JP6176089B2 - LAMINATE AND METHOD FOR PRODUCING LAMINATE - Google Patents

Description

  The present invention relates to a laminate suitably used as a printed wiring board and the like, and a method for producing the laminate, and more specifically, heat resistant used as a resin substrate in a layer made of copper used to form a wiring. In addition, the present invention relates to a laminate in which a layer made of a resin having low water absorption and excellent electrical properties is firmly bonded, and the strong adhesion is maintained even after a thermal history.

  As a resin substrate used for a printed wiring board or the like, a substrate using an epoxy resin or a polyimide resin is widely used. However, in view of the increasing demand for higher frequency signals and higher circuit density for electrical circuits in recent years, epoxy resins and polyimide resins have low water absorption and electrical properties (low dielectric constant Low dielectric loss tangent) tended to be insufficient.

  Then, utilization of cyclic olefin resin is examined as an electrical insulation material used as a material of a resin substrate. For example, in Patent Document 1, a norbornene-based ring-opening polymer hydrogenated substance, which is a kind of cyclic olefin resin, is excellent in low water absorption, low dielectric constant, and the like, and is used for forming an electrical insulating material. It is disclosed that it is suitable as such. However, the norbornene-based ring-opening polymer hydrogenated product disclosed in Patent Document 1 has a problem that heat resistance may be insufficient for use as a resin substrate material, and a circuit is formed. There is also a problem that it is difficult to firmly bond to a metal such as copper used for the purpose.

  For cyclic olefin resins such as norbornene-based ring-opening polymer hydrogenated products, as a method for improving the adhesion to metal, for example, by methods such as modification and copolymerization disclosed in Patent Documents 2 to 5 It is known to introduce functional groups into cyclic olefin resins. However, when a functional group is introduced into the cyclic olefin resin, there is a problem that the low water absorption and electrical characteristics that are characteristic of the cyclic olefin resin are impaired.

  By the way, in order to improve the mechanical strength and heat resistance of a cyclic olefin resin which is an amorphous resin in many cases, norbornene having a melting point, that is, having crystallinity, as disclosed in Patent Document 6, is disclosed. System ring-opening polymer hydrides have been proposed. By using a specific ring-opening polymerization catalyst as disclosed in Patent Literature 6, a norbornene-based ring-opening polymer hydride having crystallinity is obtained, and various kinds of materials utilizing its excellent mechanical strength and heat resistance. Application to applications is under consideration. However, even a crystalline norbornene-based ring-opening polymer hydride has a problem that it is difficult to firmly bond to a metal in order to use it as a resin substrate material.

JP 7-41550 A JP-A-10-158367 JP 2002-363263 A International Publication No. 2001/042332 Japanese Patent Laid-Open No. 5-214079 JP 2002-20464 A

  Therefore, the present invention provides a printed wiring in which copper is firmly bonded to a resin having excellent heat resistance, low water absorption and electrical characteristics, and the strong bonding is maintained even after a thermal history. It aims at providing the laminated body used suitably as a board etc.

  As a result of diligent research to achieve the above object, the present inventor uses an alicyclic structure-containing resin satisfying specific conditions as an adhesive, whereby the crystalline cyclic olefin resin and copper are firmly bonded, and It has been found that a laminate with its strong adhesion maintained can be obtained even after a thermal history. The present invention has been completed based on this finding.

  Thus, according to the present invention, the layer composed of a crystalline cyclic olefin resin having a melting point and the layer composed of copper have a glass transition temperature lower than the melting point of the crystalline cyclic olefin resin, an epoxy group, a carboxyl group, Bonded via a layer made of an alicyclic structure-containing resin containing a functional group selected from the group consisting of a carboxylic acid anhydride group and an oxysilyl group in a proportion of 0.1 to 20 mol% with respect to all repeating units A laminated body is provided.

  Further, according to the present invention, the layer made of a crystalline cyclic olefin resin having a melting point and the layer made of copper have a glass transition temperature lower than the melting point of the crystalline cyclic olefin resin, an epoxy group, a carboxyl group, Laminated through a layer made of an alicyclic structure-containing resin containing 0.1 to 20 mol% of a functional group selected from the group consisting of a carboxylic acid anhydride group and an oxysilyl group with respect to all repeating units Then, by heating these at a temperature not lower than the glass transition temperature of the alicyclic structure-containing resin and not higher than the melting point of the crystalline cyclic olefin resin, the layer composed of the crystalline cyclic olefin resin and the layer composed of the copper are formed. There is provided a method for producing a laminate, which is adhered through a layer made of the alicyclic structure-containing resin.

  According to the present invention, copper is firmly bonded to a resin excellent in heat resistance, low water absorption, and electrical characteristics, and the strong bond is maintained even after a thermal history. A laminate suitably used as a wiring board or the like can be provided.

  In the laminate of the present invention, a layer made of a crystalline cyclic olefin resin having a melting point and a layer made of copper have a glass transition temperature lower than the melting point of the crystalline cyclic olefin resin, and epoxy group, carboxyl group, carboxylic acid Bonded via an alicyclic structure-containing resin layer containing 0.1 to 20 mol% of a functional group selected from the group consisting of an anhydride group and an oxysilyl group with respect to all repeating units. It will be.

  In the laminate of the present invention, the crystalline cyclic olefin resin having a melting point used for constituting a layer composed of a crystalline cyclic olefin resin having a melting point contains an alicyclic structure in the main chain and / or side chain. It is a resin that is made of a polymer and whose crystal melting point can be observed with a differential scanning calorimeter (DSC). The cyclic olefin resin is generally a resin having low water absorption and excellent electrical properties. However, in the laminate of the present invention, by using the crystalline cyclic olefin resin, not only low water absorption and electrical properties, but also heat resistance. In addition, the adhesion to copper becomes strong, and the strong adhesion is maintained even after a thermal history.

  Examples of the crystalline cyclic olefin resin include a dicyclopentadiene ring-opening polymer hydride having syndiotactic stereoregularity as described in WO2012 / 033076, and described in JP-A No. 2002-249553. And dicyclopentadiene ring-opened polymer hydride having such isotactic stereoregularity, and norbornene ring-opened polymer hydride as described in JP-A-2007-16102. In the laminate of the present invention, a known crystalline cyclic olefin resin can be used without any particular limitation. From the viewpoint of easy production of the laminate, the crystalline cyclic olefin resin having a melting point is syndiotactic. Dicyclopentadiene ring-opening polymer hydride having stereoregularity is particularly preferably used.

  Dicyclopentadiene ring-opening polymer hydride having syndiotactic stereoregularity is obtained by performing ring-opening polymerization using dicyclopentadiene as the main monomer, and the carbon-carbon double bond present in the resulting ring-opening polymer. Can be obtained by hydrogenation (hydrogenation) of at least a part thereof. However, in order to give syndiotactic stereoregularity to the finally obtained dicyclopentadiene ring-opening polymer hydride, synergistic stereoregularity is added to the resulting ring-opening polymer in performing ring-opening polymerization. It is necessary to select a ring-opening polymerization catalyst that can be imparted.

The degree of stereoregularity of the dicyclopentadiene ring-opening polymer hydride is not particularly limited as long as it has syndiotactic stereoregularity, but the crystallinity of the dicyclopentadiene ring-opening polymer hydride is increased. From the viewpoint of particularly improving the heat resistance, those having a higher degree of stereoregularity are preferred. More specifically, the ratio of racemo dyad to the repeating unit obtained by ring-opening polymerization of dicyclopentadiene and then hydrogenating is preferably 51% or more, more preferably 60% or more. It is preferably 70% or more. The higher the ratio of racemo dyad, that is, the higher the syndiotactic stereoregularity, the more dicyclopentadiene ring-opening polymer hydride having a higher melting point. The ratio of racemo dyad can be measured and quantified by ¹³ C-NMR spectrum analysis. As a specific quantitative method, ortho-dichlorobenzene-d4 was used as a solvent and an inverse-gated decoupling method was applied at 150 ° C. to perform ¹³ C-NMR measurement, and a 127.5 ppm peak of orthodichlorobenzene-d4 was obtained. As a reference shift, a method of determining the ratio of racemo dyad from the intensity ratio of 43.35 ppm signal derived from meso dyad and 43.43 ppm signal derived from racemo dyad can be mentioned.

  Dicyclopentadiene used as a monomer to obtain a dicyclopentadiene ring-opening polymer hydride has endo and exo stereoisomers, both of which can be used as monomers. One isomer may be used alone, or a mixture of isomers in which an endo isomer and an exo isomer are present in an arbitrary ratio can be used. However, from the viewpoint of increasing the crystallinity of the dicyclopentadiene ring-opening polymer hydride and making the heat resistance particularly good, it is preferable to increase the ratio of one stereoisomer, for example, an endo or exo The body ratio is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more. In addition, it is preferable that the stereoisomer which makes a ratio high is an end body from a viewpoint of synthetic | combination ease.

  The monomer used to obtain the dicyclopentadiene ring-opened polymer hydride may contain a compound copolymerizable with dicyclopentadiene as long as dicyclopentadiene is the main monomer. Examples of such compounds include norbornenes other than dicyclopentadiene, and cyclic olefins or dienes. However, the content of the compound other than dicyclopentadiene in the monomer is preferably 10% by weight or less, and more preferably 5% by weight or less.

  As long as the ring-opening polymerization catalyst is capable of ring-opening polymerization of dicyclopentadiene and can impart syndiotactic stereoregularity to the target dicyclopentadiene ring-opening polymer hydride, particularly, It is not limited. Examples of the ring-opening polymerization catalyst preferably used include a ring-opening polymerization catalyst comprising a metal compound represented by the following formula (1).

M (NR ¹ ) X _4-a (OR ² ) _a · L _b (1)

(In the formula (1), M is a metal atom selected from Group 6 transition metal atoms in the periodic table, and R ¹ has a substituent at at least one of the 3, 4, and 5 positions. Or a group represented by —CH ₂ R ³ , wherein R ² is a group selected from an optionally substituted alkyl group and an optionally substituted aryl group X is a group selected from a halogen atom, an alkyl group, an aryl group and an alkylsilyl group, L is an electron-donating neutral ligand, a is 0 or 1, and b is 0 And R ³ is a group selected from a hydrogen atom, an alkyl group which may have a substituent, and an aryl group which may have a substituent.

  The metal atom (M in formula (1)) constituting the metal compound represented by formula (1) is selected from group 6 transition metal atoms (chromium, molybdenum, tungsten) in the periodic table. Among these, molybdenum or tungsten is preferably used, and tungsten is particularly preferably used.

The metal compound represented by Formula (1) comprises a metal imide bond. The substituent on the nitrogen atom constituting the metal imide bond (R ¹ in the formula (1)) is a phenyl group which may have a substituent at at least one of the 3, 4, and 5 positions, or- A group represented by CH ₂ R ³ (wherein R ³ is a group selected from a hydrogen atom, an alkyl group which may have a substituent and an aryl group which may have a substituent); It is. Examples of the substituent that the phenyl group which may have a substituent at at least one of the 3, 4, and 5 positions include an alkyl group such as a methyl group and an ethyl group; a fluorine atom, a chlorine atom, and a bromine atom A halogen atom such as; an alkoxy group such as a methoxy group, an ethoxy group, and an isopropoxy group; and the like, and further, substituents present in at least two positions of the 3, 4, and 5 positions are bonded to each other. Also good. Specific examples of the phenyl group which may have a substituent at at least one of the 3, 4, and 5 positions include an unsubstituted phenyl group, a 4-methylphenyl group, a 4-chlorophenyl group, and 3-methoxyphenyl. Groups, monosubstituted phenyl groups such as 4-cyclohexylphenyl group, 4-methoxyphenyl group; 3,5-dimethylphenyl group, 3,5-dichlorophenyl group, 3,4-dimethylphenyl group, 3,5-dimethoxyphenyl group Disubstituted phenyl groups such as 3,4,5-trimethylphenyl groups, 3,4,5-trichlorophenyl groups and the like; 2-naphthyl groups, 3-methyl-2-naphthyl groups, 4-methyl 2-naphthyl group which may have a substituent such as a 2-naphthyl group;

In the metal compound represented by the formula (1), in the group represented by —CH ₂ R ³ that can be used as a substituent on the nitrogen atom (R ¹ in the formula (1)), R ³ is a hydrogen atom. Represents a group selected from an alkyl group which may have a substituent and an aryl group which may have a substituent. Although carbon number of the alkyl group which may be a group represented by this R ³ and may have a substituent is not particularly limited, it is usually 1 to 20, preferably 1 to 10. The alkyl group may be linear or branched. Although the substituent which this alkyl group may have is not specifically limited, For example, the phenyl group which may have substituents, such as a phenyl group and 4-methylphenyl group; Alkoxyl groups, such as a methoxy group and an ethoxy group; Can be mentioned.

In the metal compound represented by the formula (1), an aryl group which may be used as a substituent on the nitrogen atom (R ¹ in the formula (1)) and may have a substituent includes a phenyl group, Examples include 1-naphthyl group, 2-naphthyl group, and aryl groups in which hydrogen atoms of these groups are replaced with other substituents. Further, the substituent of this aryl group is not particularly limited, but for example, a phenyl group which may have a substituent such as a phenyl group or a 4-methylphenyl group; an alkoxyl group such as a methoxy group or an ethoxy group; Can be mentioned.

The group represented by R ³ has 1 carbon number such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, octyl group and decyl group. ˜20 alkyl groups are particularly preferably used.

  The metal compound represented by the formula (1) has 3 or 4 groups selected from a halogen atom, an alkyl group, an aryl group, and an alkylsilyl group. That is, in the formula (1), X represents a group selected from a halogen atom, an alkyl group, an aryl group, and an alkylsilyl group. In addition, when there are two or more groups represented by X in the metal compound represented by the formula (1), these groups may be bonded to each other.

  Examples of the halogen atom that can be a group represented by X include a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a neopentyl group, a benzyl group, and a neophyll group. Examples of the aryl group include a phenyl group, a 4-methylphenyl group, a 2,6-dimethylphenyl group, a 1-naphthyl group, and a 2-naphthyl group. Examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a t-butyldimethylsilyl group.

The metal compound represented by the formula (1) may have one metal alkoxide bond or one metal aryloxide bond. The substituent on the oxygen atom constituting this metal alkoxide bond or metal aryloxide bond (R ² in formula (1)) may have an alkyl group which may have a substituent and a substituent. It is a group selected from good aryl groups. The alkyl group which may have a substituent and the aryl group which may have a substituent which can be the group represented by R ² are the same as those in the group represented by R ³ described above. Can be used.

  The metal compound represented by the formula (1) may have one or two electron-donating neutral ligands. Examples of the electron-donating neutral ligand (L in the formula (1)) include electron-donating compounds containing atoms of Group 14 or Group 15 of the Periodic Table. Specific examples thereof include phosphines such as trimethylphosphine, triisopropylphosphine, tricyclohexylphosphine, and triphenylphosphine; ethers such as diethyl ether, dibutyl ether, 1,2-dimethoxyethane, and tetrahydrofuran; trimethylamine, triethylamine, pyridine, And amines such as lutidine; Of these, ethers are particularly preferably used.

As the metal compound represented by the formula (1) which is particularly preferably used as the ring-opening polymerization catalyst, a tungsten compound having a phenylimide group (M in the formula (1) is a tungsten atom and R ¹ is phenyl). A compound which is a group), and among them, a tungsten phenylimide tetrachloride (tetrahydrofuran) complex is particularly suitable.

  The metal compound represented by the formula (1) includes an oxyhalide of a Group 6 transition metal and phenyl isocyanates optionally having a substituent at at least one of the 3, 4, and 5 positions, or Mixing monosubstituted methyl isocyanates with an electron-donating neutral ligand (L) and, if necessary, alcohols, metal alkoxides, metal aryloxides (for example, JP-A-5-345817) Can be synthesized by the method described in 1). The synthesized metal compound represented by the formula (1) may be purified and isolated by crystallization or the like, or the catalyst synthesis solution may be used as it is as a ring-opening polymerization catalyst without purification. You can also.

  The amount of the metal compound represented by the formula (1) used as the ring-opening polymerization catalyst is such that the molar ratio of (metal compound: whole monomer used) is usually from 1: 100 to 1: 2,000,000, preferably Is used in an amount of 1: 500 to 1,000,000, more preferably 1: 1,000 to 1: 500,000. If the amount of catalyst is too large, it may be difficult to remove the catalyst. If the amount is too small, sufficient polymerization activity may not be obtained.

  In using the metal compound represented by the formula (1) as a ring-opening polymerization catalyst, the metal compound represented by the formula (1) can be used alone, but from the viewpoint of increasing the polymerization activity, the formula (1 It is preferable to use a metal compound represented by 1) and an organometallic reducing agent in combination. Examples of the organometallic reducing agent that can be used include organometallic compounds of Groups 1, 2, 12, 13, and 14 of the periodic table having a hydrocarbon group having 1 to 20 carbon atoms. Among these, organolithium, organomagnesium, organozinc, organoaluminum, or organotin is preferably used, and organoaluminum or organotin is particularly preferably used. Examples of the organic lithium include n-butyl lithium, methyl lithium, and phenyl lithium. Examples of the organic magnesium include butylethylmagnesium, butyloctylmagnesium, dihexylmagnesium, ethylmagnesium chloride, n-butylmagnesium chloride, and allylmagnesium bromide. Examples of the organic zinc include dimethyl zinc, diethyl zinc, and diphenyl zinc. Examples of organic aluminum include trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum ethoxide, diisobutylaluminum isobutoxide, ethylaluminum diethoxide, isobutylaluminum diisobutoxide, etc. Can be mentioned. Examples of the organic tin include tetramethyltin, tetra (n-butyl) tin, and tetraphenyltin. The amount of the organometallic reducing agent used is preferably 0.1 to 100 moles, more preferably 0.2 to 50 moles, and 0.5 to 20 moles relative to the metal compound represented by the formula (1). Double is particularly preferred. If the amount used is too small, the polymerization activity may not be improved, and if it is too much, side reactions may easily occur.

  The polymerization reaction for obtaining the ring-opened polymer is usually carried out in an organic solvent. The organic solvent to be used is not particularly limited as long as the resulting ring-opening polymer or a hydrogenated product thereof can be dissolved or dispersed under predetermined conditions and does not inhibit the polymerization reaction or the hydrogenation reaction. Specific examples of the organic solvent include aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, and tricyclodecane. , Hexahydroindene, cyclooctane and other alicyclic hydrocarbons; benzene, toluene, xylene and other aromatic hydrocarbons; dichloromethane, chloroform, 1,2-dichloroethane and other halogenated aliphatic hydrocarbons; chlorobenzene, dichlorobenzene, etc. Halogen-containing aromatic hydrocarbons; nitrogen-containing hydrocarbon solvents such as nitromethane, nitrobenzene and acetonitrile; ethers such as diethyl ether and tetrahydrofuran; Others can be mixtures of these solvents. Of these solvents, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and ethers are preferably used.

  The ring-opening polymerization reaction can be started by mixing the monomer, the metal compound represented by the formula (1), and, if necessary, an organometallic reducing agent. The order in which these components are added is not particularly limited. For example, a mixture of a metal compound represented by the formula (1) and the organometallic reducing agent may be added to the monomer and mixed, or the organometallic reducing agent may be represented by the monomer and the formula (1). A mixture with a metal compound to be added may be added and mixed, or a metal compound represented by formula (1) may be added to and mixed with a mixture of a monomer and an organometallic reducing agent. . Moreover, when mixing each component, the whole quantity of each component may be added at once, may be added in multiple times, and it is continuous over a comparatively long time (for example, 1 minute or more). It can also be added.

  The concentration of the monomer during the polymerization reaction in the organic solvent is not particularly limited, but is preferably 1 to 50% by weight, more preferably 2 to 45% by weight, and particularly 3 to 40% by weight. preferable. If the monomer concentration is too low, the productivity of the polymer may be deteriorated. If it is too high, the solution viscosity after polymerization is too high, and the subsequent hydrogenation reaction may be difficult.

  An activity regulator may be added to the polymerization reaction system. The activity adjusting agent can be used for the purpose of stabilizing the ring-opening polymerization catalyst, adjusting the polymerization reaction rate and the molecular weight distribution of the polymer. The activity regulator is not particularly limited as long as it is an organic compound having a functional group, but is preferably an oxygen-containing, nitrogen-containing, or phosphorus-containing organic compound. Specifically, ethers such as diethyl ether, diisopropyl ether, dibutyl ether, anisole, furan and tetrahydrofuran; ketones such as acetone, benzophenone and cyclohexanone; esters such as ethyl acetate; nitriles such as acetonitrile benzonitrile; triethylamine , Triisopropylamine, quinuclidine, amines such as N, N-diethylaniline; pyridines such as pyridine, 2,4-lutidine, 2,6-lutidine, 2-t-butylpyridine; triphenylphosphine, tricyclohexylphosphine Phosphines such as triphenyl phosphate and trimethyl phosphate; triphenyl phosphine, tricyclohexyl phosphine, triphenyl phosphate, trimethyl phosphate - phosphines such as preparative; phosphine oxides such as triphenylphosphine oxide; but like, but not limited to. These activity regulators can be used singly or in combination of two or more. The amount of the activity regulator to be added is not particularly limited, but it may be usually selected between 0.01 and 100 mol% with respect to the metal compound used as the ring-opening polymerization catalyst.

  Further, a molecular weight modifier may be added to the polymerization reaction system in order to adjust the molecular weight of the ring-opening polymer. Examples of molecular weight modifiers include α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; aromatic vinyl compounds such as styrene and vinyltoluene; ethyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether, acetic acid Oxygen-containing vinyl compounds such as allyl, allyl alcohol and glycidyl methacrylate; halogen-containing vinyl compounds such as allyl chloride; nitrogen-containing vinyl compounds such as acrylamide; 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1 , 6-heptadiene, 2-methyl-1,4-pentadiene, non-conjugated dienes such as 2,5-dimethyl-1,5-hexadiene; 1,3-butadiene, 2-methyl-1,3-butadiene, 2, 3-dimethyl-1,3-butadiene, 1 3-pentadiene, a conjugated diene such as 1,3-hexadiene; can be mentioned. The amount of the molecular weight modifier to be added may be determined according to the target molecular weight, but is usually selected in the range of 0.1 to 50 mol% with respect to the monomer used.

  Although there is no restriction | limiting in particular in superposition | polymerization temperature, Usually, it is the range of -78 degreeC-+200 degreeC, Preferably it is the range of -30 degreeC-+180 degreeC. The polymerization time is not particularly limited and depends on the reaction scale, but is usually in the range of 1 minute to 1000 hours.

  By using the ring-opening polymerization catalyst containing the metal compound represented by the formula (1) as described above, the ring-opening polymerization reaction of dicyclopentadiene is performed under the conditions as described above, thereby syndiotactic stereoregularity is achieved. A dicyclopentadiene ring-opening polymer can be obtained. If the conditions of the hydrogenation reaction are set appropriately, the tacticity of the ring-opening polymer will not change during the hydrogenation reaction, so this ring-opening polymer having syndiotactic stereoregularity should be used in the hydrogenation reaction. Thus, a dicyclopentadiene ring-opened polymer hydride having the desired syndiotactic stereoregularity can be obtained. The degree of syndiotactic stereoregularity of the ring-opening polymer can be adjusted by selecting the type of ring-opening polymerization catalyst.

  The weight average molecular weight (Mw) measured by gel permeation chromatography of the ring-opening polymer subjected to the hydrogenation reaction is not particularly limited, but is preferably 1,000 to 1,000,000 in terms of polystyrene. More preferably, it is 2,000 to 500,000. By subjecting the ring-opening polymer having such a weight average molecular weight to a hydrogenation reaction, it is possible to obtain a dicyclopentadiene ring-opening polymer hydride having an excellent balance between molding processability and heat resistance. The weight average molecular weight of the ring-opening polymer can be adjusted by adjusting the amount of the molecular weight modifier used during polymerization.

  The molecular weight distribution of the ring-opening polymer to be subjected to the hydrogenation reaction [ratio of polystyrene-equivalent number average molecular weight and weight average molecular weight (Mw / Mn) measured by gel permeation chromatography] is not particularly limited. It is 0-4.0, Preferably it is 1.5-3.5. By subjecting the ring-opening polymer having such a molecular weight distribution to a hydrogenation reaction, a dicyclopentadiene ring-opening polymer hydride having particularly excellent molding processability can be obtained. The molecular weight distribution of the ring-opening polymer can be adjusted by the monomer addition method and the monomer concentration during the polymerization reaction.

  The hydrogenation reaction of the ring-opening polymer can be performed by supplying hydrogen into the reaction system in the presence of a hydrogenation catalyst. Any hydrogenation catalyst can be used as long as it is generally used in the hydrogenation of olefin compounds, and is not particularly limited. Examples thereof include the following.

  As the homogeneous catalyst, a catalyst system comprising a combination of a transition metal compound and an alkali metal compound, such as cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec- Examples include butyl lithium, tetrabutoxy titanate / dimethyl magnesium, and the like. Further, dichlorobis (triphenylphosphine) palladium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, chlorohydridocarbonylbis (tricyclohexylphosphine) ruthenium, bis (tricyclohexylphosphine) benzilidineruthenium (IV) dichloride, chlorotris (triphenyl) Mention may be made of noble metal complex catalysts such as phosphine) rhodium.

  As the heterogeneous catalyst, nickel, palladium, platinum, rhodium, ruthenium, or a solid catalyst in which these metals are supported on a support such as carbon, silica, diatomaceous earth, alumina, titanium oxide, for example, nickel / silica, nickel / Examples of the catalyst system include diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, and palladium / alumina.

  The hydrogenation reaction is usually performed in an inert organic solvent. Examples of such inert organic solvents include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as pentane and hexane; alicyclic hydrocarbons such as cyclohexane and decahydronaphthalene; tetrahydrofuran, ethylene glycol dimethyl ether, and the like. Ethers; and the like. The inert organic solvent is usually the same as the solvent used in the polymerization reaction, and the hydrogenation catalyst may be added to the polymerization reaction solution as it is and reacted.

  Although the suitable range of conditions varies depending on the hydrogenation catalyst system used, the reaction temperature is usually -20 ° C to + 250 ° C, preferably -10 ° C to + 220 ° C, more preferably 0 ° C to 200 ° C. . If the hydrogenation temperature is too low, the reaction rate may be too slow, and if it is too high, side reactions may occur. The hydrogen pressure is usually 0.01 to 20 MPa, preferably 0.05 to 15 MPa, and more preferably 0.1 to 10 MPa. If the hydrogen pressure is too low, the hydrogenation rate may be too slow, and if it is too high, there will be restrictions on the apparatus in that a high pressure reactor is required. Although reaction time will not be specifically limited if it can be set as the desired hydrogenation rate, Usually, it is 0.1 to 10 hours. After the hydrogenation reaction, the target dicyclopentadiene ring-opened polymer hydride may be recovered according to a conventional method, and the catalyst residue can be removed by a technique such as filtration.

  The hydrogenation rate (ratio of hydrogenated main chain double bonds) in the hydrogenation reaction of the ring-opening polymer is not particularly limited, but is preferably 98% or more, more preferably 99% or more. The higher the hydrogenation rate, the better the heat resistance of the finally obtained dicyclopentadiene ring-opening polymer hydride.

  In the laminate of the present invention, as long as the melting point of the crystalline cyclic olefin resin used for constituting the layer composed of the crystalline cyclic olefin resin is higher than the glass transition temperature of the alicyclic structure-containing resin described later. Although it does not specifically limit, Preferably it is 180-350 degreeC, More preferably, it is 200-320 degreeC, Especially preferably, it is 220-300 degreeC. When the melting point of the crystalline cyclic olefin resin is within this range, the balance between moldability and heat resistance is improved. In addition, the dicyclopentadiene ring-opening polymer hydride having syndiotactic stereoregularity usually has a melting point within such a temperature range.

  For the crystalline cyclic olefin resin, if necessary, an antioxidant, a crystal nucleating agent, a filler, a flame retardant, a flame retardant aid, a colorant, an antistatic agent, a plasticizer, an ultraviolet absorber, a light stabilizer, You may add various additives, such as a near-infrared absorber and a lubricant. Examples of the antioxidant include phenol-based antioxidants such as (tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, and phosphorus-based antioxidants. , Sulfur-based antioxidants, etc., can be used without any particular limitation The amount of the antioxidant added to the crystalline cyclic olefin resin is not particularly limited, but is 100 parts by weight of the crystalline cyclic olefin resin. The amount is usually 0.001 to 5 parts by weight, preferably 0.01 to 4 parts by weight, more preferably 0.1 to 3 parts by weight.

  Moreover, the form of the crystalline cyclic olefin resin to be laminated is not particularly limited, but the form of a film is preferable in order to make the obtained laminate have excellent flexibility. In the case where the crystalline cyclic olefin resin is a film, the thickness is not particularly limited, but is preferably 10 to 150 μm, and more preferably 15 to 100 μm. The crystalline cyclic olefin resin may be subjected to known surface treatments such as plasma treatment, ultraviolet (UV) treatment, corona discharge treatment, etc., as necessary, for the purpose of further strengthening the adhesive strength. .

  In the laminate of the present invention, the form of copper used for constituting the layer made of copper is not particularly limited. However, when the purpose is to obtain an electric circuit using the copper layer, the form of copper foil is used. Is preferred. What is necessary is just to select suitably the thickness and roughening state of copper foil according to the intended purpose. Moreover, you may process to a copper foil with a silane coupling agent, a titanate coupling agent, etc. as needed for the purpose of making adhesive strength stronger. In addition, when using what contains a carboxyl group or a carboxylic acid anhydride group as alicyclic structure containing resin mentioned later, when the surface of copper foil is processed using an aminosilane coupling agent, what has stronger adhesive force It can be.

  In the laminate of the present invention, the resin used for constituting the layer comprising the alicyclic structure-containing resin has a glass transition temperature lower than the melting point of the crystalline cyclic olefin resin, and has an epoxy group, a carboxyl group, and a carboxylic acid. An alicyclic structure-containing resin containing a functional group selected from the group consisting of an anhydride group and an oxysilyl group in a proportion of 0.1 to 20 mol% based on all repeating units.

  The alicyclic structure-containing resin is not particularly limited as long as it is a resin composed of a polymer containing an alicyclic structure in the main chain and / or side chain. For example, a ring-opening polymer of a monomer having a norbornene ring and its hydrogen And an aromatic ring hydride of an aromatic ring-containing polymer, an addition polymer of a monomer having a norbornene ring and an α-olefin, an addition polymer of a cyclic olefin or a cyclic diene, and a hydride thereof. These alicyclic structure-containing resins are commercially available, and specific examples of commercially available products include ZEONEX (registered trademark), ZEONOR (registered trademark) manufactured by Zeon Corporation, APEL (registered trademark), APO (registered trademark) manufactured by Mitsui Chemicals, Inc. Registered trademark) and TOPAS (registered trademark) manufactured by Polyplastics. However, from the viewpoint of making the laminate of the present invention particularly excellent in flexibility, among the alicyclic structure-containing resins, a copolymer of an aromatic vinyl monomer and a conjugated diene monomer (the following In the description, a copolymer hydride (hereinafter referred to as “copolymer A”), which can be obtained by hydrogenating the unsaturated ring in the aromatic ring and the conjugated diene monomer unit. In the description of (1), it may be simply referred to as “copolymer hydride”).

  The aromatic vinyl monomer used to obtain the copolymer A is not particularly limited as long as it is an aromatic vinyl compound. For example, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4 -Methylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 4-bromostyrene, 2-methyl-4,6-dichlorostyrene, 2,4-dibromostyrene, vinylnaphthalene and the like. Of these, styrene is preferably used. In addition, these aromatic vinyl monomers can be used alone or in combination of two or more in obtaining the copolymer A.

  The conjugated diene monomer used for obtaining the copolymer A is not particularly limited as long as it is a conjugated diene compound. For example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, Examples include 2-chloro-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene and the like. Among these, it is preferable to use 1,3-butadiene and / or isoprene. Further, when a compound having a functional group is reacted with the hydride of the copolymer as described later, the reaction becomes easy. Therefore, it is particularly preferable to use isoprene.

  The content ratio of the aromatic vinyl monomer unit and the conjugated diene monomer unit in the copolymer A is not particularly limited, but is 20% by weight ratio of the aromatic vinyl monomer unit to the conjugated diene monomer unit. : It is preferable that it is 80-65: 35, and it is more preferable that it is 30: 70-60: 40.

  In obtaining the copolymer A, monomers other than the aromatic vinyl monomer and the conjugated diene monomer may be further copolymerized without departing from the present invention. Other monomers include α, β-unsaturated nitrile monomer, unsaturated epoxy monomer, unsaturated carboxylic acid or acid anhydride monomer, unsaturated alkoxysilane monomer, unsaturated carboxylic acid Examples thereof include, but are not limited to, ester monomers and non-conjugated diene monomers. The content of other monomer units other than the aromatic vinyl monomer unit and the conjugated diene monomer unit in the copolymer A is not particularly limited. % Or less, more preferably 5% by weight or less, and particularly preferably 1% by weight or less.

  The copolymerization mode of the copolymer A is not particularly limited and may be any of random copolymerization, taper copolymerization, block copolymerization, graft copolymerization, etc., but flexibility of the resulting copolymer hydride From the viewpoint of achieving a good balance between strength and strength, at least one aromatic vinyl polymer block (a polymer block having an aromatic vinyl monomer unit as a main constituent unit) and at least one conjugated diene polymer It is preferably an aromatic vinyl-conjugated diene block copolymer comprising a block (a polymer block having a conjugated diene monomer unit as a main constituent unit), and at least two aromatic vinyl polymer blocks And at least one conjugated diene polymer block, the aromatic vinyl polymer block occupying both ends of the polymer chain And particularly preferably a conjugated di-entry block copolymer - more preferably role diene block copolymer, the aromatic vinyl aromatic vinyl polymer block at both ends of the conjugated diene polymer block formed by bonding.

  When the copolymer A is a block copolymer having an aromatic vinyl polymer block and a conjugated diene polymer block, other than the aromatic vinyl monomer unit in the aromatic vinyl polymer block The content of the monomer unit and the content of the monomer unit other than the conjugated diene monomer unit in the conjugated diene polymer block are not particularly limited, but each is preferably 10% by weight or less. It is more preferably 5% by weight or less, and particularly preferably 1% by weight or less.

  The polymerization method for obtaining the copolymer A is not particularly limited, and any of radical polymerization, anion polymerization method, cation polymerization method, coordination anion polymerization method, coordination cation polymerization method and the like may be used. When the copolymer A is a block copolymer, an anionic polymerization method is preferable, and a living anionic polymerization method is particularly preferable.

  When the living anionic polymerization method is used, examples of the initiator include monoorganolithium such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, and phenyllithium, dilithiomethane, 1,4-dilithiobutane, 1 Polyfunctional organolithium compounds such as 1,4-dilithio-2-ethylcyclohexane and the like can be used, and monoorganolithium is particularly preferred. The polymerization reaction temperature is not particularly limited, but is usually selected in the range of 0 ° C to 100 ° C, preferably 10 ° C to 80 ° C, particularly preferably 20 ° C to 70 ° C.

  The polymerization reaction form for obtaining the copolymer A is not particularly limited, and any of solution polymerization, slurry polymerization, and the like may be used. However, using solution polymerization is preferable because it is easy to remove reaction heat. Examples of the solvent used in the solution polymerization include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane, and isooctane; cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane. And alicyclic hydrocarbons such as decalin; aromatic hydrocarbons such as benzene and toluene. Among these, alicyclic hydrocarbons are preferable because they can be used as they are as an inert solvent in the hydrogenation reaction described later and the solubility of the copolymer A is good. These solvents may be used alone or in combination of two or more.

  When an anionic polymerization method is used as a polymerization method for obtaining the copolymer A, a Lewis base compound is added to the polymerization reaction system for the purpose of improving the reaction rate and controlling the microstructure of the copolymer A. can do. Examples of the Lewis base compound include ether compounds such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, diphenyl ether, ethylene glycol diethyl ether, and ethylene glycol methyl phenyl ether; tetramethylethylenediamine, trimethylamine, triethylamine, pyridine, and the like. Tertiary amine compounds; alkali metal alkoxide compounds such as potassium-t-amyl oxide and potassium-t-butyl oxide; phosphine compounds such as triphenylphosphine; and the like. These Lewis base compounds may be used alone or in combination of two or more.

The hydrogenation rate of the copolymer A in obtaining the copolymer hydride is such that at least some of the unsaturated bonds of both the aromatic ring and the conjugated diene monomer unit of the copolymer A are hydrogenated. As long as it is not particularly limited, the proportion of hydrogenated unsaturated bonds in the total unsaturated bonds in the copolymer A is preferably 90% or more, more preferably 97% or more, and particularly preferably 99%. That's it. In addition, the hydrogenation rate of the copolymer A in obtaining a copolymer hydride can be calculated | required based on < ¹ > H-NMR measurement.

  In obtaining the copolymer hydride, the hydrogenation method and reaction mode of the unsaturated bond of the copolymer A are not particularly limited, and may be performed according to a known method, but hydrogenation of the unsaturated bond containing an aromatic ring. A hydrogenation method which can increase the rate and has little polymer chain scission reaction is preferred. Examples of such a preferable hydrogenation method include a method using a catalyst containing at least one metal selected from nickel, cobalt, rhodium, palladium, platinum and the like. As the hydrogenation catalyst, either a heterogeneous catalyst or a homogeneous catalyst can be used, and the hydrogenation reaction is preferably carried out in an organic solvent.

  When a heterogeneous catalyst is used as the hydrogenation catalyst, the metal or metal compound can be used as it is or supported on a suitable carrier. Examples of the carrier include activated carbon, silica, alumina, calcium carbonate, titania, magnesia, zirconia, diatomaceous earth, silicon carbide, calcium fluoride and the like. The amount of the catalyst supported is usually 0.1 to 60% by weight, preferably 1 to 50% by weight, based on the total amount of the catalyst and the carrier.

  When a homogeneous catalyst is used as the hydrogenation catalyst, for example, a catalyst in which a nickel or cobalt compound and an organometallic compound (for example, an organoaluminum compound or an organolithium compound) are combined; an organometallic complex such as rhodium, palladium, or platinum A catalyst or the like can be used. As the nickel or cobalt compound, for example, various metal acetylacetonate compounds, carboxylates, cyclopentadienyl compounds, and the like are used. Examples of the organoaluminum compound include alkylaluminums such as triethylaluminum and triisobutylaluminum; aluminum halides such as diethylaluminum chloride and ethylaluminum dichloride; and alkylaluminum hydrides such as diisobutylaluminum hydride. Examples of the organometallic complex catalyst include transition metal complexes such as chlorotris (triphenylphosphine) rhodium, palladium acetate, and dichlorobis (triphenylphosphine) palladium.

  These hydrogenation catalysts may be used alone or in combination of two or more. The usage-amount of a hydrogenation catalyst is 0.01-100 weight part normally with respect to 100 weight part of polymers A, Preferably it is 0.05-50 weight part, More preferably, it is 0.1-30 weight part.

  Although hydrogenation reaction temperature is not specifically limited, Usually, 10 to 250 degreeC, Preferably it is 50 to 200 degreeC, More preferably, it is 80 to 180 degreeC. Also, the hydrogen pressure is not particularly limited, but is usually 0.1 MPa to 30 MPa, preferably 1 MPa to 20 MPa, more preferably 2 MPa to 10 MPa.

  The copolymer hydride obtained by the hydrogenation reaction of copolymer A was removed from the reaction solution containing the copolymer hydride by a method such as filtration or centrifugation. Later, it is recovered from the reaction solution. Examples of the method for recovering the copolymer hydride from the reaction solution include a steam coagulation method in which the solvent is removed by steam stripping from the copolymer hydride solution, a direct desolvation method in which the solvent is removed under reduced pressure heating, A publicly known method such as a coagulation method in which a solution is poured into a poor solvent of a copolymer hydride and precipitated and solidified can be exemplified.

  In the laminate of the present invention, the alicyclic structure-containing resin contains 0.1 to 0.1 functional groups selected from the group consisting of an epoxy group, a carboxyl group, a carboxylic anhydride group, and an oxysilyl group with respect to all repeating units. It is contained in a proportion of 20 mol%, preferably 0.2 to 15 mol%, particularly preferably 0.5 to 5 mol%. If the amount of the functional group contained in the alicyclic structure-containing resin is too small, there is a risk that the crystalline cyclic olefin resin and copper and the adhesive force may be insufficient. If the amount of the functional group is too large, the water absorption of the alicyclic structure-containing resin Therefore, there is a risk that the low water absorption and excellent electrical characteristics of the resulting laminate will be impaired. When the copolymer hydride has an oxysilyl group, the ratio of the oxysilyl group is determined on the basis of the number of silicon atoms in the oxysilyl group.

  The method for introducing the functional group into the alicyclic structure-containing resin is not particularly limited. For example, by using a compound having a target functional group as at least a part of the monomer for obtaining the alicyclic structure-containing resin. The alicyclic structure-containing resin may have a functional group. However, when the alicyclic structure-containing resin is a hydride of a block copolymer of an aromatic vinyl monomer and a conjugated diene monomer, the viewpoint of ease of reaction for introducing a functional group Therefore, a method of reacting a compound having a target functional group with an alicyclic structure-containing resin is preferable. Among them, a compound containing a target functional group and an ethylenically unsaturated bond in the molecule is converted to a peroxide. A method of reacting with a copolymer hydride in the presence is particularly preferred.

  Examples of the compound containing a functional group and an ethylenically unsaturated bond in the molecule that can be used for introducing the functional group into the alicyclic structure-containing resin include ethylenic groups such as aliglycidyl ether, glycidyl acrylate, and glycidyl methacrylate. Saturated group-containing epoxy compound, maleic acid, monomethyl maleate, acrylic acid, methacrylic acid, ethylenically unsaturated group-containing carboxylic acid such as 4-pentenoic acid, maleic anhydride, itaconic anhydride, 4-cyclohexene-1,2- Dicarboxylic anhydride, ethylenically unsaturated dicarboxylic anhydride such as bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic anhydride, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxy Silane, dimethoxymethyl vinyl silane, diethoxymethyl Nirushiran, p- styryl trimethoxysilane, can be mentioned ethylenically unsaturated silane compounds such as p- styryl triethoxysilane. These compounds including a functional group and an ethylenically unsaturated bond in each molecule may be used alone or in combination of two or more. The amount of the compound containing the functional group and the ethylenically unsaturated bond is usually 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, more preferably 100 parts by weight of the alicyclic structure-containing resin. Is 0.5 to 5 parts by weight.

  Examples of the peroxide that can be used to introduce a functional group into the alicyclic structure-containing resin include 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1- Di (t-butylperoxy) -2-methylcyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,2- Di (t-butylperoxy) butane, n-butyl-4,4-di (t-butylperoxy) valerate, t-butylperoxybenzoate, t-butylcumyl peroxide, dicumyl peroxide, di-t -Hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butylperoxide, t-butylperoxyisobutylene It can be used lauroyl peroxide, dipropionyl peroxide, of at least one selected from organic peroxides such as p- menthane hydroperoxide ones. These peroxides may be used alone or in combination of two or more. Although the usage-amount of a peroxide is not specifically limited, It is 0.01-2 weight part normally with respect to 100 weight part of copolymer hydrides, Preferably it is 0.05-1 weight part, More preferably, it is 0.1. -0.5 parts by weight.

  A method of reacting a compound containing a functional group and an ethylenically unsaturated bond in the molecule with an alicyclic structure-containing resin in the presence of a peroxide can be performed using a superheated kneader or a reactor. For example, a mixture of a compound to be reacted with an alicyclic structure-containing resin and a peroxide is heated and melted at a temperature equal to or higher than the melting temperature of the alicyclic structure-containing resin in a biaxial kneader and kneaded for a desired time. It can be performed. Although the reaction temperature (temperature of copolymer hydride) at this time is not particularly limited, it is usually 180 to 240 ° C, preferably 190 to 230 ° C, more preferably 200 to 220 ° C. The reaction time (heat kneading time) is usually about 0.2 to 10 minutes, preferably about 0.3 to 5 minutes, and more preferably about 0.5 to 2 minutes. When using continuous kneading equipment such as a twin-screw kneader or a short-screw extruder, kneading and extrusion may be performed continuously so that the residence time is within the above range.

  Moreover, in this invention, the alicyclic structure containing resin to be used needs to have a glass transition temperature lower than melting | fusing point of the crystalline cyclic olefin resin which comprises the layer of the crystalline cyclic olefin resin laminated | stacked. When the alicyclic structure-containing resin has such a glass transition temperature, the adhesion uniformity of the layer made of copper in the obtained laminate is improved. The glass transition temperature of the alicyclic structure-containing resin is not particularly limited as long as it is lower than the melting point of the crystalline cyclic olefin resin, but is preferably 80 to 250 ° C, more preferably 90 to 220 ° C, and particularly preferably 100. ~ 200 ° C. When the glass transition temperature of the alicyclic structure-containing resin is in this range, it becomes easy to make the obtained laminate have a uniform thickness.

  The molecular weight of the alicyclic structure-containing resin is not particularly limited, but is usually 30,000 to 200 in terms of polystyrene-converted weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. , 000, preferably 40,000-100,000, more preferably 45,000-60,000. The molecular weight of the alicyclic structure-containing resin determined as the ratio of the number average molecular weight (Mn) to the polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. The distribution (Mw / Mn) is not particularly limited, but is usually 3 or less, preferably 2 or less, more preferably 1.5 or less.

  For the alicyclic structure-containing resin, if necessary, an antioxidant, a crosslinking agent, an antioxidant, a flame retardant, a flame retardant aid, a colorant, an antistatic agent, a plasticizer, and an ultraviolet absorber Various additives such as a light stabilizer, a near-infrared absorber, and a lubricant may be added. Examples of the antioxidant include phenol-based antioxidants such as (tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, and phosphorus-based antioxidants. , Sulfur-based antioxidants, etc., can be used without any particular limitation The amount of the antioxidant added to the alicyclic structure-containing resin is not particularly limited, but is 100 parts by weight with respect to 100 parts by weight of the alicyclic structure-containing resin. The amount is usually 0.001 to 5 parts by weight, preferably 0.01 to 4 parts by weight, more preferably 0.1 to 3 parts by weight.

  Examples of the crosslinking agent include peroxides, and organic peroxides are particularly preferably used. Specifically, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-butylperoxy) -2-methylcyclohexane, 1,1-di (T-butylperoxy) cyclohexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,2-di (t-butylperoxy) butane, n-butyl-4,4-di (T-butylperoxy) valerate, t-butylperoxybenzoate, t-butylcumyl peroxide, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t- Butylperoxy) hexane, di-t-butyl peroxide, t-butylperoxyisobutyrate, lauroyl peroxide, dipropionyl peroxide, p-menta Such as hydroperoxide and the like. These organic peroxides may be used alone or in combination of two or more. Although the usage-amount of a crosslinking agent is not specifically limited, Preferably it is 0.1-20 weight part with respect to 100 weight part of alicyclic structure containing resin, More preferably, it is 1-15 weight part, Most preferably 1.5 to 10 parts by weight. As described above, the peroxide can also be used when introducing a functional group into the alicyclic structure-containing resin, but by adjusting the amount of peroxide used and the reaction temperature, the alicyclic structure-containing resin can be used. It is possible to introduce functional groups without crosslinking.

  The method for obtaining the laminate of the present invention is not particularly limited, but the method for producing the laminate of the present invention described below is preferable from the viewpoint of obtaining a laminate adhered more firmly. That is, in the method for producing a laminate of the present invention, a layer made of a crystalline cyclic olefin resin having a melting point and a layer made of copper have a glass transition temperature lower than the melting point of the crystalline cyclic olefin resin, an epoxy group, A layer made of an alicyclic structure-containing resin containing a functional group selected from the group consisting of a carboxyl group, a carboxylic acid anhydride group, and an oxysilyl group in a proportion of 0.1 to 20 mol% with respect to all repeating units. Then, these layers are heated at a temperature not lower than the glass transition temperature of the alicyclic structure-containing resin and not higher than the melting point of the crystalline cyclic olefin resin. It is the manufacturing method of a laminated body made to adhere through the layer which consists of cyclic structure containing resin.

  In the method for producing a laminate of the present invention, the temperature for adhering each layer of the laminate needs to be not lower than the glass transition temperature of the alicyclic structure-containing resin and not higher than the melting point of the crystalline cyclic olefin resin. By heating in such a temperature range, it is possible to obtain a laminate in which the layers are more firmly bonded. If the heating temperature is lower than the glass transition temperature of the alicyclic structure-containing resin, the adhesive strength of the laminate may be insufficient, and if the heating temperature exceeds the melting point of the crystalline cyclic olefin resin, the laminate is deformed. There is a risk that.

  There is no particular limitation on the method of heating the layers made of the alicyclic structure-containing resin by interposing the layers made of the crystalline cyclic olefin resin and the layer made of copper, and for example, the alicyclic structure-containing resin is added to the film. As a form, a method in which the film is interposed between a layer made of a crystalline cyclic olefin resin and a layer made of copper, hot pressing, or an alicyclic structure-containing resin in the form of a solution, a crystalline cyclic olefin An alicyclic structure-containing resin layer is formed by applying to at least one of a resin layer and a copper layer, and the alicyclic structure-containing resin layer is composed of a cyclic olefin resin layer and a copper layer. The method of hot pressing so that it may interpose may be mentioned.

  The molding method for forming the alicyclic structure-containing resin in the form of a film is not particularly limited. For example, a conventionally known method such as melt extrusion molding using an extruder equipped with a T die is employed without any particular limitation. can do. Although the thickness of this film is not specifically limited, It is preferable that it is 5-100 micrometers, and it is more preferable that it is 10-50 micrometers.

  In addition, when the alicyclic structure-containing resin is applied to a layer made of a crystalline cyclic olefin resin or a layer made of copper, the alicyclic structure-containing resin is added to an organic solvent such as cyclohexane, toluene, tetrahydrofuran, or dichloromethane. After dissolving and applying as a solution form using a doctor blade or a wire bar, the solvent may be evaporated. Although the thickness of the layer which consists of alicyclic structure containing resin formed at this time is not specifically limited, It is preferable that it is 1-50 micrometers, and it is more preferable that it is 2-20 micrometers. In addition, the thickness of the layer made of the alicyclic structure-containing resin can be controlled by the concentration of the solution to be applied and the coating amount.

  The hot press conditions that can be performed to firmly bond the laminate are not particularly limited as long as the heating temperature is not lower than the glass transition temperature of the alicyclic structure-containing resin and not higher than the melting point of the crystalline cyclic olefin resin. For example, using a device such as a laminator, the temperature can be 80 to 250 ° C., the pressure is 0.1 to 10 MPa, and the pressure is 0.1 to 3000 seconds. Further, in order to remove bubbles from the adhesive layer, a hot press may be performed under reduced pressure using a vacuum laminator or the like.

  For example, the use of the laminate of the present invention obtained as described above is not particularly limited. For a crystalline cyclic olefin resin excellent in heat resistance, low water absorption, electrical characteristics (low dielectric constant / low dielectric loss tangent), etc. It can be used for various applications utilizing a structure in which copper is firmly bonded, and among them, it can be suitably used for obtaining a circuit board such as a printed wiring board.

    Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. The “parts” in each example are based on weight unless otherwise specified.

Moreover, the measurement and evaluation in each example were performed by the following methods.
[Glass transition temperature and melting point]
The glass transition temperature and melting point of the resin were determined by raising the temperature at 10 ° C./min using a differential scanning calorimeter (DSC).
[Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)]
Using a gel permeation chromatography (GPC) system “HLC-8220” (manufactured by Tosoh Corporation), using an “H type column” (manufactured by Tosoh Corporation) and measuring tetrahydrofuran at 40 ° C. as a polystyrene equivalent value Asked.
[Hydrogenation rate of unsaturated bond]
^It calculated | required based on < ¹ > H-NMR measurement.
[Functional group content]
^{Based on 1} H-NMR measurement, the content (ratio) of the functional group with respect to all repeating units constituting the polymer (hydride) was determined.
[Stripping strength]
After cutting the laminated film (laminated body) as a sample to a size of 10 × 100 mm, a part of the copper foil of the laminated film is peeled off, and fixed to a tensile tester so that only the copper foil can be pulled, and 10 mm / The stress when the copper foil was pulled perpendicularly to the laminated film at a rate of minutes was measured and used as the peel strength of the sample. In addition, this measurement was performed twice immediately after preparation of the laminated film (laminate) used as a sample and after standing in an oven at 150 ° C. for 7 days. The higher the value immediately after the production of the laminated resin film (laminated body), the stronger the adhesion, and the higher the value after measurement after standing in an oven for 7 days, It can be said that the adhesion at is stronger.

[Production Example 1] (Production of crystalline cyclic olefin resin film (A-1))
After fully drying, in a pressure-resistant reaction vessel made of nitrogen-substituted glass, 40 parts of a 75% by weight cyclohexane solution (30 parts as the amount of dicyclopentadiene) of dicyclopentadiene (endo content 99% or more) and 1-hexene 1.0 part was added, and 76 parts of cyclohexane was further added. Subsequently, 0.46 part of a 19 wt% n-hexane solution of diethylaluminum ethoxide was added and stirred. Next, a solution in which 0.11 part of tetrachlorotungstenphenylimide (tetrahydrofuran) complex was dissolved in 2 parts of toluene was added and heated to 50 ° C. to initiate a ring-opening polymerization reaction. After 3 hours, a small amount of isopropanol was added to stop the polymerization reaction, and then the polymerization reaction solution was poured into a large amount of isopropanol to solidify the ring-opened polymer. The solidified ring-opening polymer was separated from the solution by filtration and collected, and then dried at 40 ° C. for 20 hours under vacuum. The yield of the obtained ring-opening polymer was 29 parts (yield 97%). Next, 10 parts of the obtained ring-opening polymer and 44 parts of cyclohexane were added to a pressure-resistant reaction vessel and stirred to dissolve the ring-opening polymer in cyclohexane, and then chlorohydridocarbonyltris (triphenylphosphine) ruthenium. A hydrogenation catalyst solution prepared by dissolving 0065 parts in 6 parts of toluene was added, and a hydrogenation reaction was performed at a hydrogen pressure of 4 MPa and 160 ° C. for 5 hours. The obtained hydrogenation reaction liquid is poured into a large amount of isopropyl alcohol to completely precipitate the polymer, washed by filtration and dried under reduced pressure at 60 ° C. for 24 hours to obtain a crystalline cyclic olefin resin (a-1). It was. The obtained resin (a-1) had a glass transition temperature of 98 ° C. and a melting point of 265 ° C.

  To 100 parts of the obtained crystalline cyclic olefin resin (a-1), an antioxidant (tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, commodity 0.8 parts of the name “Irganox 1010” (manufactured by BASF Japan) was added, melt kneaded at a resin temperature average of 280 ° C. with a twin-screw extruder, and pelletized with a pelletizer to obtain raw resin pellets. This pellet was melt extruded at a speed of 1.5 m / min using an extruder (barrel temperature: 280 ° C., T die temperature: 290 ° C., cooling roll temperature: 90 ° C.) equipped with a T die having a width of 300 mm, Thereafter, a crystallization annealing treatment was performed at 200 ° C. to form a film having a thickness of 50 μm to obtain a crystalline cyclic olefin resin film (A-1).

[Production Example 2] (Production of crystalline cyclic olefin resin film (A-2))
In a glass reactor equipped with a stirrer, the bis {3,3′-di (t-butyl) -5,5 ′, 6,6′-tetramethyl-2,2′-biphenoxy} phenylimidotungsten obtained in the synthesis example ( VI) 0.0556 parts and 4 parts of toluene were added and cooled to -78 ° C. And what melt | dissolved 0.00726 part of n-butyllithium in 1 part of hexane was further added, this was returned to room temperature, and it was made to react for 15 minutes. Next, 7.5 parts of dicyclopentadiene, 27 parts of cyclohexane and 0.32 part of 1-hexene were added to the obtained reaction mixture, and a polymerization reaction was performed at 80 ° C. A white precipitate immediately precipitated after the polymerization reaction started. After reacting for 2 hours, a large amount of acetone was poured into the polymerization reaction solution to aggregate the precipitate, washed by filtration, and dried under reduced pressure at 40 ° C. for 24 hours. The yield of the obtained ring-opening polymer was 7.4 parts, and the number average molecular weight was 17,800. Next, 3.0 parts of the obtained ring-opening polymer and 47 parts of cyclohexane were added to an autoclave equipped with a stirrer. Then, a solution obtained by dispersing 0.00157 parts of RuHCl (CO) (PPh ₃ ) _{2 in} 10 parts of cyclohexane was further added, and a hydrogenation reaction was performed at a hydrogen pressure of 4.0 MPa and 160 ° C. for 8 hours. The hydrogenated ring-opening polymer produced by pouring this hydrogenation reaction liquid into a large amount of acetone is completely precipitated, washed by filtration, and then dried under reduced pressure at 40 ° C. for 24 hours to obtain a crystalline cyclic olefin resin (a-2) Got. The hydrogenation rate of the obtained ring-opening polymer hydride was 99% or more. The glass transition temperature was 102 ° C. and the melting point was 296 ° C.

  To 100 parts of the obtained crystalline cyclic olefin resin (a-2), an antioxidant (tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, commodity 0.8 parts of the name “Irganox 1010” (manufactured by BASF Japan) was added, melt kneaded at a resin temperature average of 320 ° C. with a twin-screw extruder, and pelletized with a pelletizer to obtain raw resin pellets. This pellet was melt extruded at a speed of 1.5 m / min using an extruder (barrel temperature: 320 ° C., T die temperature: 320 ° C., cooling roll temperature: 90 ° C.) equipped with a T die having a width of 300 mm, Thereafter, a crystallization annealing treatment was performed at 200 ° C. to form a film having a thickness of 50 μm to obtain a crystalline cyclic olefin resin film (A-2).

[Production Example 3] (Production of oxysilyl group-containing alicyclic structure-containing resin film (B-1))
A reactor equipped with a nitrogen-substituted stirring apparatus was charged with 550 parts of dehydrated cyclohexane, 25 parts of dehydrated styrene and 0.475 part of di-n-butyl ether and stirred at 60 ° C. with n-butyllithium (15% by weight cyclohexane). Solution) 0.68 part was further added to initiate polymerization, and the mixture was reacted at 60 ° C. for 60 minutes with stirring. Next, 50 parts of dehydrated isoprene was added and reacted at 60 ° C. for 30 minutes with stirring. Next, 25 parts of dehydrated styrene was added and reacted at 60 ° C. for 30 minutes with stirring. Then, 0.5 parts of isopropyl alcohol was added and reaction was stopped, and the copolymer which is a styrene-isoprene-styrene triblock copolymer was obtained. Next, the obtained copolymer solution was transferred to a pressure-resistant reactor equipped with a stirrer, and a silica-alumina supported nickel catalyst (trade name “T-8400RL”, manufactured by Zude Chemie Catalysts) was used as a hydrogenation catalyst. 5 parts and 50 parts of dehydrated cyclohexane were added and mixed. Then, the gas inside the reactor was replaced with hydrogen gas, and hydrogen was supplied while stirring the solution. A hydrogenation reaction was performed at a temperature of 170 ° C. and a pressure of 4.5 MPa for 6 hours. The obtained hydrogenation reaction solution was poured into a large amount of isopropyl alcohol to completely precipitate the copolymer hydride, washed by filtration and dried under reduced pressure at 60 ° C. for 24 hours to obtain a copolymer hydride. The weight average molecular weight (Mw) of the copolymer hydride after the hydrogenation reaction was 65,300, the molecular weight distribution (Mw / Mn) was 1.06, and the hydrogenation rate of all unsaturated bonds was 99% or more. . Next, 2.0 parts of vinyltrimethoxysilane and 0.2 part of di-t-butyl peroxide were added to 100 parts of the obtained copolymer hydride. This mixture was kneaded at a resin temperature of 210 ° C. and a residence time of 80 to 90 seconds using a twin screw extruder (trade name “TEM37B”, manufactured by Toshiba Machine Co., Ltd.), and an oxysilyl group-containing alicyclic structure-containing resin (b -1) was obtained. With respect to the alicyclic structure-containing resin (b-1), the content of the functional group (trimethoxysilyl group) and the glass transition temperature were measured, and the content of the functional group was based on all repeating units constituting the polymer. The glass transition temperature was 122 ° C. at 1.4 mol%.

  Antioxidant (tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, product, 100 parts of oxysilyl group-containing alicyclic structure-containing resin (b-1) The name "Irganox 1010" (manufactured by BASF Japan) 0.8 parts was added, melt kneaded at a resin temperature average of 210 ° C by a twin screw extruder, and pelletized by a pelletizer to obtain raw resin pellets. The pellets were melt extruded at a speed of 1.5 m / min using an extruder (barrel temperature: 210 ° C., T die temperature: 210 ° C., cooling roll temperature: 50 ° C.) equipped with a T die having a width of 300 mm, Thereafter, a crystallization annealing treatment was performed at 200 ° C. to form a film having a thickness of 50 μm, and an oxysilyl group-containing alicyclic structure-containing resin film (B-1) was obtained.

[Production Example 4] (Synthesis of carboxylic acid anhydride group-containing alicyclic structure-containing resin (b-2))
A carboxylic acid anhydride group-containing alicyclic ring was prepared in the same manner as in Production Example 3 except that 3.0 parts of maleic anhydride was added to 100 parts of hydride of the copolymer instead of vinyltrimethoxysilane. A structure-containing resin (b-2) was obtained. For this alicyclic structure-containing resin (b-2), the content of the functional group (carboxylic anhydride group) and the glass transition temperature were measured, and the content of the functional group was based on the total repeating units constituting the polymer. The glass transition temperature was 123 ° C. at 2.5 mol%.

[Production Example 5] (Synthesis of oxysilyl group-containing alicyclic structure-containing resin (b-3))
To 100 parts of a commercially available thermoplastic norbornene-based resin (trade name “ZEONEX 280”, hydrogenation rate 99.7% or more, manufactured by Nippon Zeon Co., Ltd.), 3.0 parts of vinyltrimethoxysilane and 0. 3 dicumyl peroxide. Two parts were added. This mixture was kneaded using a twin screw extruder (trade name “TEM37B”, manufactured by Toshiba Machine Co., Ltd.) at a resin temperature of 240 ° C. and a residence time of 80 to 90 seconds, and an oxysilyl group-containing alicyclic structure-containing resin (b -3) was obtained. With respect to this alicyclic structure-containing resin (b-3), the content of the functional group (trimethoxysilyl group) and the glass transition temperature were measured. The content of the functional group was based on the total repeating units constituting the polymer. The glass transition temperature was 140 ° C. at 1.5 mol%.

[Production Example 6] (Synthesis of carboxylic acid anhydride group-containing alicyclic structure-containing resin (b-4))
A carboxylic acid anhydride group-containing alicyclic ring was prepared in the same manner as in Production Example 5, except that 3.0 parts of maleic anhydride was added to 100 parts of the thermoplastic norbornene resin instead of vinyltrimethoxysilane. A structure-containing resin (b-4) was obtained. With respect to this alicyclic structure-containing resin (b-4), the content of the functional group (carboxylic anhydride group) and the glass transition temperature were measured, and the content of the functional group was based on the total repeating units constituting the polymer. The glass transition temperature was 141 ° C. at 3.5 mol%.

[Production Example 7] (Synthesis of carboxyl group-containing alicyclic structure-containing resin (b-5))
Carboxyl group-containing alicyclic structure-containing resin by operating in the same manner as in Production Example 3, except that 3.0 parts of monomethyl maleate was added to 100 parts of copolymer hydride instead of vinyltrimethoxysilane. (B-5) was obtained. With respect to this alicyclic structure-containing resin (b-5), the content of the functional group (carboxyl group) and the glass transition temperature were measured, and the content of the functional group was 2. for all the repeating units constituting the polymer. The glass transition temperature was 123 ° C. at 1 mol%.

[Production Example 8] (Synthesis of epoxy group-containing alicyclic structure-containing resin (b-6))
In place of vinyltrimethoxysilane, an epoxy group-containing alicyclic structure-containing resin was prepared by the same operation as in Production Example 3, except that 3.0 parts of allyl glycidyl ether was added to 100 parts of hydride of the copolymer. (B-6) was obtained. With respect to this alicyclic structure-containing resin (b-6), the functional group (epoxy group) content and glass transition temperature were measured. The functional group content was 1. The glass transition temperature was 122 ° C. at 2 mol%.

[Comparative Production Example 1] (Preparation of Amorphous Cyclic Olefin Resin Film (A′-1)) In a nitrogen-substituted glass reactor, 0.77 part of (allyl) palladium (tricyclohexylphosphine) chloride and lithium tetrakis (pentafluoro) were prepared. Phenyl) borate (1.14 parts) was added, and then 2 parts of toluene was added to prepare a catalyst solution, which was then added to nitrogen-substituted pressure-resistant glass reactor equipped with a stirrer and 1,650 parts of 2-norbornene, 5-ethyl- 915 parts of 2-norbornene, 1,300 parts of styrene as a molecular weight adjusting agent, and 7,200 parts of toluene as a polymerization solvent were added, and the polymerization was started by adding the above catalyst solution, which was reacted at 45 ° C. for 4.5 hours. Thereafter, the polymerization reaction solution was poured into a large amount of methanol to completely precipitate the polymer, washed by filtration, dried under reduced pressure at 50 ° C. for 18 hours, and dried. 2,462 parts of a polymer was obtained, and the glass transition temperature of this polymer was measured and found to be 281 ° C. A 10 wt% toluene solution of the obtained polymer was cast on a flat glass plate, Toluene was removed by evaporation under an air stream at room temperature for 24 hours, followed by vacuum drying at 80 ° C. for 24 hours to obtain a film having a thickness of 50 μm.

[Comparative Production Example 2] (Synthesis of aromatic ring structure-containing resin (b′-1) containing an oxysilyl group)
A reactor equipped with a nitrogen-substituted stirring apparatus was charged with 550 parts of dehydrated cyclohexane, 25 parts of dehydrated styrene and 0.475 part of di-n-butyl ether and stirred at 60 ° C. with n-butyllithium (15% by weight cyclohexane). Solution) 0.68 part was further added to initiate polymerization, and the mixture was reacted at 60 ° C. for 60 minutes with stirring. Next, 50 parts of dehydrated isoprene was added and reacted at 60 ° C. for 30 minutes with stirring. Next, 25 parts of dehydrated styrene was added and reacted at 60 ° C. for 30 minutes with stirring. Then, 0.5 parts of isopropyl alcohol was added and reaction was stopped, and the copolymer which is a styrene-isoprene-styrene triblock copolymer was obtained. Next, 300 parts of the obtained copolymer solution was transferred to a pressure-resistant reactor equipped with a stirrer, and 0.035 part of chlorohydridocarbonyltris (triphenylphosphine) ruthenium was added to 10 parts of toluene as a hydrogenation catalyst. A hydrogenation catalyst solution obtained by dissolution was added, and a hydrogenation reaction was performed at a hydrogen pressure of 4.5 MPa and 160 ° C. for 5 hours. The obtained hydrogenation reaction solution was poured into a large amount of isopropyl alcohol to completely precipitate the copolymer hydride, washed by filtration and dried under reduced pressure at 60 ° C. for 24 hours to obtain a copolymer hydride. The weight average molecular weight (Mw) of the copolymer hydride after the hydrogenation reaction is 63,200, the molecular weight distribution (Mw / Mn) is 1.05, and the unsaturated bond of the isoprene unit portion is hydrogenated by 99% or more. Unsaturated bonds (aromatic rings) in the styrene unit portion remained almost 100% unhydrogenated. Next, 2.0 parts of vinyltrimethoxysilane and 0.2 part of di-t-butyl peroxide were added to 100 parts of the obtained aromatic ring structure-containing resin. This mixture is kneaded using a twin screw extruder (trade name “TEM37B”, manufactured by Toshiba Machine Co., Ltd.) at a resin temperature of 210 ° C. and a residence time of 80 to 90 seconds to contain an aromatic ring structure-containing resin containing an oxysilyl group. (B′-1) was obtained. With respect to this aromatic ring structure-containing resin (b′-1), the content of the functional group (trimethoxysilyl group) and the glass transition temperature were measured, and the content of the functional group was based on all the repeating units constituting the polymer. The glass transition temperature was 100 ° C. at 1.5 mol%.

[Comparative Production Example 3] (Preparation of polyethylene film (B′-2) containing oxysilyl group)
With respect to 100 parts of pellets of commercially available linear low density polyethylene (trade name “Umerit 20B”, melting point 119 ° C., manufactured by Ube Maruzen Polyethylene), 2.0 parts of vinyltrimethoxysilane and 2,5-dimethyl-2 , 5-di (t-butylperoxyhexane) 0.2 part was added. This mixture was kneaded using a twin-screw extruder (trade name “TEM37B”, manufactured by Toshiba Machine Co., Ltd.) at a resin temperature of 200 ° C. and a residence time of 80 to 90 seconds to obtain polyethylene (b′−) containing an oxysilyl group. 2) was obtained. With respect to the polyethylene (b′-2) containing this oxysilyl group, the content of the functional group (trimethoxysilyl group) and the glass transition temperature were measured, and the content of the functional group was 0 with respect to all the repeating units of the polyethylene. The glass transition temperature was 119 ° C. at 3 mol%.

  Antioxidant (tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane was added to 100 parts of polyethylene (b′-2) containing the obtained oxysilyl group. , Trade name “Irganox 1010” (manufactured by BASF Japan Ltd.) was added, melt kneaded at a resin temperature average of 210 ° C. with a twin screw extruder, and pelletized with a pelletizer. The pellets were melt extruded using an extruder (barrel temperature: 210 ° C., T die temperature: 210 ° C., cooling roll temperature: 50 ° C.) equipped with a 300 mm wide T die to form a 50 μm thick film. The polyethylene film (B'-2) containing an oxysilyl group was obtained.

[Example 1]
A 30% by weight toluene solution of the oxysilyl group-containing alicyclic structure-containing resin (b-1) obtained in Production Example 3 was applied to the crystalline cyclic olefin resin film (A-1) obtained in Production Example 1 using a doctor blade. Then, this is heated in an inert oven at 200 ° C. for 30 minutes, whereby a 10 μm thick oxysilyl group-containing copolymer hydride (b-1) is formed on the crystalline cyclic olefin resin film (A-1). ) Was obtained. Next, on the oxysilyl group-containing copolymer hydride (b-1) layer side of this laminated film, an electrolytic copper foil having a thickness of 12 μm (trade name “F3-WS-12”, surface roughness (ten-point average roughness) Rz): 2.4 μm, manufactured by Furukawa Electric). And this laminated body was pressure-compressed to 200 Pa using a vacuum laminator equipped with heat-resistant rubber press plates at the top and bottom, and thermocompression bonded at a temperature of 170 ° C. and a compression pressure of 1 MPa for 60 seconds to obtain a copper foil laminated resin. A film was prepared. About the obtained copper foil laminated resin film, peel strength was measured, and then the peel strength after standing in an oven at 150 ° C. for 7 days was also measured. These results are summarized in Table 1.

[Example 2]
Crystalline cyclic olefin resin film (A-1) obtained in Production Example 1, oxysilyl group-containing alicyclic structure-containing resin film (B-1) obtained in Production Example 3, and electrolytic copper foil having a thickness of 12 μm (trade name) “F3-WS-12”, surface roughness (ten-point average roughness Rz): 2.4 μm, manufactured by Furukawa Electric Co., Ltd.) are stacked in this order, and the laminated body is a vacuum equipped with heat-resistant rubber press plates at the top and bottom. Using a laminator, the atmosphere was reduced to 200 Pa, and thermocompression bonded at a temperature of 170 ° C. and a pressure bonding pressure of 1 MPa for 60 seconds to prepare a copper foil laminated resin film. About the obtained copper foil laminated resin film, peel strength was measured, and then the peel strength after standing in an oven at 150 ° C. for 7 days was also measured. These results are summarized in Table 1.

[Examples 3 to 11]
A copper foil laminated resin film was produced in the same manner as in Example 1 except that the film, the resin to be used, and the laminate were subjected to thermocompression bonding as described in Table 1 except that the temperature was changed. However, about Examples 6-10, the aminosilane coupling agent process was performed to the copper foil to be used in advance. About the obtained copper foil laminated resin film, peel strength was measured, and then the peel strength after standing in an oven at 150 ° C. for 7 days was also measured. These results are summarized in Table 1.

Example 12
An oxysilyl group-containing product obtained in Production Example 3 in an electrolytic copper foil having a thickness of 12 μm (trade name “F3-WS-12”, surface roughness (10-point average roughness Rz): 2.4 μm, manufactured by Furukawa Electric Co., Ltd.) A 30 wt% toluene solution of the alicyclic structure-containing resin (b-1) was applied using a wire bar, and then heated in an inert oven at 200 ° C. for 30 minutes to form a copper foil with a thickness of 5 μm. Two laminates in which layers of the oxysilyl group-containing alicyclic structure-containing resin (b-1) were laminated were produced. Next, the crystalline cyclic olefin resin film (A-1) obtained in Production Example 1 was subjected to plasma treatment, and then the crystalline cyclic olefin resin film (A-1) was converted to an oxysilyl group-containing alicyclic structure-containing resin ( b-1) is sandwiched between two laminates so that the layer side is in contact, and the pressure is reduced to 200 Pa using a vacuum laminator equipped with heat-resistant rubber press plates at the top and bottom, and the temperature is 170 ° C. Thermocompression bonding was carried out at a pressure of 1 MPa for 60 seconds to prepare a double-sided copper foil laminated resin film. About the obtained double-sided copper foil laminated resin film, the peel strength was measured, and then the peel strength after standing in an oven at 150 ° C. for 7 days was also measured. These results are summarized in Table 1.

[Examples 13 to 19 and Comparative Example 1]
A double-sided copper foil laminated resin film was produced in the same manner as in Example 12 except that the film, the resin to be used, and the laminate were subjected to thermocompression bonding as described in Table 1 except that the temperature was changed as shown in Table 1. However, about Examples 16-19, the aminosilane coupling agent process was performed to the copper foil to be used in advance. About the obtained double-sided copper foil laminated resin film, the peel strength was measured, and then the peel strength after standing in an oven at 150 ° C. for 7 days was also measured. These results are summarized in Table 1.

[Comparative Example 2]
A double-sided copper foil laminated resin film was obtained in the same manner as in Comparative Example 1 except that the temperature when thermocompression bonding the laminated body was changed to 300 ° C., but the amorphous cyclic olefin resin film (A′- 1) was hard and brittle and cracked, and a double-sided copper foil laminated resin film could not be obtained.

[Comparative Example 3]
An oxysilyl group-containing product obtained in Production Example 3 in an electrolytic copper foil having a thickness of 12 μm (trade name “F3-WS-12”, surface roughness (10-point average roughness Rz): 2.4 μm, manufactured by Furukawa Electric Co., Ltd.) A 30 wt% toluene solution of the alicyclic structure-containing resin (b-1) was applied using a wire bar, and then heated in an inert oven at 200 ° C. for 30 minutes to form a copper foil with a thickness of 5 μm. Two laminates in which layers of the oxysilyl group-containing alicyclic structure-containing resin (b-1) were laminated were produced. Next, the layer side of the oxysilyl group-containing alicyclic structure-containing resin (b-1) is in contact with the commercially available amorphous cyclic olefin resin film (A′-2) (trade name “ZEONOR FILM”, manufactured by Nippon Zeon Co., Ltd.). Sandwiched between two laminates, and using a vacuum laminator equipped with heat-resistant rubber press plates at the top and bottom, the atmosphere was reduced to 200 Pa and thermocompression bonded at a temperature of 120 ° C. and a pressure of 1 MPa for 60 seconds. A double-sided copper foil laminated resin film was prepared. About the obtained double-sided copper foil laminated resin film, the peel strength was measured, and then the peel strength after standing in an oven at 150 ° C. for 7 days was also measured. These results are summarized in Table 1.

[Comparative Example 4]
A double-sided copper foil laminated resin film was obtained in the same manner as in Comparative Example 3 except that the temperature at the time of thermocompression bonding the laminated body was changed to 180 ° C., but a commercially available amorphous cyclic olefin resin film was melted. It was deformed and a double-sided copper foil laminated resin film could not be obtained.

[Comparative Example 5]
Example 1 except that the aromatic ring structure-containing resin (b′-1) containing an oxysilyl group obtained in Comparative Production Example 2 was used instead of the oxysilyl group-containing alicyclic structure-containing resin (b-1). Similarly, a copper foil laminated resin film was produced. About the obtained copper foil laminated resin film, peel strength was measured, and then the peel strength after standing in an oven at 150 ° C. for 7 days was also measured. These results are summarized in Table 1.

[Comparative Example 6]
In place of the oxysilyl group-containing alicyclic structure-containing resin film (B-1), a copper foil laminated resin film was obtained in the same manner as in Example 2 except that an oxysilyl group-containing polyethylene film (B′-2) was used. Was made. About the obtained copper foil laminated resin film, peel strength was measured, and then the peel strength after standing in an oven at 150 ° C. for 7 days was also measured. These results are summarized in Table 1.

  As can be seen from Table 1, the copper foil laminated resin film corresponding to the laminate of the present invention has a high peel strength in the measurement immediately after the production and the measurement after standing in an oven for 7 days. It was. On the other hand, when an amorphous cyclic olefin resin film was used instead of the crystalline cyclic olefin resin film (Comparative Examples 1 and 3), the peel strength value was relatively high in the measurement immediately after the production. However, in the measurement after standing in an oven for 7 days, the value of the peel strength was greatly reduced. Moreover, it replaced with alicyclic structure containing resin, and when using other resin (comparative examples 5 and 6), all are copper foil by both the measurement immediately after preparation, and the measurement after leaving still in an oven for 7 days. The peel strength of the laminated resin film was low. From the above, it can be said that in the laminate of the present invention, the crystalline cyclic olefin resin and copper are firmly bonded, and the strong bonding is maintained even after a thermal history.

Claims (2)

  The layer composed of a crystalline cyclic olefin resin having a melting point and the layer composed of copper have a glass transition temperature lower than the melting point of the crystalline cyclic olefin resin, and include an epoxy group, a carboxyl group, a carboxylic acid anhydride group, and an oxysilyl group. The laminated body adhere | attached through the layer which consists of alicyclic structure containing resin which contains the functional group selected from the group which consists of groups in the ratio of 0.1-20 mol% with respect to all the repeating units.   A layer composed of a crystalline cyclic olefin resin having a melting point and a layer composed of copper have a glass transition temperature lower than the melting point of the crystalline cyclic olefin resin, and have an epoxy group, a carboxyl group, a carboxylic acid anhydride group, and an oxysilyl group. After laminating through a layer made of an alicyclic structure-containing resin containing a functional group selected from the group consisting of groups in a proportion of 0.1 to 20 mol% with respect to all repeating units, these are then alicyclic The layer made of the crystalline cyclic olefin resin and the layer made of copper are made of the alicyclic structure-containing resin by heating at a temperature not lower than the glass transition temperature of the structure-containing resin and not higher than the melting point of the crystalline cyclic olefin resin. The manufacturing method of a laminated body made to adhere through a layer.