the surface of the electronic component 12B was 200 μm.

[0513] Thereafter, the electronic substrate on which the exposed curable composition was laminated was heated on a hot plate at 150 °C for 1 hour, thereby forming an insulating layer. Thus, a laminate having the insulating layer 31 on the electronic substrate 10 was obtained. Figure 3 as shown in

[0514] [Formation of Conductive Layer]

[0515] The conductive ink obtained by the above method was filled into an ink cartridge (for 10 picoliters) of an inkjet recording device (product name "DMP-2850", manufactured by FUJIFILM DIMATIX). Regarding the image recording conditions, the resolution was set to 1270 dpi, and the droplet volume was set to 10 picoliters per dot.

[0516] The electronic substrate 10 on which the insulating layer 31 was formed was preheated to 60 °C. The cycle of applying the conductive ink onto the insulating layer 31 by the above inkjet recording device and heating at 160 °C for 1 hour using an oven was repeated 8 times.

[0517] Thus, a conductive layer having a metallic luster and a thickness of 3.2 μm was formed on the insulating layer 31.

[0518] Through the above steps, a laminate having the electronic substrate 10, the insulating layer 31, and the conductive layer 32 in this order was obtained. Figure 4 as shown in

[0519] [Evaluation]

[0520] [Adhesion]

[0521] The adhesion between the conductive layer and the insulating layer was evaluated according to the following steps.

[0522] After manufacturing the laminates of each example and each comparative example, they were left at 25 °C for 1 hour. Thereafter, a tape piece of Cellotape (registered trademark, No. 405, manufactured by Nichiban Co., Ltd., width 12 mm, hereinafter also simply referred to as "tape") was attached to the conductive layer of the laminates of each example and each comparative example. Then, the adhesion between the conductive layer and the insulating layer was evaluated by peeling the tape piece from the conductive layer. The attachment and peeling of the tape were performed by the following method.

[0523] The tape was taken out at a prescribed speed and cut into a length of about 20 mm to obtain a tape piece. The obtained tape piece was laminated on the exposed conductive layer of the laminates of each example and each comparative example, and the region with a width of 9 mm and a length of 9 mm at the center of the tape piece was attached with a finger, and rubbed forcefully with a fingertip. After attaching the tape piece, the end of the tape piece was grasped and peeled at an angle close to 60° over 0.5 to 1.0 seconds.

[0524] The presence or absence of adherends on the peeled tape pieces and the peeling of the conductive layer in the laminate were visually observed. The adhesion between the conductive layer and the insulating layer was evaluated according to the following evaluation criteria.

[0525] A: No adherends were observed on the tape piece, and no peeling of the conductive layer was observed.

[0526] B: Some adherends were observed on the tape piece and no peeling of the conductive layer was observed, or no adherends were observed on the tape piece and some peeling of the conductive layer was observed, but within the allowable range.

[0527] C: Adherends were observed on the tape piece, and peeling was observed on most of the conductive layer, outside the allowable range.

[0528] 〔Smoothness〕

[0529] Using a laser microscope (VK-X3000, manufactured by KEYENCE CORPORATION), the surface roughness of the exposed conductive layer of the laminate of each example and each comparative example was measured. Based on the obtained value of the arithmetic mean roughness Ra, the smoothness of the conductive layer was evaluated according to the following evaluation criteria.

[0530] A: The arithmetic mean roughness Ra is less than 20 μm

[0531] B: The arithmetic mean roughness Ra is 20 μm or more and less than 50 μm

[0532] C: The arithmetic mean roughness Ra is 50 μm or more and less than 80 μm

[0533] D: The arithmetic mean roughness Ra is 80 μm or more

[0534] 〔Crack Inhibition〕

[0535] According to the steps of the above [Fabrication of Laminate], a laminate having an insulating layer 31 on the electronic substrate 10 was obtained. Figure 3 as shown.

[0536] The obtained laminate was placed in a small environmental test chamber SH-242 (manufactured by ESPEC Corporation), and a heating and cooling cycle from -40°C to 100°C was performed at 2 cycles / hour for 100 cycles.

[0537] Thereafter, the appearance of the laminate was observed with a magnifying glass, the number of sites where cracks occurred in the insulator was counted, and the crack inhibition was evaluated according to the following evaluation criteria.

[0538] A: 0 sites

[0539] B: 1 site

[0540] C: 2 or more sites

[0541] [Peelability]

[0542] The peelability of the insulating layer from the module was evaluated by the following steps.

[0543] According to the steps of [Fabrication of the laminate] described above, a laminate as shown in Figure 3 was obtained, which had an insulating layer 31 on the electronic substrate 10.

[0544] Thereafter, using a hot plate, the laminate was heated to 120 °C and the insulating layer was peeled off from the electronic substrate sequentially from the four corners using tweezers, and the range where the insulating layer could be peeled off was visually observed. The peelability was evaluated according to the ratio of the area where the insulating layer could be peeled off to the printing area based on the following evaluation criteria.

[0545] A: 80% or more of the printing area

[0546] B: 50% or more and less than 80% of the printing area

[0547] C: Less than 50% of the printing area

[0548] [Results]

[0549] Table 1 shows the compositions of the curable compositions of each example and each comparative example, and the evaluation results of the adhesion between the conductive layer and the insulating layer and the smoothness of the conductive layer.

[0550] Moreover, Table 2 shows the evaluation results of the crack suppression property and peelability of each example.

[0551] In Table 2, the column "A / B" represents the mass ratio of the content of the A) cyclopolymerizable monomer to the content of the B) monomer containing a thermally crosslinkable group (content of cyclopolymerizable monomer / content of monomer containing a thermally crosslinkable group).

[0552] In Table 2, the column "A / C" represents the mass ratio of the content of the A) cyclopolymerizable monomer to the content of the C) polyfunctional monomer (content of cyclopolymerizable monomer / content of polyfunctional monomer).

[0553]

[0554] [Table 2]

[0555] A / B A / C Crack inhibition Peelability Example 1 27.5 1.7 A A Example 2 10.4 1.6 A B Example 3 1.8 1.1 A B Example 4 2.6 2.9 A B Example 5 27.5 1.7 B A Example 6 27.5 1.7 B B Example 7 27.5 1.7 A B Example 8 27.5 1.7 A A Example 9 27.5 1.7 A A Example 10 27.5 1.7 A A Example 11 16.5 0.6 A A Example 12 40.0 10.1 B B Example 13 4.0 0.1 A B Example 14 112.8 1.7 B B Example 15 27.5 1.7 B B Example 16 25.0 1.8 B B Example 17 27.5 1.7 A A

[0556] From the results shown in Table 1 above, it was confirmed that the curable composition of the present invention was more excellent in effects than the curable compositions of Comparative Examples 1 to 8 which did not contain any of the cyclopolymerizable monomer, the monomer containing a thermally crosslinkable group, the polyfunctional monomer, and the surface modifier not containing any of fluorine atoms and silicon atoms.

[0557] It was confirmed that when the cyclopolymerizable monomer contains AOMA, the peelability is more excellent, and when the cyclopolymerizable monomer is AOMA, the smoothness and crack inhibition property of the conductive layer are further excellent (comparison between Example 1 and Examples 5 to 6).

[0558] It was confirmed that when the content of the monomer containing a thermally crosslinkable group is 0.5% by mass or more and less than 5.0% by mass relative to the total mass of the curable composition, the effects and peelability of the present invention are more excellent (comparison between Examples 1 to 4 and Example 14).

[0559] It was confirmed that when the monomer containing a thermally crosslinkable group is the compound represented by the formula (B2), the smoothness of the conductive layer is more excellent. In the case of the compound represented by the formula (B2) in which the number of carbon atoms of R 3 is 2 or more, the adhesion between the conductive layer and the insulating layer, the crack inhibition property, and the peelability are further excellent (comparison between Example 1 and Examples 15 to 16).

[0560] It was confirmed that when the mass ratio of the content of the cyclopolymerizable monomer to the content of the monomer containing a thermally crosslinkable group is 5.0 to 40.0, the effects and peelability of the present invention are excellent (comparison between Example 1, Examples 3 to 4, and Examples 13 to 14).

[0561] It was confirmed that when the mass ratio of the content of the cyclopolymerizable monomer to the content of the polyfunctional monomer is 1.0 or more, the adhesion between the conductive layer and the insulating layer is more excellent. Further, it was confirmed that when the mass ratio of the content of the cyclopolymerizable monomer to the content of the polyfunctional monomer is 7.0 or less, the smoothness, crack inhibition property, and peelability of the conductive layer are more excellent (comparison between Example 1 and Examples 11 to 12).

[0562] It was confirmed that when the mass ratio of the content of the alkylbenzophenone compound to the content of the thioxanthone compound is 1.5 or less, the effects and peelability of the present invention are more excellent (comparison between Example 1 and Example 7).

[0563] Symbol Explanation

[0564] 10 - electronic substrate, 11 - wiring substrate, 12, 12A, 12B - electronic components, 13 - ground electrode, 31 - insulating layer, 32 - conductive layer.

Claims

1. A curable composition for forming an insulating layer adjacent to a conductive layer, wherein the curable composition contains a cyclopolymerizable monomer, a monomer having a thermally crosslinkable group, a polyfunctional monomer, a photoinitiator, and a surface modifier containing neither a fluorine atom nor a silicon atom.

2. The curable composition according to claim 1, wherein the mass ratio of the content of the cyclopolymerizable monomer to the content of the monomer having a thermally crosslinkable group is 5.0 to 40.0, and the mass ratio of the content of the cyclopolymerizable monomer to the content of the polyfunctional monomer is 1.0 to 7.

0.

3. The curable composition according to claim 1, wherein the cyclopolymerizable monomer is α-allyloxymethyl methacrylate.

4. The curable composition according to claim 1, wherein the content of the monomer having a thermally crosslinkable group is 0.5% by mass or more and less than 5.0% by mass relative to the total mass of the curable composition.

5. The curable composition according to claim 1, wherein the monomer having a thermally crosslinkable group is a compound represented by formula (B2), [Chemical formula 1] In formula (B2), R 1 and R 2 each independently represents a hydrogen atom or an alkyl group, R 3 represents an alkylene group which may have an ether bond.

6. The curable composition according to claim 1, wherein the conductive layer contains silver or copper.

7. A laminate containing a conductive layer and an insulating layer formed using the curable composition according to any one of claims 1 to 6.

8. The laminate according to claim 7, wherein, The laminate is used as an electromagnetic wave shielding member disposed on a printed wiring board.

9. A method for manufacturing a laminate, comprising: Step 1, forming an insulating layer by an inkjet recording method using the curable composition according to any one of claims 1 to 6; and Step 2, forming a conductive layer on the insulating layer using a conductive ink.

10. The method for manufacturing a laminate according to claim 9, wherein Step 1 includes a step of irradiating the coating film of the curable composition with active energy rays and then heating it.

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