Copper-clad laminate, copper foil with resin, and circuit board using them

Abstract

To provide a copper-clad laminate reducing transmission loss of a high-speed signal transmission substrate, and excellent in adhesion and heat resistance, and to provide a copper foil with a resin, and a circuit board using the laminate and the foil.SOLUTION: A copper-clad laminate includes: an insulation layer containing an aromatic polymer having a structural unit derived from a bifunctional aromatic compound where two carbon-carbon unsaturated double bonds are bonded to an aromatic ring; and a surface-treated copper foil having a copper fine roughened particle treatment layer on at least one surface side of the copper foil, on one surface or both surfaces of the insulation layer. The fine roughened particle treatment layer is composed of fine copper particles each having a particle diameter of 40-200 nm, has a heatproof treatment layer composed of nickel, or nickel and phosphorus on the fine roughened particle treatment layer, has a corrosion prevention treatment layer containing at least chrome on the heatproof treatment layer, and has a silane coupling agent layer on the corrosion prevention treatment layer. A nickel attachment amount in the heatproof treatment layer is 30-60 mg / m2.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a copper-clad laminate, a copper foil with resin, and a circuit board using them.

Background Art

[0002] For high-frequency compatible high-speed signal transmission substrates, various metal foils, particularly copper foils, are used as conductors. However, in the future, it is necessary to support 5G, WiGig (Wireless Gigabit), etc. that use signals at even higher frequencies than currently. Therefore, it is required to further reduce the transmission loss of the substrate.

[0003] In such problems, in order to reduce transmission loss, it is necessary to improve the resin base material and copper foil constituting the substrate. That is, it is necessary to reduce the transmission loss caused by the dielectric of the resin base material and further reduce the conductor loss of the copper foil.

[0004] Regarding the improvement on the copper foil side, conventionally, the conductor loss has been reduced by reducing the surface roughness, etc. However, there are problems that when the surface roughness is reduced, the adhesion and heat resistance to the resin, which are essential as the basic characteristics of the copper foil used for the substrate, decrease, and when the surface roughness is increased, the transmission loss increases, and it has been considered difficult to achieve both transmission characteristics and basic characteristics. This is presumably because when the roughness is reduced, the adhesion area with the resin decreases and it becomes difficult to obtain adhesion due to the anchor effect. As a result, the peel strength decreases and the heat resistance deteriorates. When the roughness is increased, the resistance of the current flowing on the copper foil surface increases, resulting in an increase in transmission loss.

[0005] In addition, as a surface-treated copper foil for forming a high-frequency signal transmission circuit, it has been reported that the roughened layer that affects the transmission characteristics is composed of a non-conductive copper composite compound instead of conventional metallic copper to prevent electricity from flowing and reduce the conductive loss due to the roughening treatment (Patent Document 1).

[0006] In addition, in the surface-treated copper foil for printed wiring boards, it is also known to adjust the average height of roughened particles in the silane coupling agent layer that affects transmission characteristics, or to adjust the amount of nickel element in the metal treatment layer containing nickel (Patent Document 2).

[0007] On the other hand, it has been reported that the low dielectric characteristics can be improved by using a resin containing a modified polyphenylene ether compound from the side surface of the resin substrate (Patent Document 3).

[0008] However, in the technique described in Patent Document 1 above, since barrier treatment, chromate treatment, etc. are not performed, there is a problem that it is particularly inferior in heat resistance.

[0009] On the other hand, in the technique described in Patent Document 2 above, since the treatment amount of the metal treatment layer that functions as a barrier treatment layer is small, there is a problem that it becomes difficult to ensure heat resistance in a high temperature range (for example, 150 °C or higher).

[0010] Furthermore, at present, in order to obtain more excellent transmission characteristics for the resin substrate, resins containing compounds having a lower dielectric tangent are being searched for.

Prior Art Documents

Patent Documents

[0011]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

[0012] The present invention has been made in view of such circumstances, and an object thereof is to provide a copper-clad laminate, a copper foil with resin, and a highly reliable circuit board using them, which can reduce the transmission loss of a high-speed signal transmission board and are excellent in adhesion and heat resistance.

[0013] The copper-clad laminate according to one aspect of the present invention is a copper-clad laminate including an insulating layer containing a cured product of a resin composition and surface-treated copper foil on one or both sides of the insulating layer, wherein the resin composition contains a polymer having a structural unit represented by the following formula (1) in the molecule,

Chemical formula

[0014] 2 It is characterized by being so.

Brief Description of the Drawings

[0015] ​

Figure 1

Figure 2

Figure 3

Figure 4

Mode for Carrying Out the Invention

[0016] The copper-clad laminate according to one aspect of the present invention is a copper-clad laminate including an insulating layer containing a cured product of a resin composition and surface-treated copper foil on one or both sides of the insulating layer. Further, the copper foil with resin according to another aspect of the present invention is a copper foil with resin including a resin layer containing a resin composition or a semi-cured product of the resin composition and surface-treated copper foil on one side of the resin layer.

[0017] According to the present invention, it is possible to reduce the transmission loss of a high-speed signal transmission substrate, and to provide a copper-clad laminate, a copper foil with resin, and a highly reliable circuit board using them, which are excellent in adhesion and heat resistance.

[0018] Hereinafter, each configuration of the copper-clad laminate and the copper foil with resin according to the present embodiment will be specifically described. In the following description, each reference numeral represents: 1 copper foil, 2 fine roughened particle treatment layer, 3 heat treatment layer, 4 rust prevention treatment layer, 5 silane coupling agent layer, 11 copper-clad laminate, 12, 32 insulating layer, 13 surface-treated copper foil, 14 wiring, 21 wiring board, 31 copper foil with resin.

[0019] <Copper-Clad Laminate> As shown in Fig. 2, the copper-clad laminate 11 of the present embodiment includes an insulating layer 12 containing a cured product of a resin composition described below, and copper foil (surface-treated copper foil) 13 described below on one or both sides of the insulating layer 12. With such a configuration, it is possible to provide a highly reliable copper-clad laminate with reduced transmission loss while having adhesiveness and heat resistance.

[0020] <Insulating layer> First, in the present embodiment, the cured product of the resin composition refers to a product in which the curing reaction has proceeded and the resin has crosslinked to a state where it does not melt even when heated. Further, the semi-cured product of the resin composition is a state in which the resin composition has been cured halfway to such an extent that it can be further cured. That is, the semi-cured product is a semi-cured (B-staged) resin composition. For example, when the resin composition is heated, first, the viscosity gradually decreases, and then, curing starts and the viscosity gradually increases. In such a case, examples of the semi-cured state include the state after the viscosity starts to increase and before complete curing.

[0021] The insulating layer included in the copper-clad laminate of the present embodiment contains a cured product of the resin composition described below. Further, the insulating layer may contain a glass substrate described later. The thickness of the insulating layer is not particularly limited, but is about 20 to 800 μm.

[0022] The resin composition constituting the insulating layer of the present embodiment is a resin composition characterized by containing a polymer having a structural unit represented by the following formula (1) in the molecule.

[0023] [Chemical formula] In formula (1), Z represents an arylene group. R1 to R3 are each independent. That is, R1 to R3 may each be the same group or different groups. Further, R1 to R3 represent a hydrogen atom or an alkyl group. R4 to R6 are each independent. That is, R4 to R6 may each be the same group or different groups. Further, R4 to R6 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0024] The present inventors have made various studies to provide a resin composition having excellent heat resistance and low dielectric properties as compared with conventional resin compositions, for example, the resin composition described in Patent Document 1. Specifically, the present inventors focused on the polymer, that is, a polymer having a structural unit represented by the following formula (1) in the molecule, and found that a cured product obtained by curing this has excellent heat resistance and low dielectric properties.

[0025] From the above, the resin composition is a resin composition from which a cured product having low dielectric properties and high heat resistance can be obtained.

[0026] (Polymer) The polymer is not particularly limited as long as it has a structural unit represented by the formula (1) in the molecule. Further, the polymer may have a structural unit other than the structural unit represented by the formula (1) as long as it has a structural unit represented by the formula (1) in the molecule. Further, the polymer may contain a repeating unit in which the structural unit represented by the formula (1) is repeatedly bonded, or a repeating unit in which the structural unit represented by the formula (1) is repeatedly bonded and a repeating unit in which a structural unit other than the structural unit represented by the formula (1) is repeatedly bonded are randomly bonded polymers. That is, when having a structural unit other than the structural unit represented by the formula (1), it may be a block copolymer or a random copolymer.

[0027] The arylene group in the formula (1) is not particularly limited. Examples of this arylene group include monocyclic aromatic groups such as a phenylene group, and polycyclic aromatic groups in which the aromatic is not a monocyclic ring but a polycyclic aromatic such as a naphthalene ring. Further, the arylene group includes derivatives in which a hydrogen atom bonded to the aromatic ring is substituted with a functional group such as an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group.

[0028] In the formula (1), the alkyl groups represented by R1 to R3 are not particularly limited. For example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. Specifically, for example, a methyl group, an ethyl group, a propyl group, a hexyl group, and a decyl group can be mentioned.

[0029] In the formula (1), the alkyl groups having 1 to 6 carbon atoms represented by R4 to R6 are not particularly limited. Specifically, for example, a methyl group, an ethyl group, a propyl group, and a hexyl group can be mentioned.

[0030] The polymer preferably includes an aromatic polymer having, as a structural unit represented by the formula (1), a structural unit derived from a bifunctional aromatic compound in which two carbon-carbon unsaturated double bonds are bonded to an aromatic ring. The structural unit derived from the bifunctional aromatic compound is a structural unit obtained by polymerizing the bifunctional aromatic compound. Further, in the present specification, the aromatic polymer is also referred to as a divinyl aromatic polymer.

[0031] The bifunctional aromatic compound is not particularly limited as long as it is a bifunctional aromatic compound having two carbon-carbon unsaturated double bonds bonded to an aromatic ring. Examples of the bifunctional aromatic compound include m-divinylbenzene, p-divinylbenzene, 1,2-diisopropenylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,3-divinylnaphthalene, 1,8-divinylnaphthalene, 1,4-divinylnaphthalene, 1,5-divinylnaphthalene, 2,3-divinylnaphthalene, 2,7-divinylnaphthalene, 2,6-divinylnaphthalene, 4,4'-divinylbiphenyl, 4,3'-divinylbiphenyl, 4,2'-divinylbiphenyl, 3,2'-divinylbiphenyl, 3,3'-divinylbiphenyl, 2,2'-divinylbiphenyl, 2,4-divinylbiphenyl, 1,2-divinyl-3,4-dimethylbenzene, 1,3-divinyl-4,5,8-tributylnaphthalene, and 2,2'-divinyl-4-ethyl-4'-propylbiphenyl. These may be used alone or in combination of two or more. Among these, divinylbenzenes such as m-divinylbenzene and p-divinylbenzene are preferable as the bifunctional aromatic compound, and p-divinylbenzene is more preferable.

[0032] The aromatic polymer may have not only a structural unit derived from the bifunctional aromatic compound but also other structural units. Examples of these other structural units include a structural unit derived from a monofunctional aromatic compound having one carbon-carbon unsaturated double bond bonded to an aromatic ring, a structural unit derived from a trifunctional aromatic compound having three carbon-carbon unsaturated double bonds bonded to an aromatic ring, a structural unit derived from indenes, and a structural unit derived from acenaphthylenes. The structural unit derived from the monofunctional aromatic compound is a structural unit obtained by polymerizing the monofunctional aromatic compound. The structural unit derived from the trifunctional aromatic compound is a structural unit obtained by polymerizing the trifunctional aromatic compound. The structural unit derived from indenes is a structural unit obtained by polymerizing indenes. The structural unit derived from acenaphthylenes is a structural unit obtained by polymerizing acenaphthylenes.

[0033] The monofunctional aromatic compound only needs to have one carbon-carbon unsaturated double bond bonded to the aromatic ring, and other groups other than the carbon-carbon unsaturated double bond may be bonded to the aromatic ring. Examples of the monofunctional aromatic compound include a monofunctional aromatic compound having one carbon-carbon unsaturated double bond bonded to the aromatic ring and no other groups other than this carbon-carbon unsaturated double bond, and a monofunctional aromatic compound having one carbon-carbon unsaturated double bond bonded to the aromatic ring and further having an alkyl group such as an ethyl group bonded to the aromatic ring.

[0034] Examples of the monofunctional aromatic compound having one carbon-carbon unsaturated double bond bonded to the aromatic ring and no other groups other than this carbon-carbon unsaturated double bond include styrene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, and α-alkyl-substituted styrene. Examples of α-alkyl-substituted styrene include α-methylstyrene, α-ethylstyrene, α-propylstyrene, α-n-butylstyrene, α-isobutylstyrene, α-t-butylstyrene, α-n-pentylstyrene, α-2-methylbutylstyrene, α-3-methylbutyl-2-styrene, α-t-butylstyrene, α-t-butylstyrene, α-n-pentylstyrene, α-2-methylbutylstyrene, α-3-methylbutylstyrene, α-t-pentylstyrene, α-n-hexylstyrene, α-2-methylpentylstyrene, α-3-methylpentylstyrene, α-1-methylpentylstyrene, α-2,2-dimethylbutylstyrene, α-2,3-dimethylbutylstyrene, α-2,4-dimethylbutylstyrene, α-3,3-dimethylbutylstyrene, α-3,4-dimethylbutylstyrene, α-4,4-dimethylbutylstyrene, α-2-ethylbutylstyrene, α-1-ethylbutylstyrene, α-cyclohexylstyrene, and α-cyclohexylstyrene. These may be used alone or in combination of two or more.

[0035] Examples of the monofunctional aromatic compound in which a carbon-carbon unsaturated double bond is bonded to one aromatic ring and an alkyl group is further bonded to the aromatic ring include nuclear alkyl-substituted aromatic compounds and alkoxy-substituted styrenes.

[0036] Examples of the nuclear alkyl-substituted aromatic compound include ethyl vinyl aromatic compounds in which the alkyl group bonded to the aromatic ring is an ethyl group, nuclear alkyl-substituted styrenes in which an alkyl group is bonded to styrene as the aromatic ring, and nuclear alkyl-substituted aromatic compounds other than the ethyl vinyl aromatic compound and the nuclear alkyl-substituted styrene (other nuclear alkyl-substituted aromatic compounds).

[0037] Examples of the ethyl vinyl aromatic compound include o-ethyl vinyl benzene, m-ethyl vinyl benzene, p-ethyl vinyl benzene, 2-vinyl-2'-ethyl biphenyl, 2-vinyl-3'-ethyl biphenyl, 2-vinyl-4'-ethyl biphenyl, 3-vinyl-2'-ethyl biphenyl, 3-vinyl-3'-ethyl biphenyl, 3-vinyl-4'-ethyl biphenyl, 4-vinyl-2'-ethyl biphenyl, 4-vinyl-3'-ethyl biphenyl, 4-vinyl-4'-ethyl biphenyl, 1-vinyl-2-ethyl naphthalene, 1-vinyl-3-ethyl naphthalene, 1-vinyl-4-ethyl naphthalene, 1-vinyl-5-ethyl naphthalene, 1-vinyl-6-ethyl naphthalene, 1-vinyl-7-ethyl naphthalene, 1-vinyl-8-ethyl naphthalene, 2-vinyl-1-ethyl naphthalene, 2-vinyl-3-ethyl naphthalene, 2-vinyl-4-ethyl naphthalene, 2-vinyl-5-ethyl naphthalene, 2-vinyl-6-ethyl naphthalene, 2-vinyl-7-ethyl naphthalene, and 2-vinyl-8-ethyl naphthalene.

[0038] Examples of the nuclear alkyl-substituted styrene include m-methylstyrene, p-methylstyrene, m-propylstyrene, p-propylstyrene, m-n-butylstyrene, p-n-butylstyrene, m-t-butylstyrene, p-t-butylstyrene, m-n-hexylstyrene, p-n-hexylstyrene, m-cyclohexylstyrene, p-cyclohexylstyrene, and the like.

[0039] Examples of the other nuclear alkyl-substituted aromatic compounds include 2-vinyl-2'-propylbiphenyl, 2-vinyl-3'-propylbiphenyl, 2-vinyl-4'-propylbiphenyl, 3-vinyl-2'-propylbiphenyl, 3-vinyl-3'-propylbiphenyl, 3-vinyl-4'-propylbiphenyl, 4-vinyl-2'-propylbiphenyl, 4-vinyl-3'-propylbiphenyl, 4-vinyl-4'-propylbiphenyl, 1-vinyl-2-propylnaphthalene, 1-vinyl-3-propylnaphthalene, 1-vinyl-4-propylnaphthalene, 1-vinyl-5-propylnaphthalene, 1-vinyl-6-propylnaphthalene, 1-vinyl-7-propylnaphthalene, 1-vinyl-8-propylnaphthalene, 2-vinyl-1-propylnaphthalene, 2-vinyl-3-propylnaphthalene, 2-vinyl-4-propylnaphthalene, 2-vinyl-5-propylnaphthalene, 2-vinyl-6-propylnaphthalene, 2-vinyl-7-propylnaphthalene, and 2-vinyl-8-propylnaphthalene.

[0040] Examples of the alkoxy-substituted styrene include o-ethoxystyrene, m-ethoxystyrene, p-ethoxystyrene, o-propoxystyrene, m-propoxystyrene, p-propoxystyrene, o-n-butoxystyrene, m-n-butoxystyrene, p-n-butoxystyrene, o-isobutoxystyrene, m-isobutoxystyrene, p-isobutoxystyrene, o-t-butoxystyrene, m-t-butoxystyrene, p-t-butoxystyrene, o-n-pentoxystyrene, m-n-pentoxystyrene, p-n-pentoxystyrene, α-methyl-o-butoxystyrene, α-methyl-m-butoxystyrene, α-methyl-p-butoxystyrene, o-t-pentoxystyrene, m-t-pentoxystyrene, p-t-pentoxystyrene, o-n-hexoxystyrene, m-n-hexoxystyrene, p-n-hexoxystyrene, α-methyl-o-pentoxystyrene, α-methyl-m-pentoxystyrene, α-methyl-p-pentoxystyrene, o-cyclohexoxystyrene, m-cyclohexoxystyrene, p-cyclohexoxystyrene, o-phenoxystyrene, m-phenoxystyrene, and p-phenoxystyrene.

[0041] As the monofunctional aromatic compound, the exemplified compounds may be used alone or in combination of two or more. Among the exemplified compounds, styrene and p-ethylvinylbenzene are preferred as the monofunctional aromatic compound.

[0042] Examples of the trifunctional aromatic compound having three carbon-carbon unsaturated double bonds bonded to an aromatic ring include 1,2,4-trivinylbenzene, 1,3,5-trivinylbenzene, 1,2,4-triisopropenylbenzene, 1,3,5-triisopropenylbenzene, 1,3,5-trivinylnaphthalene, and 3,5,4'-trivinylbiphenyl. The trifunctional aromatic compound may be used alone or in combination of two or more of the exemplified compounds.

[0043] Examples of the indenes include indene, alkyl-substituted indene, and alkoxy indene. Examples of the alkyl-substituted indene include methyl indene, ethyl indene, propyl indene, butyl indene, t-butyl indene, sec-butyl indene, n-pentyl indene, 2-methyl-butyl indene, 3-methyl-butyl indene, n-hexyl indene, 2-methyl-pentyl indene, 3-methyl-pentyl indene, 4-methyl-pentyl indene, and the like. Examples of the alkoxy indene include methoxy indene, ethoxy indene, propoxy indene, butoxy indene, t-butoxy indene, sec-butoxy indene, n-pentoxy indene, 2-methyl-butoxy indene, 3-methyl-butoxy indene, n-hexoxy indene, 2-methyl-pentoxy indene, 3-methyl-pentoxy indene, 4-methyl-pentoxy indene, and other alkoxy indenes. The indenes may be used alone or in combination of two or more of the exemplified compounds.

[0044] Examples of the acenaphthylenes include acenaphthylene, alkyl acenaphthylenes, halogenated acenaphthylenes, and phenyl acenaphthylenes. Examples of the alkyl acenaphthylenes include 1-methyl acenaphthylene, 3-methyl acenaphthylene, 4-methyl acenaphthylene, 5-methyl acenaphthylene, 1-ethyl acenaphthylene, 3-ethyl acenaphthylene, 4-ethyl acenaphthylene, 5-ethyl acenaphthylene, and the like. Examples of the halogenated acenaphthylenes include 1-chloro acenaphthylene, 3-chloro acenaphthylene, 4-chloro acenaphthylene, 5-chloro acenaphthylene, 1-bromo acenaphthylene, 3-bromo acenaphthylene, 4-bromo acenaphthylene, 5-bromo acenaphthylene, and the like. Examples of the phenyl acenaphthylenes include 1-phenyl acenaphthylene, 3-phenyl acenaphthylene, 4-phenyl acenaphthylene, 5-phenyl acenaphthylene, and the like. The acenaphthylenes may be used alone or in combination of two or more of the exemplified compounds.

[0045] When the aromatic polymer has not only the structural unit derived from the bifunctional aromatic compound but also other structural units, it is a copolymer of the structural unit derived from the bifunctional aromatic compound and other structural units such as the structural unit derived from the monofunctional aromatic compound. This copolymer may be a block copolymer or a random copolymer.

[0046] As described above, the polymer is not particularly limited as long as it has the structural unit represented by the formula (1) in the molecule. And the structural unit represented by the formula (1) preferably includes the structural unit represented by the following formula (2). That is, the polymer preferably has the structural unit represented by the following formula (2) in the molecule.

[0047]

Chemical formula

[0048] The arylene group having 6 to 12 carbon atoms in the formula (2) is not particularly limited. Examples of this arylene group include monocyclic aromatic groups such as a phenylene group, and bicyclic aromatic groups such as naphthalene rings where the aromatic is not monocyclic. Also, derivatives in which a hydrogen atom bonded to the aromatic ring is substituted with a functional group such as an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group are also included in this arylene group.

[0049] The structural unit represented by the formula (2) preferably includes the structural unit represented by the following formula (3). That is, in the structural unit represented by the formula (2), R7 is preferably a phenylene group. Among the phenylene groups, a p-phenylene group is more preferable.

[0050]

Chem.

[0051] The polymer preferably includes a polymer further having a structural unit represented by the following formula (4) in the molecule. That is, the polymer preferably includes, as the structural unit represented by the following formula (4), a structural unit derived from a monofunctional aromatic compound having one carbon-carbon unsaturated double bond bonded to an aromatic ring. Therefore, the polymer preferably is a polymer having the structural unit represented by the formula (1) and the structural unit represented by the following formula (4) in the molecule. That is, as long as the polymer has the structural unit represented by the formula (1) and the structural unit represented by the following formula (4) in the molecule, it may have structural units other than the structural unit represented by the formula (1) and the following formula (4) (structural units other than (1) and (4)). Further, the polymer may contain structural units other than (1) and (4), or may be a polymer in which a repeating unit in which the structural unit represented by the formula (1) is repeatedly bonded, a repeating unit in which the repeating unit represented by the following formula (4) is repeatedly bonded, and a repeating unit in which the structural units other than (1) and (4) are repeatedly bonded are randomly bonded, or a block copolymer, or a random copolymer.

[0052]

Chem.

[0053] In the formula (4), R8 to R10 The alkyl group having 1 to 6 carbon atoms represented by the formula may not be particularly limited and may be the same as the alkyl group having 1 to 6 carbon atoms represented by R4 to R6 in the formula (1). In the formula (4), R8 to R 10 The alkyl group having 1 to 6 carbon atoms represented by the formula specifically includes, for example, a methyl group, an ethyl group, a propyl group, and a hexyl group.

[0054] The aryl group in the formula (4) is not particularly limited and may be an unsubstituted aryl group or an aryl group in which a hydrogen atom bonded to an aromatic ring is substituted with an alkyl group or the like. Further, the unsubstituted aryl group may be a group obtained by removing one hydrogen atom from an aromatic hydrocarbon having one aromatic ring, or a group obtained by removing one hydrogen atom from an aromatic hydrocarbon having two or more independent aromatic rings (for example, biphenyl). The aryl group in the formula (4) includes, for example, an unsubstituted aryl group having 6 to 12 carbon atoms, and an arylene group having 6 to 18 carbon atoms in which a hydrogen atom of an aryl group having 6 to 12 carbon atoms is substituted with an alkyl group having 1 to 6 carbon atoms. Further, examples of the unsubstituted aryl group having 6 to 12 carbon atoms include a phenyl group, a naphthyl group, and a biphenylyl group. The aryl group in the formula (4), that is, R 11 More specifically, aryl groups described in Table 1 and Table 2 below are included.

[0055]

Table 1

[0056]

Table 2

[0057] It is preferable that the weight average molecular weight of the polymer is from 1,500 to 40,000, and more preferably from 1,500 to 35,000. When the weight average molecular weight is too low, the heat resistance and the like tend to decrease. Further, when the weight average molecular weight is too high, the moldability and the like tend to decrease. Therefore, when the weight average molecular weight of the resin composition is within the above range, it has excellent heat resistance and moldability. Here, the weight average molecular weight may be measured by a general molecular weight measurement method. Specifically, values measured using gel permeation chromatography (GPC) and the like can be mentioned.

[0058] In the polymer, when the total of the structural units in the polymer is 100 mol%, the molar content of the structural unit represented by the formula (1) is preferably a molar content within the range of the above polymerization average molecular weight. Specifically, it is preferably 2 to 95 mol%, and more preferably 8 to 81 mol%. Further, the molar content of the structural unit represented by the formula (2) and the molar content of the structural unit represented by the formula (3) are the same as the molar content of the structural unit represented by the formula (1). Specifically, it is preferably 2 to 95 mol%, and more preferably 8 to 81 mol%. Further, when the polymer has a structural unit represented by the formula (1) and a structural unit represented by the following formula (4) in the molecule, the molar content of the structural unit represented by the formula (1) is preferably 2 to 95 mol%, and more preferably 8 to 81 mol%. The molar content of the structural unit represented by the formula (4) is preferably 5 to 98 mol%, and more preferably 19 to 92 mol%.

[0059] In the polymer, the average number of structural units represented by the formula (1) is preferably a number within the range of the above polymerization average molecular weight. Specifically, it is preferably 1 to 160, and more preferably 3 to 140. Also, the average number of structural units represented by the formula (2) and the average number of structural units represented by the formula (3) are the same as the average number of structural units represented by the formula (1). Specifically, it is preferably 1 to 160, and more preferably 3 to 140. Further, when the polymer has a structural unit represented by the formula (1) and a structural unit represented by the following formula (4) in the molecule, the average number of structural units represented by the formula (1) is preferably 1 to 160, and more preferably 3 to 140. The average number of structural units represented by the formula (4) is preferably 2 to 350, and more preferably 4 to 300.

[0060] Specific examples of the polymer include polymers containing a structural unit represented by the following formula (8) in the molecule and further containing at least one of a structural unit represented by the following formula (7) and a structural unit represented by the following formula (9). This polymer may be a block copolymer or a random copolymer.

[0061]

Chemical formula

[0062]

Chemical formula

[0063]

Chemical formula

[0064] A polymer containing a structural unit represented by the formula (8) in the molecule and further containing at least one of the structural unit represented by the formula (7) and the structural unit represented by the formula (9), wherein the molar content ratios of the structural unit represented by the formula (7), the structural unit represented by the formula (8), and the structural unit represented by the formula (9) are preferably 0 to 92 mol%, 8 to 54 mol%, and 0 to 89 mol%, respectively. Also, the average number of the structural units represented by the formula (7) is preferably 0 to 350, the average number of the structural units represented by the formula (8) is preferably 1 to 160, and the average number of the structural units represented by the formula (9) is preferably 0 to 270.

[0065] The equivalent weight of the vinyl group contained in the structural unit represented by the formula (1) in which R1 to R3 are hydrogen atoms in the polymer is preferably 250 to 1200, more preferably 300 to 1100. If the equivalent weight is too small, there are too many vinyl groups, the reactivity becomes too high, and problems such as a decrease in the storage stability of the resin composition or a decrease in the fluidity of the resin composition may occur. When using a resin composition with too small an equivalent weight, molding defects such as the generation of voids during multi-layer molding may occur due to insufficient fluidity, etc., and there may be a problem with moldability that it is difficult to obtain a highly reliable wiring board. Also, if the equivalent weight is too large, the vinyl group becomes too few, and the heat resistance of the cured product tends to be insufficient. Therefore, when the equivalent weight is within the above range, it will be excellent in heat resistance and moldability. Note that the equivalent weight of the vinyl group contained in the structural unit represented by the formula (1) in which R1 to R3 are hydrogen atoms is the so-called vinyl equivalent weight.

[0066] (Modified PPE compound) In addition to the above polymer, the resin composition of this embodiment may further contain a modified polyphenylene ether compound whose terminal is modified with a group represented by the following formula (5) or (6).

[0067] [Chemical formula]

[0068]

Chem.

[0069] As a result, a laminate having excellent low dielectric properties such as a lower dielectric constant and a lower dielectric tangent can be obtained, and it is considered to be very useful as various electronic materials.

[0070] In the formula (5), s represents an integer from 0 to 10. Also, Z represents an arylene group. Also, R 12 ~R 14 are each independent. That is, R 12 ~R 14 may be the same group or different groups. Also, R 12 ~R 14 represents a hydrogen atom or an alkyl group.

[0071] In the formula (6), when p is 0, it indicates that Z is directly bonded to the end of the polyphenylene ether.

[0072] This arylene group is not particularly limited. Examples of this arylene group include monocyclic aromatic groups such as a phenylene group, and polycyclic aromatic groups such as polycyclic aromatic groups where the aromatic ring is not monocyclic but a polycyclic aromatic such as a naphthalene ring. Also, derivatives in which a hydrogen atom bonded to the aromatic ring is substituted with a functional group such as an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group are also included. Also, the alkyl group is not particularly limited, and for example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. Specifically, for example, a methyl group, an ethyl group, a propyl group, a hexyl group, and a decyl group can be mentioned.

[0073] In the formula (6), R 15represents a hydrogen atom or an alkyl group. The alkyl group is not particularly limited, and for example, an alkyl group having 1 to 18 carbon atoms is preferred, and an alkyl group having 1 to 10 carbon atoms is more preferred. Specifically, for example, a methyl group, an ethyl group, a propyl group, a hexyl group, a decyl group and the like can be mentioned. Further, examples of the substituent represented by the formula (6) include an acrylate group and a methacrylate group.

[0074] Further, examples of the substituent containing the vinylbenzyl group include a substituent represented by the following formula (10).

[0075] [Chemical formula]

[0076] More specifically, examples of the group represented by the formula (10) include vinylbenzyl groups (ethenylbenzyl groups) such as p-ethenylbenzyl group and m-ethenylbenzyl group, vinylphenyl group, acrylate group, and methacrylate group.

[0077] The modified polyphenylene ether compound has a polyphenylene ether chain in the molecule, and for example, preferably has a repeating unit represented by the following formula (11) in the molecule.

[0078] [Chemical formula] In the formula (11), t represents 1 to 50. Also, R 16 ~R 19 are each independent. That is, R 16 ~R 19 may be the same group or different groups. Also, R 16 ~R 19 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. Among these, a hydrogen atom and an alkyl group are preferred.

[0079] R 16 ~R 19 In R and ~R, each of the functional groups listed specifically includes the following.

[0080] The alkyl group is not particularly limited, but for example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. Specifically, for example, a methyl group, an ethyl group, a propyl group, a hexyl group, a decyl group, etc. may be mentioned.

[0081] The alkenyl group is not particularly limited, but for example, an alkenyl group having 2 to 18 carbon atoms is preferable, and an alkenyl group having 2 to 10 carbon atoms is more preferable. Specifically, for example, a vinyl group, an allyl group, a 3-butenyl group, etc. may be mentioned.

[0082] The alkynyl group is not particularly limited, but for example, an alkynyl group having 2 to 18 carbon atoms is preferable, and an alkynyl group having 2 to 10 carbon atoms is more preferable. Specifically, for example, an ethynyl group, a prop-2-yn-1-yl group (propargyl group), etc. may be mentioned.

[0083] The alkylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkyl group. For example, an alkylcarbonyl group having 2 to 18 carbon atoms is preferable, and an alkylcarbonyl group having 2 to 10 carbon atoms is more preferable. Specifically, for example, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a hexanoyl group, an octanoyl group, a cyclohexylcarbonyl group, etc. may be mentioned.

[0084] The alkenylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkenyl group. For example, an alkenylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkenylcarbonyl group having 3 to 10 carbon atoms is more preferable. Specifically, for example, an acryloyl group, a methacryloyl group, a crotonoyl group, etc. may be mentioned.

[0085] The alkynylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkynyl group. For example, an alkynylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkynylcarbonyl group having 3 to 10 carbon atoms is more preferable. Specifically, for example, a propioloyl group and the like can be mentioned.

[0086] The weight average molecular weight (Mw) of the modified polyphenylene ether compound used in this embodiment is not particularly limited. Specifically, it is preferably 500 to 5000, more preferably 800 to 4000, and even more preferably 1000 to 3000. Here, the weight average molecular weight may be measured by a general molecular weight measurement method. Specifically, values measured using gel permeation chromatography (GPC) and the like can be mentioned. Further, when the modified polyphenylene ether compound has a repeating unit represented by the above formula (8) in the molecule, t is preferably a numerical value such that the weight average molecular weight of the modified polyphenylene ether compound is within such a range. Specifically, t is preferably 1 to 50.

[0087] When the weight average molecular weight of the modified polyphenylene ether compound is within such a range, it has excellent low dielectric properties of polyphenylene ether, not only has excellent heat resistance of the cured product, but also has excellent moldability. This is considered to be due to the following reasons. In ordinary polyphenylene ether, when its weight average molecular weight is within such a range, since it is a relatively low molecular weight, the heat resistance of the cured product tends to decrease. In this regard, since the modified polyphenylene ether compound according to this embodiment has one or more unsaturated double bonds at the terminals, it is considered that a cured product with sufficiently high heat resistance can be obtained. Also, when the weight average molecular weight of the modified polyphenylene ether compound is within such a range, since it is a relatively low molecular weight, it is considered to have excellent moldability. Therefore, it is considered that such a modified polyphenylene ether compound can obtain not only excellent heat resistance of the cured product but also excellent moldability.

[0088] In addition, in the modified polyphenylene ether compound used in the present embodiment, the average number (terminal functional group number) of the substituents at the molecular terminals per molecule of the modified polyphenylene ether is not particularly limited. Specifically, it is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1.5 to 3. If the number of terminal functional groups is too small, it tends to be difficult to obtain a cured product with sufficient heat resistance. On the other hand, if the number of terminal functional groups is too large, the reactivity becomes too high, and for example, there may be problems such as a decrease in the storage stability of the resin composition or a decrease in the fluidity of the resin composition. That is, when such a modified polyphenylene ether is used, molding defects such as the generation of voids during multi-layer molding may occur due to insufficient fluidity, etc., and there may be a problem with moldability that it is difficult to obtain a highly reliable printed wiring board.

[0089] The number of terminal functional groups of the modified polyphenylene ether compound includes numerical values representing the average value of the substituents per molecule of all the modified polyphenylene ether compounds present in 1 mol of the modified polyphenylene ether compound. This number of terminal functional groups can be measured, for example, by measuring the number of hydroxyl groups remaining in the obtained modified polyphenylene ether compound and calculating the decrease from the number of hydroxyl groups of the polyphenylene ether before modification. The decrease from the number of hydroxyl groups of the polyphenylene ether before modification is the number of terminal functional groups. The method for measuring the number of hydroxyl groups remaining in the modified polyphenylene ether compound can be determined by adding a quaternary ammonium salt (tetraethylammonium hydroxide) that associates with the hydroxyl group to a solution of the modified polyphenylene ether compound and measuring the UV absorbance of the mixed solution.

[0090] In addition, the intrinsic viscosity of the modified polyphenylene ether compound used in this embodiment is not particularly limited. Specifically, it may be 0.03 to 0.12 dl / g, preferably 0.04 to 0.11 dl / g, and more preferably 0.06 to 0.095 dl / g. If this intrinsic viscosity is too low, the molecular weight tends to be low, and it tends to be difficult to obtain low dielectric properties such as low dielectric constant and low dielectric tangent. On the other hand, if the intrinsic viscosity is too high, the viscosity is high, sufficient fluidity cannot be obtained, and the moldability of the cured product tends to decrease. Therefore, if the intrinsic viscosity of the modified polyphenylene ether compound is within the above range, excellent heat resistance and moldability of the cured product can be realized.

[0091] Here, the intrinsic viscosity is the intrinsic viscosity measured in methylene chloride at 25°C. More specifically, for example, it is a value measured with a viscometer for a methylene chloride solution (liquid temperature 25°C) of 0.18 g / 45 ml. Examples of this viscometer include the AVS500 Visco System manufactured by Schott.

[0092] More specific examples of the modified polyphenylene ether compound include, for example, the modified polyphenylene ether compound represented by the following formula (12), and the modified polyphenylene ether compound represented by the following formula (13). Further, as the modified polyphenylene ether compound, these modified polyphenylene ether compounds may be used alone, or a combination of these two modified polyphenylene ether compounds may be used.

[0093]

Chemical formula

[0094]

Chemical formula

[0095] In formulas (12) and (13), R 20 ~R 27 as well as R 28 ~R 35Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. X1 and X2 each independently represent a group represented by the above formula (5) or (6). A and B each represent a repeating unit represented by the following formula (14) and the following formula (15). Further, in formula (13), Y represents a linear, branched, or cyclic hydrocarbon having 20 or fewer carbon atoms.

[0096]

Chemical formula

[0097]

Chemical formula

[0098] In formula (14) and formula (15), m and n each represent 0 to 20. R 36 ~R 39 As well as R 40 ~R 43 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group.

[0099] The modified polyphenylene ether compound represented by the above formula (12) and the modified polyphenylene ether compound represented by the above formula (13) are not particularly limited as long as they are compounds satisfying the above configuration. Specifically, in the above formula (12) and the above formula (13), R 20 ~R 27 As well as R 28 ~R 35 Are each independent as described above. That is, R 20 ~R 27 As well as R 28 ~R 35 May be the same group or different groups. Also, R 20 ~R 27 As well as R 28 ~R 35represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. Among these, a hydrogen atom and an alkyl group are preferred.

[0100] In addition, in Formula (14) and Formula (15), m and n preferably represent 0 to 20 respectively as described above. Further, m and n preferably represent numerical values such that the total value of m and n is 1 to 30. Therefore, more preferably, m represents 0 to 20, n represents 0 to 20, and the total of m and n represents 1 to 30. Also, R 36 ~R 39 as well as R 40 ~R 43 are each independent. That is, R 36 ~R 39 as well as R 40 ~R 43 may be the same group or different groups. Also, R 36 ~R 39 as well as R 40 ~R 43 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. Among these, a hydrogen atom and an alkyl group are preferred.

[0101] R 20 ~R 43 is the same as R 16 ~R 19 in the above Formula (11).

[0102] In the above Formula (13), Y is a linear, branched, or cyclic hydrocarbon having 20 or fewer carbon atoms as described above. Examples of Y include a group represented by the following Formula (16).

[0103]

Chemical formula

[0104] In the above Formula (16), R44 and R 45 each independently represents a hydrogen atom or an alkyl group. Examples of the alkyl group include a methyl group and the like. Examples of the group represented by the formula (16) include a methylene group, a methylmethylene group, and a dimethylmethylene group, among which a dimethylmethylene group is preferable.

[0105] In the formula (12) and the formula (13), X1 and X2 each independently represent a group represented by the formula (5) or the formula (6). In the modified polyphenylene ether compound represented by the formula (12) and the modified polyphenylene ether compound represented by the formula (13), X1 and X2 may be the same substituent or different substituents.

[0106] More specific examples of the modified polyphenylene ether compound represented by the formula (12) include, for example, a modified polyphenylene ether compound represented by the following formula (17).

[0107]

Chemical formula

[0108] More specific examples of the modified polyphenylene ether compound represented by the formula (13) include, for example, a modified polyphenylene ether compound represented by the following formula (18), a modified polyphenylene ether compound represented by the following formula (19), and the like.

[0109]

Chemical formula

[0110]

Chemical formula

[0111] In the above formulas (17) to (19), m and n are the same as m and n in the above formulas (14) and (15). Also, in the above formulas (17) and (18), R 12 ~R 14 and s are the same as R 12 ~R 14 and s in the above formula (5). Also, in the above formulas (18) and (19), Y is the same as Y in the above formula (13). Also, in the above formula (19), R 15 is the same as R 15 in the above formula (6).

[0112] Moreover, as the average number (terminal functional group number) of the above-mentioned substituents possessed at the molecular terminals per molecule of the modified polyphenylene ether in the modified polyphenylene ether compound used in the present embodiment, the above-mentioned range can be mentioned. For example, in the case of the modified polyphenylene ether compound represented by the above formulas (17) to (19), specifically, it is preferably 1 to 2, and more preferably 1.5 to 2.

[0113] The method for synthesizing the modified polyphenylene ether compound used in the present embodiment is not particularly limited as long as a modified polyphenylene ether compound terminal-modified with a group represented by the above formula (5) or (6) (hereinafter also referred to as a substituent) can be synthesized. Specifically, a method of reacting a polyphenylene ether with a compound in which the above-mentioned substituent and a halogen atom are bonded can be mentioned.

[0114] Examples of the compound in which the above-mentioned substituent and a halogen atom are bonded include compounds in which the substituents represented by the above formulas (5) to (6) and a halogen atom are bonded. Specific examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. Among these, a chlorine atom is preferable. More specifically, examples of the compound in which the above-mentioned substituent and a halogen atom are bonded include chloromethylstyrenes such as o-chloromethylstyrene, p-chloromethylstyrene, and m-chloromethylstyrene.

[0115] The polyphenylene ether as the raw material is not particularly limited as long as it can finally synthesize a predetermined modified polyphenylene ether compound. Specifically, polyphenylene ethers composed of 2,6-dimethylphenol and at least one of a bifunctional phenol and a trifunctional phenol, and those mainly composed of polyphenylene ethers such as poly(2,6-dimethyl-1,4-phenylene oxide) can be mentioned. Further, the bifunctional phenol is a phenol compound having two phenolic hydroxyl groups in the molecule, and examples thereof include tetramethylbisphenol A. Further, the trifunctional phenol is a phenol compound having three phenolic hydroxyl groups in the molecule. In particular, the polyphenylene ether compound of the present embodiment preferably contains a structure derived from 2,6-dimethylphenol and a bifunctional phenol.

[0116] Examples of the method for synthesizing the modified polyphenylene ether compound include the method described above. Specifically, the above-described polyphenylene ether and a compound in which the substituent and the halogen atom are bonded are dissolved in a solvent and stirred. By doing so, the polyphenylene ether and the compound in which the substituent and the halogen atom are bonded react to obtain the modified polyphenylene ether compound used in the present embodiment.

[0117] During the above reaction, it is preferably carried out in the presence of an alkali metal hydroxide. By doing so, it is considered that this reaction proceeds favorably. This is presumably because the alkali metal hydroxide functions as a dehydrohalogenating agent, specifically, a dehydrochlorinating agent. That is, it is considered that the alkali metal hydroxide eliminates hydrogen halide from the phenol group of the polyphenylene ether and the compound in which the substituent and the halogen atom are bonded, and thereby the substituent binds to the oxygen atom of the phenol group instead of the hydrogen atom of the phenol group of the polyphenylene ether.

[0118] The alkali metal hydroxide is not particularly limited as long as it can function as a dehalogenating agent, and examples thereof include sodium hydroxide. Further, the alkali metal hydroxide is usually used in an aqueous solution state, and specifically, it is used as an aqueous sodium hydroxide solution.

[0119] Reaction conditions such as reaction time and reaction temperature vary depending on the compound in which the substituent and the halogen atom are bonded, and are not particularly limited as long as the reaction proceeds preferably under the conditions as described above. Specifically, the reaction temperature is preferably from room temperature to 100 °C, more preferably from 30 to 100 °C. Further, the reaction time is preferably from 0.5 to 20 hours, more preferably from 0.5 to 10 hours.

[0120] The solvent used during the reaction is not particularly limited as long as it can dissolve the polyphenylene ether and the compound in which the substituent and the halogen atom are bonded, and does not inhibit the reaction between the polyphenylene ether and the compound in which the substituent and the halogen atom are bonded. Specifically, toluene and the like can be mentioned.

[0121] The above reaction is preferably carried out in the presence of not only an alkali metal hydroxide but also a phase transfer catalyst. That is, the above reaction is preferably carried out in the presence of an alkali metal hydroxide and a phase transfer catalyst. By doing so, it is considered that the above reaction proceeds more favorably. This is considered to be due to the following reasons. A phase transfer catalyst has a function of incorporating an alkali metal hydroxide, is soluble in both a phase of a polar solvent such as water and a phase of a nonpolar solvent such as an organic solvent, and can move between these phases. Specifically, when an aqueous sodium hydroxide solution is used as the alkali metal hydroxide and an organic solvent such as toluene that is immiscible with water is used as the solvent, even if the aqueous sodium hydroxide solution is dropped into the solvent used in the reaction, the solvent and the aqueous sodium hydroxide solution are separated, and it is considered that sodium hydroxide hardly migrates into the solvent. Then, it is considered that the aqueous sodium hydroxide solution added as the alkali metal hydroxide hardly contributes to promoting the reaction. On the other hand, when the reaction is carried out in the presence of an alkali metal hydroxide and a phase transfer catalyst, it is considered that the alkali metal hydroxide migrates into the solvent in a state of being incorporated into the phase transfer catalyst, and the aqueous sodium hydroxide solution easily contributes to promoting the reaction. Therefore, when the reaction is carried out in the presence of an alkali metal hydroxide and a phase transfer catalyst, it is considered that the above reaction proceeds more favorably.

[0122] The phase transfer catalyst is not particularly limited, and examples thereof include quaternary ammonium salts such as tetra-n-butylammonium bromide.

[0123] The resin composition used in this embodiment preferably contains, in addition to the above polymer, the modified polyphenylene ether compound obtained as described above as the modified polyphenylene ether compound.

[0124] In addition, the resin composition of the present embodiment may include thermosetting resins other than the polymers and polyphenylene ether compounds as described above. For example, other thermosetting resins that can be used include epoxy resins, phenolic resins, amine resins, unsaturated polyester resins, thermosetting polyimide resins, and the like.

[0125] (Other components) The resin composition according to the present embodiment may contain components other than the polymer (other components) as necessary, as long as the effects of the present invention are not impaired. Examples of the other components contained in the resin composition according to the present embodiment include additives such as curing agents, silane coupling agents, flame retardants, initiators, defoaming agents, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, dyes and pigments, lubricants, and inorganic fillers. Further, the resin composition may contain resins such as polyphenylene ether, epoxy resin, unsaturated polyester resin, and thermosetting polyimide resin in addition to the polymer.

[0126] In particular, the curing agent is not particularly limited as long as it is a curing agent (crosslinking type crosslinking agent) that can react with the polymer and, if necessary, the modified polyphenylene ether compound to crosslink the polymer and the curing agent and cure the resin composition. Examples of the crosslinking type curing agent include compounds having two or more unsaturated double bonds in the molecule, alkenyl isocyanurate compounds, styrene, styrene derivatives, allyl compounds having at least one allyl group in the molecule, polyfunctional maleimide compounds having at least two maleimide groups in the molecule, modified maleimide compounds, and acenaphthylene compounds having an acenaphthylene structure in the molecule.

[0127] In addition, examples of the compound having two or more unsaturated double bonds in the molecule include polyfunctional methacrylate compounds having two or more methacryloyl groups in the molecule, polyfunctional acrylate compounds having two or more acryloyl groups in the molecule, and polyfunctional vinyl compounds having two or more vinyl groups in the molecule. Examples of the polyfunctional vinyl compound include divinylbenzene and polybutadiene. The alkenyl isocyanurate compound may be any compound having an isocyanurate structure and an alkenyl group in the molecule, and examples thereof include trialkenyl isocyanurate compounds such as triallyl isocyanurate (TAIC).

[0128] Examples of the styrene derivative include bromostyrene such as dibromostyrene. Examples of the modified maleimide compound include a modified maleimide compound in which a part of the molecule is amine-modified, a modified maleimide compound in which a part of the molecule is silicone-modified, and a modified maleimide compound in which a part of the molecule is amine-modified and silicone-modified.

[0129] Examples of the allyl compound include monofunctional allyl compounds having one allyl group in the molecule and polyfunctional allyl compounds having two or more allyl groups in the molecule. Examples of the polyfunctional allyl compound include diallyl phthalate (DAP).

[0130] The polyfunctional maleimide compound having at least two or more maleimide groups in the molecule is not particularly limited. Examples of the polyfunctional maleimide compound include phenylenebismaleimides such as 4,4'-diphenylmethanebismaleimide, polyphenylmethanemaleimide, and m-phenylenebismaleimide; bisphenol A diphenyl ether bismaleimide; 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide; 4-methyl-1,3-phenylenebismaleimide; 1,6'-bismaleimide-(2,2,4-trimethyl)hexane; 4,4'-diphenyl ether bismaleimide; 4,4'-diphenyl sulfone bismaleimide; 1,3-bis(3-maleimidophenoxy)benzene; 1,3-bis(4-maleimidophenoxy)benzene; maleimide compounds having a biphenyl structure; and the like. Examples of the modified maleimide compound include a modified maleimide compound having a maleimide group in the molecule and a part of the molecule modified with an amine compound; a modified maleimide compound having a part of the molecule modified with a silicone compound; and a modified maleimide compound having a part of the molecule modified with an amine compound and a silicone compound by amine modification and silicone modification.

[0131] Examples of the acenaphthylene compound include acenaphthylene, alkyl acenaphthylenes, halogenated acenaphthylenes, and phenyl acenaphthylenes. Examples of the alkyl acenaphthylenes include 1-methylacenaphthylene, 3-methylacenaphthylene, 4-methylacenaphthylene, 5-methylacenaphthylene, 1-ethylacenaphthylene, 3-ethylacenaphthylene, 4-ethylacenaphthylene, and 5-ethylacenaphthylene. Examples of the halogenated acenaphthylenes include 1-chloroacenaphthylene, 3-chloroacenaphthylene, 4-chloroacenaphthylene, 5-chloroacenaphthylene, 1-bromoacenaphthylene, 3-bromoacenaphthylene, 4-bromoacenaphthylene, and 5-bromoacenaphthylene. Examples of the phenyl acenaphthylenes include 1-phenylacenaphthylene, 3-phenylacenaphthylene, 4-phenylacenaphthylene, and 5-phenylacenaphthylene. The acenaphthylene compound may be a monofunctional acenaphthylene compound having one acenaphthylene structure in the molecule as described above, or a polyfunctional acenaphthylene compound having two or more acenaphthylene structures in the molecule.

[0132] Among these, the alkenyl isocyanurate compound, the polyfunctional acrylate compound, the polyfunctional methacrylate compound, and the polyfunctional vinyl compound are preferable in that they can further enhance the heat resistance of the cured product of the resin composition. This is presumably because by using these crosslinking type curing agents, crosslinking of the resin composition is more preferably formed by the curing reaction. Further, the crosslinking type curing agent may be used alone or in combination of two or more of the exemplified crosslinking type curing agents. Further, as the crosslinking type curing agent, not only the crosslinking type curing agents exemplified above such as a compound having two or more unsaturated double bonds in the molecule, but also a compound having one unsaturated double bond in the molecule may be used in combination. Examples of the compound having one unsaturated double bond in the molecule include a monovinyl compound having one vinyl group in the molecule.

[0133] Examples of the polyfunctional acrylate compound include polyfunctional acrylate compounds having two or more acryloyl groups in the molecule, such as tricyclodecane dimethanol diacrylate.

[0134] Examples of the polyfunctional methacrylate compound include compounds having a polyphenylene ether structure and two or more methacryloyl groups in the molecule, and tricyclodecane dimethanol dimethacrylate. Examples of the compound having a polyphenylene ether structure and two or more methacryloyl groups in the molecule include methacryl-modified polyphenylene ether compounds obtained by modifying the terminal hydroxyl groups of polyphenylene ether with methacryl groups.

[0135] The above curing agent may be used alone or in combination of two or more.

[0136] The curing agent preferably has a weight average molecular weight of 100 to 5000, more preferably 100 to 4000, and even more preferably 100 to 3000. If the weight average molecular weight of the curing agent is too low, the curing agent may be likely to volatilize from the compounding component system of the resin composition. Also, if the weight average molecular weight of the curing agent is too high, the viscosity of the varnish of the resin composition and the melt viscosity during heat molding may become too high. Therefore, when the weight average molecular weight of the curing agent is within such a range, a resin composition with excellent heat resistance of the cured product can be obtained. This is presumably because the resin composition of the present embodiment can be suitably cured by the reaction with the polymer or the modified polyphenylene ether compound. Here, the weight average molecular weight may be measured by a general molecular weight measurement method. Specifically, values measured using gel permeation chromatography (GPC) etc. may be mentioned.

[0137] Also, as described above, the resin composition according to this embodiment may contain a silane coupling agent. The silane coupling agent may be contained in the resin composition, or may be contained as a silane coupling agent pre-surface-treated on the inorganic filler contained in the resin composition. Among these, it is preferable to contain the silane coupling agent as a silane coupling agent pre-surface-treated on the inorganic filler. Containing it as a silane coupling agent pre-surface-treated on the inorganic filler in this way, and further, it is more preferable to also contain a silane coupling agent in the resin composition. In addition, in the case of a prepreg, the prepreg may contain a silane coupling agent pre-surface-treated on the fibrous substrate.

[0138] Examples of the silane coupling agent include a silane coupling agent having at least one functional group selected from the group consisting of a vinyl group, a styryl group, a methacryloyl group, an acryloyl group, and a phenylamino group. That is, this silane coupling agent has at least one of a vinyl group, a styryl group, a methacryloyl group, an acryloyl group, and a phenylamino group as a reactive functional group, and further includes compounds having a hydrolyzable group such as a methoxy group or an ethoxy group.

[0139] Examples of the silane coupling agent having a vinyl group include vinyltriethoxysilane and vinyltrimethoxysilane. Examples of the silane coupling agent having a styryl group include p-styryltrimethoxysilane and p-styryltriethoxysilane. Examples of the silane coupling agent having a methacryloyl group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropylethyldiethoxysilane. Examples of the silane coupling agent having an acryloyl group include 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane. Examples of the silane coupling agent having a phenylamino group include N-phenyl-3-aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltriethoxysilane.

[0140] As described above, the resin composition according to this embodiment may contain a flame retardant. By containing a flame retardant, the flame retardancy of the cured product of the resin composition can be enhanced. The flame retardant is not particularly limited. Specifically, in fields where halogen-based flame retardants such as bromine-based flame retardants are used, for example, ethylenedipentabromobenzene, ethylenebistetrabromoimide, decabromodiphenyl oxide, and tetradecabromodiphenoxybenzene having a melting point of 300°C or higher are preferred. It is considered that by using a halogen-based flame retardant, the desorption of halogen at high temperatures can be suppressed, and a decrease in heat resistance can be suppressed. Also, in fields where halogen-free is required, phosphate ester-based flame retardants, phosphazene-based flame retardants, bisdiphenylphosphine oxide-based flame retardants, and phosphinate-based flame retardants can be mentioned. Specific examples of phosphate ester-based flame retardants include condensed phosphate esters of dixylenyl phosphate. Specific examples of phosphazene-based flame retardants include phenoxyphosphazene. Specific examples of bisdiphenylphosphine oxide-based flame retardants include xylylenebisdiphenylphosphine oxide. Specific examples of phosphinate-based flame retardants include, for example, metal phosphinates such as aluminum dialkylphosphinate. As the flame retardant, each of the exemplified flame retardants may be used alone, or two or more of them may be used in combination.

[0141] As described above, the resin composition according to this embodiment may contain an initiator (reaction initiator). Even if the resin composition consists only of the polymer, the curing reaction can proceed. However, depending on the process conditions, it may be difficult to raise the temperature to a high level until the curing progresses, so a reaction initiator may be added. The reaction initiator is not particularly limited as long as it can promote the curing reaction between the polymer and, if necessary, the modified polyphenylene ether compound. Specifically, for example, oxidizing agents such as α,α'-di(t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne, benzoyl peroxide, 3,3',5,5'-tetramethyl-1,4-diphenoquinone, chloranil, 2,4,6-tri-t-butylphenoxyl, t-butylperoxyisopropyl monocarbonate, azobisisobutyronitrile can be mentioned. Also, if necessary, a metal carboxylate salt or the like can be used in combination. By doing so, the curing reaction can be further promoted. Among these, α,α'-di(t-butylperoxy) diisopropylbenzene is preferably used. Since α,α'-di(t-butylperoxy) diisopropylbenzene has a relatively high reaction start temperature, it can suppress the promotion of the curing reaction at the time when curing is not required, such as during prepreg drying, and can suppress the deterioration of the storage stability of the resin composition. Furthermore, since α,α'-di(t-butylperoxy) diisopropylbenzene has low volatility, it does not volatilize during prepreg drying or storage and has good stability. Also, the reaction initiator may be used alone or in combination of two or more.

[0142] As described above, the resin composition according to this embodiment may contain fillers such as inorganic fillers. Examples of the filler include those added to enhance the heat resistance and flame retardancy of the cured product of the resin composition, and are not particularly limited. Further, by containing the filler, the heat resistance, flame retardancy, etc. can be further enhanced. Specific examples of the filler include silica such as spherical silica, metal oxides such as alumina, titanium oxide, and mica, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, talc, aluminum borate, barium sulfate, and calcium carbonate. Among these, silica, mica, and talc are preferable as the filler, and spherical silica is more preferable. The filler may be used alone or in combination of two or more. Further, the filler may be used as it is or may be surface-treated with the silane coupling agent. When the filler is contained, its content (filler content) is preferably 30 to 270% by mass, more preferably 50 to 250% by mass, based on the resin composition.

[0143] The content ratio of the polymer in the resin composition of this embodiment is not particularly limited as long as it can form a cured product that can become an insulating layer. For example, it is preferably about 30 to 95 parts by mass, more preferably 40 to 90 parts by mass, and even more preferably 50 to 90 parts by mass, based on the total amount (100 parts by mass) of the resin composition.

[0144] When the resin composition of this embodiment further contains a modified polyphenylene ether compound, its content is preferably about 5 to 30 parts by mass, more preferably 5 to 20 parts by mass, and even more preferably 10 to 20 parts by mass, based on the total amount (100 parts by mass) of the resin composition.

[0145] When further containing a curing agent, the content ratio of the curing agent is preferably about 5 to 70 parts by mass, more preferably 10 to 70 parts by mass, and even more preferably 10 to 50 parts by mass, based on the total amount (100 parts by mass) of the resin composition.

[0146] When manufacturing a copper-clad laminate, the resin composition as described above is usually prepared in a varnish form and often used as a resin varnish. Such a resin varnish is prepared, for example, as follows.

[0147] First, a polymer, and if necessary, components such as a modified polyphenylene ether compound, a curing agent, and various additives that can be dissolved in an organic solvent are put into the organic solvent and dissolved. At this time, heating may be performed if necessary. Then, if necessary, components that are insoluble in the organic solvent, inorganic fillers, etc. are added, and using a ball mill, bead mill, planetary mixer, roll mill, etc., they are dispersed until they reach a predetermined dispersed state, thereby preparing a varnish-like resin composition. The organic solvent used here is not particularly limited as long as it can dissolve the polymer, curing agent, etc. and does not inhibit the curing reaction. Specifically, for example, toluene, cyclohexanone, methyl ethyl ketone, and propylene glycol monomethyl ether acetate, etc. can be mentioned. These may be used alone or in combination of two or more.

[0148] It is preferable that the insulating layer of this embodiment further contains a glass substrate in addition to the cured product of the above resin composition. Thereby, there are advantages such as suppressing processing troubles (such as cracking), reducing dimensional changes, reducing linear expansion, and suppressing warping.

[0149] When the insulating layer of this embodiment contains a glass substrate, it may be used as a prepreg obtained by impregnating the above resin composition into the glass substrate. As a method for manufacturing such a prepreg, for example, a method of impregnating the above resin varnish (the resin composition prepared in a varnish form) into the glass substrate and then drying it can be mentioned.

[0150] The impregnation of the resin varnish into the glass substrate is performed by dipping, coating, or the like. This impregnation can be repeated multiple times as necessary. Further, at this time, it is also possible to repeat the impregnation using a plurality of resin varnishes having different compositions and concentrations, and finally adjust to the desired composition and resin amount.

[0151] The glass substrate impregnated with the resin varnish is heated at a desired heating condition of 80 to 170 ° C for 1 to 10 minutes to obtain a resin layer (A stage) containing a resin composition before curing or a resin layer in a semi-cured state (B stage). After applying the resin varnish (in the case of a prepreg, impregnating with the resin varnish), the organic solvent can be volatilized from the varnish by heating, and the organic solvent can be reduced or removed.

[0152] (Surface-treated copper foil) As shown in FIG. 1, the surface-treated copper foil according to the present embodiment is a surface-treated copper foil having a fine roughened particle treatment layer 2 of copper on at least one surface side of the copper foil 1, and the fine roughened particle treatment layer 2 is composed of fine copper particles having a particle diameter of 40 to 200 nm. It has a heat-resistant treatment layer 3 containing nickel on the fine roughened particle treatment layer 2, has a rust-proof treatment layer 4 containing at least chromium on the heat-resistant treatment layer 3, has a silane coupling agent treatment layer 5 on the rust-proof treatment layer, and the nickel adhesion amount in the heat-resistant treatment layer is 30 to 60 mg / m 2 It is characterized by being.

[0153] With such a configuration, by providing a fine roughened particle treatment layer composed of fine roughened particles on the surface of the untreated copper foil, the adhesion to the resin substrate is enhanced, and further, by adjusting the size of the fine roughened particles and particularly the nickel adhesion amount in the heat-resistant treatment layer, both the transmission characteristics and the basic characteristics (adhesion and heat resistance to the resin substrate) can be achieved.

[0154] Hereinafter, first, each configuration of the surface-treated copper foil of the present embodiment will be specifically described.

[0155] (Copper foil) Conventionally, electrolytic copper foil has generally been used for rigid substrates and the like, and rolled copper foil has generally been used for flexible substrates and the like. In recent years, however, with the booming of the flexible substrate market in particular, electrolytic copper foil with properties comparable to those of rolled copper foil has been developed, and currently, rolled copper foil or electrolytic copper foil is used regardless of the type of substrate. Therefore, the untreated copper foil used in this embodiment is not limited to rolled copper foil or electrolytic copper foil, and any copper foil may be used.

[0156] (Fine roughened particle treatment layer) The fine roughened particle treatment layer is the first surface treatment layer formed on the untreated copper foil, and is a layer provided to increase the surface area and improve the peel strength from the resin base material, and is composed of fine copper particles having a particle diameter of 40 to 200 nm.

[0157] In this embodiment, the particle diameter is used in the following meaning. That is, using a field emission scanning electron microscope FE-SEM (JSM-7800F manufactured by JEOL Ltd.), the sample stage is tilted at 40° and observed at a magnification of 80,000 times, and the height of the observed copper particles is taken as the value of the particle diameter. And the particle diameter of the fine copper particles in the fine roughened particle treatment layer of this embodiment has a maximum value of 200 nm and a minimum value of 40 nm in the range observed and measured by the above method.

[0158] Note that the fine copper particle treatment layer in this embodiment does not exclude the inclusion of copper particles having a particle diameter exceeding 200 nm or less than 40 nm. However, if there are many particles exceeding 200 nm, there is a risk that the transmission loss will increase, and if there are many particles less than 40 nm, there is a risk that sufficient adhesion cannot be ensured, and neither case is preferable. For example, it is preferable that the fine copper particle treatment layer in this embodiment contains 90% or more, and more preferably 95% or more, of copper particles having a particle diameter of 40 to 200 nm.

[0159] The fine roughened particle treatment layer can be formed by an electrolytic plating method.

[0160] The particle size of the fine copper particles in this embodiment is strongly affected by the electrolytic current density in addition to the bath composition of the plating treatment. For example, when the electrolytic current density is high, the particle size of the roughened particles tends to be small, and conversely, when the electrolytic current density is low, the particle size of the roughened particles tends to be large. Therefore, in order to obtain roughened particles with a target particle size, the electrolytic current density must be appropriately set.

[0161] Examples of the bath composition and electrolysis conditions for forming the copper fine roughened particle treatment layer are given below, but are not particularly limited thereto.

[0162] (Bath composition) Copper sulfate pentahydrate: 10 to 70 g / L (particularly preferably 30 to 50 g / L) Sodium diethylenetriaminepentaacetate (hereinafter DTPA·5Na): 50 to 150 g / L (particularly preferably 80 to 120 g / L) pH: 3.0 to 6.0 (particularly preferably 3.5 to 5.5) The pH is adjusted using sulfuric acid and sodium hydroxide

[0163] (Electrolysis conditions) Current density: 0.5 to 10.0 A / dm 2 (Particularly preferably 1.0 to 6.0 A / dm 2 ) Electric quantity: 10 to 130 A·sec / dm 2 (Particularly preferably 30 to 110 A·sec / dm 2 ) Liquid temperature: 25 to 50 °C (particularly preferably 30 to 45 °C) Anode: Copper plate.

[0164] The concentration of DTPA·5Na is suitably 50 to 150 g / L, but outside this range, when it is less than 50 g / L, it is difficult to obtain a sufficient refinement effect and the roughened particles become coarser. When it exceeds 150 g / L, it causes a decrease in current efficiency and the deposition amount of the roughening treatment extremely decreases, and further the voltage also increases, which is uneconomical.

[0165] Also, the electric quantity is 10 to 130 A·sec / dm 2is good, and in this range, there is an advantage that copper particles with a particle size of 40 to 200 nm can be obtained and it is easy to ensure the adhesion to the resin. Conversely, when the electric quantity is less than 10 A·sec / dm 2 , the amount of copper particles with a particle size of less than 40 nm increases, and there is a risk of reduced adhesion. Also, when it is more than 130 A·sec / dm 2 , the particle shape tends to be dendritic and the particle size tends to become coarser. As a result, problems such as low adhesion to the untreated copper foil, increased powder falling, and increased surface roughness of the laminate surface occur.

[0166] (Heat-resistant treatment layer) The heat-resistant treatment layer is a layer for heat resistance and rust prevention provided to protect the copper foil including the micro-roughened particle treatment layer from stresses such as chemical solutions and heat, and is sometimes called a barrier treatment layer. The heat-resistant treatment layer of the present embodiment contains nickel or nickel and phosphorus, and the nickel adhesion amount in the heat-resistant treatment layer is 30 to 60 mg / m 2 .

[0167] When the nickel adhesion amount is 30 to 60 mg / m 2 , the transmission characteristics and the basic characteristics can be compatible. When this nickel adhesion amount is less than 30 mg / m 2 , the heat resistance decreases. For example, swelling may occur at the interface between the resin and the copper foil, and as a result, the adhesion may decrease. When it exceeds 60 mg / m 2 , the transmission loss may increase. A more preferable range of the nickel adhesion amount is 40 to 50 mg / m 2 .

[0168] In the present embodiment, the "adhesion amount" refers to the mass per unit area of nickel deposited on the micro-roughened particle treatment layer side of the copper foil by plating (for example, the electrolytic plating method). Also, the adhesion amount can be measured by a method of dissolving and diluting the copper foil to be treated with nitric acid or the like and analyzing the concentration of nickel using an ICP emission spectroscopic analyzer.

[0169] The heat treatment resistant layer of this embodiment is preferably composed of nickel (Ni) or nickel (Ni) and phosphorus (P).

[0170] The heat treatment resistant layer of this embodiment is the second surface treatment layer formed after forming the above-mentioned finely roughened particle treatment layer, and can be formed by an electrolytic plating method. The nickel deposition amount can be adjusted according to the current conditions when performing this electrolytic plating.

[0171] Examples of the bath composition and electrolysis conditions for forming the heat treatment resistant layer of this embodiment composed of nickel and phosphorus are given below, but it is not particularly limited thereto.

[0172] (Bath composition) Nickel sulfate hexahydrate 10 - 100 g / L (particularly preferably 20 - 60 g / L) Sodium acetate trihydrate 2 - 40 g / L (particularly preferably 5 - 30 g / L) Sodium hypophosphite monohydrate 0.1 - 10 g / L (particularly preferably 1.0 - 6.0 g / L) pH 3.0 - 5.5 (particularly preferably 3.5 - 5.0)

[0173] (Electrolysis conditions) Current density: 0.5 - 3.5 A / dm 2 (Particularly preferably 1.0 - 2.0 A / dm 2 ) Electric quantity: 1.8 - 2.7 A·sec / dm 2 (Particularly preferably 2.0 - 2.5 A·sec / dm 2 ) Liquid temperature: 25 - 50 °C (particularly preferably 30 - 40 °C) Anode: An insoluble electrode such as a platinum group oxide-coated titanium.

[0174] As the supply source of nickel ions, nickel sulfate hexahydrate, nickel chloride hexahydrate, nickel acetate tetrahydrate, etc. can be used. As the supply source of phosphorus ions, sodium phosphite, sodium hypophosphite, nickel phosphite, etc. can be used. Also, sodium sulfate may be added for imparting conductivity.

[0175] (Rust prevention treatment layer) The rust prevention treatment layer is a layer provided to prevent oxidation during heating and storage. The rust prevention treatment layer of this embodiment contains at least chromium (Cr) and may also be called a chromate treatment layer. Furthermore, it may contain zinc (Zn).

[0176] The rust prevention treatment layer of this embodiment is the third surface treatment layer formed after forming the above heat treatment layer and can be formed by an electrolytic plating method.

[0177] The bath composition for forming the rust prevention treatment layer of this embodiment may be a known one. For example, a bath composition having hexavalent chromium such as chromic acid, sodium dichromate, and potassium dichromate can be mentioned. Note that the deposition form of chromium after forming the rust prevention treatment layer is a state in which Cr(OH)3 and Cr2O3 are mixed, and there is no hexavalent chromium that has an adverse effect on the human body, and it is deposited in the form of trivalent chromium. The chromic acid solution can be either alkaline or acidic.

[0178] Also, an alkaline zinc chromate solution containing zinc ions and hexavalent chromium ions described in Japanese Patent Publication No. 58-15950 may be used as the alkaline chromic acid solution. By using this chromic acid solution, the rust prevention property can be improved compared to the rust prevention treatment layer from a chromic acid solution alone.

[0179] Examples of the electrolytic bath and electrolytic conditions for applying the rust prevention treatment layer of this embodiment include, but are not particularly limited to, the bath compositions and conditions shown below.

[0180] (Bath composition) Sodium dichromate: 2.5 - 60 g / L (particularly preferably 5 - 30 g / L) Zinc ions: 0.25 - 16 g / L (particularly preferably 0.5 - 8 g / L) Sodium hydroxide: 10 - 180 g / L (particularly preferably 20 - 90 g / L)

[0181] (Electrolytic conditions) Current density: 1.5 - 8.0 A / dm 2 (Particularly preferably 3.0 - 4.0 A / dm 2 ) Electric quantity: 4.5 - 6.5 A·sec / dm 2 (Particularly preferably 5.0 - 6.0 A·sec / dm 2 ) Liquid temperature: 25 - 50°C (particularly preferably 30 - 40°C) Anode: An insoluble electrode such as a platinum group oxide-coated titanium etc.

[0182] (Silane coupling agent treatment layer) The silane coupling agent treatment layer of the present embodiment is the fourth surface treatment layer formed after forming the above rust prevention treatment layer, and is a layer provided to further improve the adhesion to the resin base material. Furthermore, by providing the silane coupling agent treatment layer, not only can the peel strength be improved, but also the deterioration of the peel strength after the severe test can be suppressed, and furthermore, the rust prevention property can be improved, resulting in a copper foil for circuit boards with excellent versatility.

[0183] The silane coupling agent treatment layer of the present embodiment can be formed by adding an appropriate amount of a silane coupling agent to water etc., applying it as an aqueous solution by immersion treatment or spray treatment etc., and then washing with water and drying. As the silane coupling agent, it can be selected and used from a variety of types such as epoxy group, amino group, mercapto group, vinyl group, methacryloxy group, styryl group etc. However, since they have different characteristics and also have compatibility with the base material, it is necessary to select and use them appropriately.

[0184] Examples of the bath for forming the silane coupling agent treatment layer include the following compositions and conditions, but it is not particularly limited thereto.

[0185] (Bath composition, conditions) γ-aminopropyltriethoxysilane: 1 - 5 mL / L (particularly preferably 2 - 4 mL / L) Liquid temperature: 25 - 35°C (particularly preferably 28 - 32°C) Immersion time: 15 seconds.

[0186] (Method for manufacturing copper-clad laminate) The copper-clad laminate of the present embodiment can be produced, for example, by stacking one or more prepregs containing the resin composition as described above, and further stacking copper foils as described above on both sides or one side of the upper and lower sides thereof, with the silane coupling agent layer in contact with the prepreg, and heating and pressing this to integrally laminate, thereby producing a double-sided copper foil-clad or single-sided copper foil-clad laminate.

[0187] The heating and pressing conditions can be appropriately set according to the thickness of the laminate to be manufactured, the type of resin composition, etc. For example, the temperature can be 170 to 220°C, the pressure can be 1.5 to 5.0 MPa, and the time can be 60 to 150 minutes.

[0188] <Copper foil with resin>[[]] As described above, the resin-coated copper foil 31 of the present embodiment has a structure in which a resin layer 32 containing a resin composition or a semi-cured product of the resin composition and a copper foil 13 provided on one side of the resin layer are laminated (see Fig. 4). That is, the resin-coated copper foil of the present embodiment may be a resin-coated copper foil including a resin layer containing the resin composition before curing (resin composition at stage A) and a copper foil, or may be a resin-coated copper foil including a resin layer containing a semi-cured product of the resin composition (resin composition at stage B) and a copper foil.

[0189] As the resin composition used for the resin layer and the copper foil, those similar to those described for the copper-clad laminate above can be used.

[0190] In the resin-coated copper foil of the present embodiment, the resin composition or its semi-cured product may be the resin composition dried or heat-dried.

[0191] Examples of the method for manufacturing the resin-coated copper foil include, for example, a method of applying the resin varnish obtained above to the surface on which the silane coupling agent layer of the copper foil is formed and then drying to semi-cure the resin composition.

[0192] Since the resin layer of the copper-clad resin film usually does not contain a glass substrate, the application of the resin varnish to the copper foil is carried out by coating or the like, which can be repeated a plurality of times as necessary. Further, at this time, it is also possible to repeat the coating using a plurality of resin varnishes having different compositions and concentrations and finally adjust to the desired composition (content ratio) and resin amount.

[0193] When the resin varnish is to be in a semi-cured state after being applied, it is heated under desired heating conditions, for example, at 80 to 170 ° C for 1 to 10 minutes to obtain a resin layer (A stage) containing the resin composition before curing or a semi-cured resin layer (B stage). After the resin varnish is applied (in the case of a prepreg, impregnated with the resin varnish), the organic solvent can be volatilized from the varnish by heating, and the organic solvent can be reduced or removed.

[0194] The copper-clad resin film of the present embodiment also has the same effects and advantages as the above-described copper-clad laminate.

[0195] <Circuit board> The copper-clad laminate and the copper-clad resin film of the present embodiment can be used as a circuit board 21 having a conductor pattern as a circuit 14 on the surface as shown in FIG. 3 by etching the copper foil on the surface or the like to form a circuit. Examples of the circuit forming method include circuit formation by a semi-additive method (SAP: Semi Additive Process) or a modified semi-additive method (MSAP: Modified Semi Additive Process) in addition to the method described above. The circuit board obtained by using the copper-clad laminate and the copper-clad resin film of the present embodiment is a highly reliable circuit board with reduced transmission loss while having heat resistance.

[0196] This specification discloses various aspects of technology as described above, and the main technologies are summarized below.

[0197] The copper-clad laminate according to one aspect of the present invention is a copper-clad laminate including an insulating layer containing a cured product of a resin composition and surface-treated copper foil on one or both sides of the insulating layer, wherein the resin composition contains a polymer having a structural unit represented by the following formula (1): [Chemical Formula] (In formula (1), Z represents an arylene group, R1 to R3 each independently represent a hydrogen atom or an alkyl group, and R4 to R6 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) Further, the surface-treated copper foil is a surface-treated copper foil having a fine roughened particle treatment layer on at least one surface side of the copper foil. The fine roughened particle treatment layer is composed of fine copper particles having a particle diameter of 40 to 200 nm. The fine roughened particle treatment layer has a heat-resistant treatment layer containing nickel thereon, and at least a rust-preventive treatment layer containing chromium thereon. The rust-preventive treatment layer has a silane coupling agent layer thereon, and the nickel adhesion amount in the heat-resistant treatment layer is 30 to 60 mg / m 2 This is characterized by the above.

[0198] With such a configuration, it is possible to reduce the transmission loss of a high-speed signal transmission substrate and provide a copper-clad laminate excellent in adhesion and heat resistance.

[0199] In the resin composition, it is preferable that the structural unit represented by the formula (1) contains a structural unit represented by the following formula (2).

[0200] [Chemical Formula] In formula (2), R4 to R6 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R7 represents an arylene group having 6 to 12 carbon atoms.

[0201] According to such a configuration, a copper-clad laminate having an insulating layer with lower dielectric properties and higher heat resistance can be obtained.

[0202] In the resin composition, it is preferable that the structural unit represented by the formula (2) includes a structural unit represented by the following formula (3).

[0203]

Chemical formula

[0204] According to such a configuration, a copper-clad laminate having an insulating layer with lower dielectric properties and higher heat resistance can be obtained.

[0205] In the resin composition, it is preferable that the polymer further includes a polymer having a structural unit represented by the following formula (4) in the molecule.

[0206]

Chemical formula

[0207] According to such a configuration, a copper-clad laminate having an insulating layer with lower dielectric properties and higher heat resistance can be obtained.

[0208] In the resin composition, it is preferable that the aryl group in the structural unit represented by the formula (4) includes an aryl group having an alkyl group having 1 to 6 carbon atoms.

[0209] According to such a configuration, a copper-clad laminate having an insulating layer with lower dielectric properties and higher heat resistance can be obtained.

[0210] In the resin composition, it is preferable that the weight average molecular weight of the polymer is 1500 to 40000.

[0211] According to such a configuration, a copper-clad laminate having an insulating layer with lower dielectric properties and higher heat resistance can be obtained.

[0212] In the resin composition, it is preferable that the equivalent weight of the vinyl group contained in the structural unit represented by the formula (1) of the polymer, where R1 to R3 are hydrogen atoms, is 250 to 1200.

[0213] According to such a configuration, a copper-clad laminate having an insulating layer with lower dielectric properties, higher heat resistance, and excellent moldability can be obtained.

[0214] In the copper-clad laminate, it is preferable that the resin composition contains a modified polyphenylene ether compound end-modified with a group represented by the above formula (5) or (6). Thereby, more excellent low dielectric properties can be obtained.

[0215] In the surface-treated copper foil, it is preferable that the heat treatment layer is composed of nickel or nickel and phosphorus. Thereby, the above-described effects can be obtained more reliably.

[0216] The copper foil with resin according to a further aspect of the present invention includes a resin layer containing the resin composition as described above or a semi-cured product of the resin composition, and the surface-treated copper foil as described above on one side of the resin layer.

[0217] Furthermore, the present invention also includes a circuit board including the above copper-clad laminate or the above copper foil with resin and having a conductor pattern as a circuit on its surface.

[0218] Also, the present invention provides a resin composition for forming an insulating layer in a copper-clad laminate including an insulating layer containing a cured product of the resin composition and the surface-treated copper foil on one or both sides of the insulating layer, the resin composition containing a polymer having a structural unit represented by the following formula (1) in the molecule.

Chemical formula

[0219] Hereinafter, the present invention will be described more specifically by way of examples, but the scope of the present invention is not limited thereto.

Examples

[0220] First, in this example, each component used when preparing the resin composition will be described.

[0221] · Modified PPE1 Polyphenylene ether and chloromethylstyrene were reacted to obtain modified polyphenylene ether 1 (modified PPE1).

[0222] Specifically, first, 200 g of polyphenylene ether (polyphenylene ether, SA90 manufactured by SABIC Innovative Plastics, having 2 terminal hydroxyl groups and a weight average molecular weight Mw of 1700), 30 g of a mixture of p-chloromethylstyrene and m-chloromethylstyrene with a mass ratio of 50:50 (chloromethylstyrene: CMS manufactured by Tokyo Chemical Industry Co., Ltd.), 1.227 g of tetra-n-butylammonium bromide as a phase transfer catalyst, and 400 g of toluene were charged into a 1-liter three-necked flask equipped with a temperature controller, a stirrer, a cooling facility, and a dropping funnel, and stirred. Then, the polyphenylene ether, chloromethylstyrene, and tetra-n-butylammonium bromide were stirred until they were dissolved in toluene. At that time, it was gradually heated and finally heated until the liquid temperature reached 75°C. Then, an aqueous sodium hydroxide solution (20 g of sodium hydroxide / 20 g of water) was dropped into the solution over 20 minutes as an alkali metal hydroxide. Then, it was further stirred at 75°C for 4 hours. Next, after neutralizing the contents of the flask with 10% by mass hydrochloric acid, a large amount of methanol was added. By doing so, a precipitate was formed in the liquid in the flask. That is, the product contained in the reaction solution in the flask was reprecipitated. Then, this precipitate was taken out by filtration, washed three times with a mixed solution of methanol and water with a mass ratio of 80:20, and then dried under reduced pressure at 80°C for 3 hours. And terminal vinylbenzene-modified PPE (modified PPE1) with a weight average molecular weight (Mw) of 2300 was obtained.

[0223] The obtained solid was 1 analyzed by 1H-NMR (400 MHz, CDCl3, TMS). As a result of measuring the NMR, a peak derived from ethenylbenzyl was confirmed at 5 to 7 ppm. From this, it was confirmed that the obtained solid was ethenylbenzylated polyphenylene ether.

[0224] · Modified PPE2 As the polyphenylene ether, the polyphenylene ether described later was used, and it was synthesized in the same manner as the synthesis of modified PPE1 except that the conditions described later were used.

[0225] The polyphenylene ether used was SA120 manufactured by SABIC Innovative Plastics (intrinsic viscosity (IV) 0.125 dl / g, number of terminal hydroxyl groups 1, weight average molecular weight Mw 3100).

[0226] Next, the reaction of polyphenylene ether and chloromethylstyrene was carried out in the same manner as the synthesis of modified PPE1, except that 200 g of the polyphenylene ether (SA120), 15 g of CMS, and 0.92 g of a phase transfer catalyst (tetra - n - butylammonium bromide) were used, and an aqueous sodium hydroxide solution (10 g of sodium hydroxide / 10 g of water) was used instead of the aqueous sodium hydroxide solution (20 g of sodium hydroxide / 20 g of water), to obtain vinylbenzene - modified PPE (modified PPE2) with a weight average molecular weight (Mw) of 3300.

[0227] And the obtained solid was 1 analyzed by 1H - NMR (400 MHz, CDCl3, TMS). As a result of measuring the NMR, peaks derived from ethenylbenzyl were confirmed at 5 - 7 ppm. From this, it was confirmed that the obtained solid was ethenylbenzylated polyphenylene ether.

[0228] · SA9000: SA9000 manufactured by SABIC Innovative Plastics (terminal methacryl - group - modified PPE, weight average molecular weight (Mw) 2000)

[0229] · SA90: SA90 manufactured by SABIC Innovative Plastics (unmodified PPE, weight average molecular weight (Mw) 1700)

[0230] · Polymer 1: A polymer obtained by the following method.

[0231] 2.9 mol (377 g) of divinylbenzene, 1.7 mol (224.4 g) of ethylvinylbenzene, 10.4 mol (1081.6 g) of styrene, and 15 mol (1532 g) of n-propyl acetate were charged into a 5.0 L reactor and stirred. After heating the mixture obtained by this stirring to 70°C, 600 mmol of boron trifluoride diethyl ether complex was added, and further, by stirring at 70°C for 4 hours, divinylbenzene, ethylvinylbenzene, and styrene were reacted. Then, an aqueous solution of saturated sodium hydrogen carbonate was added to the reaction solution in the reactor to stop the reaction. The organic layer separated by this addition was washed three times with pure water. The washed organic layer was devolatilized under reduced pressure at 60°C to obtain Polymer 1.

[0232] The obtained Polymer 1 is a polymer having a structural unit represented by the above formula (1) in the molecule [an aromatic polymer having a structural unit derived from a bifunctional aromatic compound in which two carbon-carbon unsaturated double bonds are bonded to an aromatic ring, a compound having structural units represented by the above formulas (5) to (7), weight average molecular weight Mw: 26300, vinyl equivalent (the equivalent of the vinyl group contained in the structural unit represented by the above formula (1) where R1 to R3 are hydrogen atoms): 510].

[0233] · Polymer 2: A polymer obtained by the following method.

[0234] 3.6 mol (468 g) of divinylbenzene, 2.2 mol (290.4 g) of ethylvinylbenzene, 9.2 mol (956.8 g) of styrene, and 15 mol (1532 g) of n-propyl acetate were charged into a 5.0 L reactor and stirred. After heating the mixture obtained by this stirring to 70°C, 600 mmol of boron trifluoride diethyl ether complex was added, and further, by stirring at 70°C for 4 hours, divinylbenzene, ethylvinylbenzene, and styrene were reacted. Then, an aqueous solution of saturated sodium hydrogen carbonate was added to the reaction solution in the reactor to stop the reaction. And the organic layer separated by this addition was washed three times with pure water. The washed organic layer was devolatilized under reduced pressure at 60°C to obtain Polymer 2.

[0235] The resulting polymer 2 is a polymer having a structural unit represented by the above formula (1) in the molecule [an aromatic polymer having a structural unit derived from a bifunctional aromatic compound in which two carbon-carbon unsaturated double bonds are bonded to an aromatic ring, a compound having structural units represented by the above formulas (5) to (7), weight average molecular weight Mw: 31,100, vinyl equivalent (equivalent of vinyl groups contained in the structural unit represented by the above formula (1) where R1 to R3 are hydrogen atoms): 380].

[0236] · Polymer 3: A polymer obtained by the following method.

[0237] 3.9 mol (507 g) of divinylbenzene, 2.3 mol (303.6 g) of ethylvinylbenzene, 8.8 mol (915.2 g) of styrene, and 15 mol (1532 g) of n-propyl acetate were charged into a 5.0 L reactor and stirred. After heating the mixture obtained by this stirring to 70°C, 600 mmol of boron trifluoride diethyl ether complex was added, and further, by stirring at 70°C for 4 hours, divinylbenzene, ethylvinylbenzene, and styrene were reacted. Then, an aqueous saturated sodium hydrogen carbonate solution was added to the reaction solution in the reactor to stop the reaction. And the organic layer separated by this addition was washed 3 times with pure water. The washed organic layer was devolatilized under reduced pressure at 60°C to obtain Polymer 3.

[0238] The resulting polymer 3 is a polymer having a structural unit represented by the above formula (1) in the molecule [an aromatic polymer having a structural unit derived from a bifunctional aromatic compound in which two carbon-carbon unsaturated double bonds are bonded to an aromatic ring, a compound having structural units represented by the above formulas (5) to (7), weight average molecular weight Mw: 39,500, vinyl equivalent (equivalent of vinyl groups contained in the structural unit represented by the above formula (1) where R1 to R3 are hydrogen atoms): 320].

[0239] The vinyl equivalent (vinyl equivalent weight) of the vinyl groups contained in the structural units represented by the above formula (1) in which R1 to R3 are hydrogen atoms in Polymers 1 to 3 was calculated by measuring the iodine value by the Wijs method. Specifically, first, the compound to be measured was dissolved in chloroform so that the concentration was 0.3 g / 35 mL to 0.3 g / 25 mL. An excess amount of iodine chloride was added to the double bonds present in this solution. By doing so, the double bonds and iodine chloride reacted, and after this reaction had proceeded sufficiently, a 20% by mass aqueous potassium iodide solution was added to the solution after the reaction, whereby the iodine content remaining in the solution after the reaction was extracted into the aqueous phase in the form of I3 - This I3 - The extracted aqueous phase was titrated with an aqueous sodium thiosulfate solution (a 0.1 mol / L standard sodium thiosulfate solution) to calculate the iodine value. The following formula was used to calculate the iodine value.

[0240] Iodine value = [(B - A) × F × 1.269] / mass of compound (g) In the above formula, B represents the titration volume (cc) of the 0.1 mol / L standard sodium thiosulfate solution required for the blank test, A represents the titration volume (cc) of the 0.1 mol / L standard sodium thiosulfate solution required for neutralization, and F represents the titer of sodium thiosulfate.

[0241] · Curing agent 1: TAIC (triallyl isocyanurate, manufactured by Nippon Kasei Co., Ltd.)

[0242] · Curing agent 2: acenaphthylene (manufactured by JFE Chemical Corporation)

[0243] · Curing agent 3: dibromostyrene (manufactured by Fujifilm Wako Pure Chemical Corporation)

[0244] · Reaction initiator: Perbutyl P: 1,3 - di(t - butylperoxyisopropyl)benzene (Perbutyl P manufactured by NOF Corporation)

[0245] <Preparation of surface - treated copper foil> (Surface - treated copper foil 1) As a pretreatment, a copper plate was used as the cathode and the untreated copper foil was used as the anode in a 100 g / L sulfuric acid aqueous solution, and electrolysis was carried out at a current density of 5 A / dm 2 for 6 seconds to remove the oxide layer and activate the surface of the untreated copper foil.

[0246] Next, by treating under the bath composition and electrolysis conditions shown below, a copper fine roughened particle treatment layer was formed on the laminate surface side of the untreated copper foil.

[0247] (Bath composition) Copper sulfate pentahydrate 35 g / L Sodium diethylenetriaminepentaacetate 100 g / L pH 4.8

[0248] (Electrolysis conditions) Current density: 6 A / dm 2 Electric quantity: 50 A·sec / dm 2 Liquid temperature: 30 °C Electrode: Copper plate

[0249] The obtained fine roughened particle treatment layer was observed at a magnification of 80,000 times while tilting the sample stage by 40° using a field emission scanning electron microscope FE-SEM (JSM-7800F manufactured by JEOL Ltd.). As a result, taking the height of the observed copper particles as the particle size value, the particle size of the roughened particles in the fine roughened particle treatment layer was 40 nm at the minimum value and 200 nm at the maximum value.

[0250] Next, after washing with water, the heat-resistant treatment layer, which is the second-layer surface treatment layer, was formed by treating under the bath composition and electrolysis conditions shown below.

[0251] (Bath composition) Nickel sulfate hexahydrate 30 g / L Sodium acetate trihydrate 10 g / L Sodium hypophosphite monohydrate 2.0 g / L

[0252] (Electrolysis conditions) Current density: 1.6 A / dm 2 Electric quantity: 2.7 A·sec / dm 2 pH 4.5 Liquid temperature: 32 °C Anode: Platinum group oxide-coated titanium plate

[0253] The nickel adhesion amount in the obtained heat treatment layer was measured by dissolving the copper foil to be treated with nitric acid, diluting it, and analyzing the nickel concentration with an ICP emission spectrometer. As a result, the nickel adhesion amount was 56 mg / m 2 It was.

[0254] Next, after washing with water, a rust preventive treatment layer serving as the third-layer surface treatment layer was treated under the electrolytic bath composition, pH, and electrolytic conditions shown below.

[0255] (Bath composition) Sodium dichromate: 10 g / L Zinc ions: 1.0 g / L Sodium hydroxide: 40 g / L Liquid temperature: 30 °C

[0256] (Electrolytic conditions) Current density: 4 A / dm 2 Electric quantity: 5.5 A·sec / dm 2 Anode: Platinum group oxide-coated titanium plate

[0257] Next, after washing with water, a silane coupling agent treatment layer serving as the fourth-layer surface treatment layer was formed by treating it under the bath composition, liquid temperature, and immersion time shown below, and the surface-treated copper foil of Example 1 was obtained.

[0258] (Bath composition) γ-Aminopropyltriethoxysilane 2 mL / L Liquid temperature: 30 °C Immersion time: 15 seconds

[0259] (Surface-treated copper foil 2) A surface-treated copper foil 2 was obtained in the same manner as the surface-treated copper foil 1, except that the second heat-treatment layer was formed by treating it under the bath composition and electrolysis conditions shown below. The nickel adhesion amount in the obtained heat-treatment layer was 32 mg / m 2 was obtained.

[0260] (Bath composition) Nickel sulfate hexahydrate 30 g / L Sodium acetate trihydrate 10 g / L Sodium hypophosphite monohydrate 2.0 g / L pH 4.5

[0261] (Electrolysis conditions) Current density: 1.0 A / dm 2 Electric quantity: 1.8 A·sec / dm 2 Liquid temperature: 32°C Electrode: Platinum group oxide-coated titanium plate

[0262] (Surface-treated copper foil 3) A surface-treated copper foil 3 was obtained in the same manner as the surface-treated copper foil 1, except that the second heat-treatment layer was not provided. The nickel adhesion amount in the obtained surface-treated copper foil 3 was 0 mg / m 2 was obtained.

[0263] (Surface-treated copper foil 4) A surface-treated copper foil 4 was obtained in the same manner as the surface-treated copper foil 1, except that the second heat-treatment layer was formed by treating it under the bath composition and electrolysis conditions shown below. The nickel adhesion amount in the obtained heat-treatment layer was 82 mg / m 2 was obtained.

[0264] (Bath composition) Nickel sulfate hexahydrate 30 g / L Sodium acetate trihydrate 10 g / L Sodium hypophosphite monohydrate 2.0 g / L

[0265] (Electrolysis conditions) Current density: 2.1 A / dm 2 Electric quantity: 3.6 A·sec / dm 2 pH 4.5 Liquid temperature: 32 °C Anode: Platinum group oxide-coated titanium plate

[0266] (Surface-treated copper foil 5) "T4X-SV" manufactured by Fukuda Metal Foil & Powder Co., Ltd. was used as the surface-treated copper foil 5. The nickel adhesion amount in the heat treatment layer of this surface-treated copper foil was 106 mg / m 2 was

[0267] (Surface-treated copper foil 6) The surface-treated copper foil 6 was obtained in the same manner as the surface-treated copper foil 1, except that the first fine roughened particle treatment layer was formed by treating under the bath composition and electrolysis conditions shown below. The particle diameter of the roughened particles in the obtained fine roughened particle treatment layer was 700 nm at the minimum value and 1400 nm at the maximum value. Also, the nickel adhesion amount in the obtained heat treatment layer was 32 mg / m 2 was

[0268] (Bath composition) Bath (1) Copper sulfate pentahydrate 47 g / L Sulfuric acid 100 g / L Bath (2) Copper sulfate pentahydrate 200 g / L Sulfuric acid 100 g / L

[0269] (Electrolysis conditions) In bath (1), electrolysis was carried out under the electrolysis conditions of a current density of 50 A / dm 2 , an electric quantity of 130 A·sec / dm 2 , and a liquid temperature of 30 °C to deposit fine copper particles. After that, electrolysis was further carried out in bath (2) under the electrolysis conditions of a current density of 5 A / dm 2 , an electric quantity of 400 A·sec / dm 2 , and a liquid temperature of 40 °C to form a fine roughened particle treatment layer.

[0270] (Surface-treated copper foil 7) The heat - treated layer on the second layer was formed by treating it under the bath composition and electrolysis conditions shown below. Except for not forming the rust - preventive treatment layer, surface - treated copper foil 7 was obtained in the same manner as surface - treated copper foil 1. The nickel adhesion amount in the obtained heat - treated layer was 42 mg / m 2 was obtained.

[0271] (Bath composition) Nickel sulfate hexahydrate 30 g / L Sodium acetate trihydrate 10 g / L Sodium hypophosphite monohydrate 2.0 g / L

[0272] (Electrolysis conditions) Current density: 1.3 A / dm 2 Electric quantity: 2.3 A·sec / dm 2 pH 4.5 Liquid temperature: 32 °C Anode: Platinum - group oxide - coated titanium plate

[0273] <Preparation of copper - clad laminates of Examples 1 - 12 and Comparative Examples 1 - 8> First, each of the above components except the initiator was added to toluene at the compositions (parts by mass) shown in Tables 1 and 2 so that the solid - content concentration became 65% by mass and mixed. The mixture was stirred for 60 minutes. Then, 1,3 - bis(butylperoxyisopropyl)benzene (Perbutyl P manufactured by NOF Corporation), which is an initiator, was added at the blending ratio shown in Table 1 to obtain varnish - like resin compositions (resin varnishes) for each of the examples and comparative examples. Using this resin varnish, the following evaluation substrates were produced.

[0274] (Substrate for heat - resistance evaluation) The resin varnishes obtained in the examples and comparative examples were each impregnated into a glass substrate (♯2116 type, "L - glass" (manufactured by Asahi Kasei Corporation, relative permittivity 4.6)), and then heated and dried at 130 °C for about 3 - 8 minutes to obtain prepregs. At that time, the content (resin content) of resin components such as polyphenylene ether and cross - linking agent was adjusted to be about 50% by mass.

[0275] Then, six obtained prepregs were stacked and laminated, and the copper foils shown in Table 1 were overlapped on both sides, and a copper-clad laminate for evaluation with a thickness of 750 μm was obtained by heating and pressing under the conditions of a temperature of 200°C, a time of 2 hours, and a pressure of 3 MPa.

[0276] [Oven Heat Resistance Test] Using the obtained copper-clad laminate, when test pieces prepared according to JIS C 6481 were treated in a thermostatic chamber with an air circulation device set at 250°C, 260°C, 280°C, and 300°C for one hour, those without any abnormality among the five test pieces were judged as "PASS", and those in which "swelling" or "peeling" occurred in one or more samples among the five test pieces were judged as "NG". In this test, samples that obtained a "PASS" evaluation at 280°C were regarded as qualified.

[0277] [Glass Transition Temperature (Tg)] The outer layer copper foil of the above copper-clad laminate was etched on the entire surface, and for the obtained sample, the Tg was measured using a viscoelastic spectrometer "DMS6100" manufactured by Seiko Instruments Inc. At this time, dynamic viscoelastic measurement (DMA) was performed in a three-point bending mode with a frequency of 10 Hz, and the temperature at which tanδ showed a maximum when the temperature was raised from room temperature to 320°C at a heating rate of 5°C / min was defined as Tg.

[0278] (Substrate for Transmission Characteristics Evaluation) The resin varnishes obtained in the examples and comparative examples were each impregnated into a glass substrate (♯1078 type, "L glass" (manufactured by Asahi Kasei Corporation, relative permittivity 4.6)), and then prepregs were obtained by heating and drying at 130°C for about 3 to 8 minutes. At that time, the content (resin content) of resin components such as polyphenylene ether and crosslinking agent was adjusted to be about 60% by mass.

[0279] Then, two obtained prepregs were stacked and laminated, and the copper foils shown in Table 1 were overlapped on both sides, and a copper-clad laminate for evaluation with a thickness of 150 μm was obtained by heating and pressing under the conditions of a temperature of 200°C, a time of 2 hours, and a pressure of 3 MPa.

[0280] [Transmission Loss Evaluation Test] After processing one side of the obtained double-sided board with a line width of 100 to 200 μm, two additional prepregs were secondarily laminated so as to sandwich the processed surface, and a three-layer board was fabricated. The line width was adjusted so that the characteristic impedance of the circuit would be 50 Ω after finishing.

[0281] Regarding the obtained laminated board, the transmission characteristics were evaluated for the through loss using a network analyzer (N5230A manufactured by Keysight Technologies). The evaluation frequency was 20 GHz.

[0282] The above test results are shown in Tables 3 and 4.

[0283] [Table 3]

[0284] [Table 4]

[0285] As is clear from the results in Table 3, it was confirmed that the laminated board using the surface-treated copper foil and the resin composition of the present invention has excellent heat resistance and is also very excellent in transmission characteristics.

[0286] Also, it was found that when using the resin composition in which the polymer of the present invention and the modified polyphenylene ether compound are used in combination, a higher Tg can be obtained.

[0287] On the other hand, in Comparative Examples 1 to 3 in which the resin composition of the present invention was not used, the transmission loss was inferior to that of the Examples. Also, in Comparative Example 4 in which the nickel adhesion amount in the heat treatment layer of the surface-treated copper foil was 0, heat resistance could not be obtained. On the other hand, in Comparative Examples 5 and 6 in which the nickel adhesion amount in the heat treatment layer was excessive, the transmission characteristics were insufficient.

[0288] In Comparative Example 7 where the copper particle size in the fine roughened particle treatment layer was large, the transmission characteristics were inferior and the heat resistance was not sufficient. In Comparative Example 8 where the rust preventive treatment layer was not formed, sufficient heat resistance could not be obtained either.

[0289] This application is based on Japanese Patent Application No. 2019-092354 filed on May 15, 2019, the content of which is incorporated herein.

[0290] In order to describe the present invention, the present invention has been appropriately and sufficiently described through embodiments with reference to specific examples, drawings, etc. above. However, it should be recognized that those skilled in the art can easily make changes and / or improvements to the above-described embodiments. Therefore, as long as the changes or improvements made by those skilled in the art do not depart from the scope of the claims described in the claims, such changes or improvements are construed to be included within the scope of the claims of the claims.

Industrial Applicability

[0291] The present invention has broad industrial applicability in technical fields such as electronic materials and electronic devices.

Claims

1. A copper-clad laminate comprising a cured product of a resin composition and a surface-treated copper foil on one or both sides of the insulating layer, wherein the resin composition contains a polymer having a structural unit represented by the following formula (1) in the molecule, 【Chemical 1】 (In formula (1), Z represents an arylene group, and R １ ~R ３ each independently represents a hydrogen atom or an alkyl group, and R ４ ~R ６ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) and the surface-treated copper foil is a surface-treated copper foil having a fine roughened particle treatment layer of copper on at least one surface side of the copper foil, the fine roughened particle treatment layer is composed of fine copper particles having a particle diameter of 40 to 200 nm, a heat-resistant treatment layer composed of nickel or nickel and phosphorus is provided on the fine roughened particle treatment layer, a rust-preventive treatment layer containing at least chromium is provided on the heat-resistant treatment layer, a silane coupling agent treatment layer is provided on the rust-preventive treatment layer, and The nickel adhesion amount in the heat-resistant treatment layer is 30 to 60 mg / m ２ which is characterized by a copper-clad laminate.

2. The copper-clad laminate according to claim 1, wherein the structural unit represented by the formula (1) contains a structural unit represented by the following formula (2). ​ (In formula (2), R ４ to R ６ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ７ represents an arylene group having 6 to 12 carbon atoms.)

3. The copper-clad laminate according to claim 2, wherein the structural unit represented by the formula (2) contains a structural unit represented by the following formula (3). 【Chemical Formula 3】 (In formula (3), R ４ to R ６ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

4. The copper-clad laminate according to any one of claims 1 to 3, wherein the polymer further contains a polymer having a structural unit represented by the following formula (4) in the molecule. 【Chemical Formula 4】 (In formula (4), R ８ to R １０ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R １１ represents an aryl group.)

5. The copper-clad laminate according to claim 4, wherein the aryl group in the structural unit represented by the formula (4) contains an aryl group having an alkyl group having 1 to 6 carbon atoms.

6. The copper-clad laminate according to any one of claims 1 to 5, wherein the weight average molecular weight of the polymer is 1500 to 40000.

7. The equivalent weight of the vinyl group contained in the structural unit represented by the formula (1) of the polymer, wherein R １ to R ３ is a hydrogen atom, is 250 to 1200. The copper-clad laminate according to any one of claims 1 to 6.

8. The copper-clad laminate according to any one of claims 1 to 7, wherein the resin composition further contains a modified polyphenylene ether compound having a terminal modified by the following formula (5) or (6). 【Chemical Formula 5】 (In formula (5), s represents an integer of 0 to 10. Z represents an arylene group. R １２ to R １４ each independently represents a hydrogen atom or an alkyl group.) 【Chemical Formula 6】 (In formula (6), R １５ represents a hydrogen atom or an alkyl group.)

9. A copper-foil with resin comprising a resin layer containing a resin composition or a semi-cured product of the resin composition and a surface-treated copper foil on one side of the resin layer, wherein the resin composition contains a polymer having a structural unit represented by the following formula (1) in the molecule, [Chemical Formula 7] (In formula (1), Z represents an arylene group, and R １ ~R ３ each independently represents a hydrogen atom or an alkyl group, and R ４ ~R ６ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) and the surface-treated copper foil is a surface-treated copper foil having a fine roughened particle treatment layer of copper on at least one surface side of the copper foil, the fine roughened particle treatment layer is composed of fine copper particles having a particle diameter of 40 to 200 nm, a heat-resistant treatment layer composed of nickel or nickel and phosphorus is provided on the fine roughened particle treatment layer, a rust-preventive treatment layer containing at least chromium is provided on the heat-resistant treatment layer, a silane coupling agent layer is provided on the rust-preventive treatment layer, and The nickel adhesion amount in the heat-resistant treatment layer is 30 to 60 mg / m ２ which is characterized by a copper-foil with resin.

10. A circuit board comprising the copper-clad laminate according to any one of Claims 1 to 8 or the copper foil with resin according to Claim 9, and having a conductor pattern as a circuit on its surface.

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