JP6357913B2 - Method for producing surface modified film, method for modifying resin layer, laminate, flexible printed circuit board, and method for producing laminate - Google Patents

Description

  The present invention provides a method for producing a surface-modified film whose surface has been modified by irradiating light using an excimer lamp, a method for modifying a resin layer irradiating light using an excimer lamp, and the production method described above. The present invention relates to a laminate obtained by using the obtained surface modified film, a flexible printed board using the laminate, and a method for producing the laminate.

In recent years, cyclic olefin resins have been studied as electrical insulating materials.
For example, in Patent Literature 1, a norbornene-based ring-opening polymer hydride that is a kind of cyclic olefin resin is excellent in low water absorption, low dielectric constant, and the like, and is suitable as an electrical insulating material when forming a circuit board or the like. It is disclosed that there is.
However, the norbornene-based ring-opening polymer hydride as disclosed in Patent Document 1 tends to be inferior in adhesion to metal and heat resistance, and further improvement is required as a circuit board forming material. .

In Patent Document 2, by using a specific ring-opening polymerization catalyst, a norbornene-based ring-opening polymer hydride having a melting point (that is, having crystallinity) can be obtained, and the norbornene-based opening having this crystallinity can be obtained. It is disclosed that the hydride of a cyclic polymer is excellent in mechanical strength and heat resistance.
However, the norbornene-based ring-opening polymer hydride having crystallinity also has insufficient adhesion to metal.

In Patent Documents 3 to 6, as a technique for improving the adhesion of cyclic olefin resins such as norbornene-based ring-opening polymer hydrides to metals, modification or copolymerization using a monomer having a functional group can be used. A method for introducing a functional group into an olefin resin is disclosed.
However, in general, when a functional group is introduced into a 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.

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

  The present invention has been made in view of the above-described prior art, and is a laminate in which a resin film excellent in all of heat resistance, low water absorption, and electrical characteristics and a metal foil are firmly bonded, and this laminate It is an object of the present invention to provide a flexible printed circuit board using the above, a method for producing the laminate, a method for producing a surface modified film useful as a material for producing the laminate, and a method for modifying a resin layer.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention irradiate a crystalline resin film mainly composed of a crystalline cyclic olefin resin with light having a central wavelength of less than 180 nm using an excimer lamp. The laminate obtained by adhering the surface-modified film obtained by the modification and the metal foil is obtained by firmly bonding the surface-modified film and the metal foil and receiving a thermal history. Even after this, it was found that it was difficult to cause yellowing and a decrease in peel strength, and the present invention was completed.

Thus, according to the present invention, the following [1] method for producing a surface-modified film, [2] a method for modifying a resin layer, [3] to [7] laminates, [8] to [12] A method for producing a laminate, the flexible printed board of [13], is provided.
[1] At least one surface of a crystalline resin film containing a crystalline cyclic olefin resin as a main component is irradiated with light having a center wavelength of less than 180 nm using an excimer lamp, thereby modifying the crystalline resin film. A method for producing a surface-modified film, characterized by comprising:
[2] The resin layer is modified by irradiating the surface of the resin layer mainly composed of a crystalline cyclic olefin resin with light having a center wavelength of less than 180 nm using an excimer lamp. A method for modifying a resin layer.
[3] A laminate in which a resin film and a metal foil are bonded via an adhesive layer, and the resin film is modified on one side or both sides obtained by the method described in [1]. A surface-modified film having a textured surface,
The laminate is characterized in that the adhesive layer is adjacent to the modified surface of the surface-modified film.
[4] The laminate according to [3], wherein the metal foil is a copper foil.
[5] The adhesive layer has a glass transition temperature lower than the melting point of the crystalline cyclic olefin resin, and is selected from the group consisting of an epoxy group, a carboxyl group, a carboxylic acid anhydride group, and an oxysilyl group. The laminate according to [3] or [4], which is mainly composed of an alicyclic structure-containing resin having a functional group.
[6] The content ratio of the functional group in the alicyclic structure-containing resin (number of functional groups: number of repeating units of the alicyclic structure-containing resin) is 0.1: 100 to 20: 100, [5 ] The laminated body as described in above.
[7] The surface modified film is a film having modified surfaces on both sides, and the laminate has a layer structure of metal foil / adhesive layer / surface modified film / adhesive layer / metal foil. The laminate according to any one of [3] to [6], which is provided.
[8] A flexible printed board using the laminate according to any one of [3] to [7].
[9] The method for producing a laminate according to any one of [3] to [7], comprising the following steps (aI) to (a-II).
Step (a-I): Step of forming an adhesive layer by applying an adhesive layer forming liquid on the modified surface of the surface modified film and drying the resulting coating film (a -II): Step of adhering the surface-modified film and the metal foil through the adhesive layer after the metal foil is overlaid on the adhesive layer formed in the step (a-I) [10] The manufacturing method of the laminated body in any one of [3]-[7] which has (b-I)-(b-II).
Step (b-I): Step of forming an adhesive layer by applying an adhesive layer forming liquid on the metal foil and drying the obtained coating film (b-II): Step ( After the surface modified film is stacked on the adhesive layer formed in b-I) so that the modified surface faces the adhesive layer, the surface modified film and the metal foil are bonded. [11] The method for producing a laminate according to any one of [3] to [7], which includes a step [11] of bonding via an agent layer.
Step (c-I): The surface-modified film, the sheet-like adhesive, and the metal foil are arranged in this order, and the modified surface of the surface-modified film faces the sheet-like adhesive. The step of adhering the surface-modified film and the metal foil through a sheet-like adhesive after being stacked [12] A glass in which the adhesive layer or the sheet-like adhesive is lower than the melting point of the crystalline cyclic olefin resin The main component is an alicyclic structure-containing resin having a transition temperature and having a functional group selected from the group consisting of an epoxy group, a carboxyl group, a carboxylic anhydride group, and an oxysilyl group. The operation of adhering the quality film and the metal foil through the adhesive layer or the sheet-like adhesive has a layer structure of a surface modified film / adhesive layer or a sheet-like adhesive / metal foil, before the adhesion treatment The laminate Or above the glass transition temperature of the structure-containing resin, and is for heating to the temperature below the melting point of the crystalline cyclic olefin resins, (9) - The method for producing a laminate according to any one of [11].
[13] The content ratio of the functional group in the alicyclic structure-containing resin (the number of functional groups: the number of repeating units of the alicyclic structure-containing resin) is 0.1: 100 to 20: 100, [12 ] The manufacturing method of the laminated body as described in above.

  According to the present invention, a laminate in which a resin film excellent in all of heat resistance, low water absorption, and electrical properties and a metal foil are firmly bonded, a flexible printed board using the laminate, and the laminate , A method for producing a surface-modified film useful as a material for producing the laminate, and a method for modifying a resin layer are provided.

  Hereinafter, the present invention will be described in detail by dividing into 1) a method for producing a surface modified film and a method for modifying a resin layer, 2) a laminate and a flexible printed circuit board, and 3) a method for producing a laminate. To do.

1) Method for producing surface modified film and method for modifying resin layer The method for producing a surface modified film of the present invention comprises an excimer formed on at least one surface of a crystalline resin film containing a crystalline cyclic olefin resin as a main component. The crystalline resin film is modified by irradiating light having a central wavelength of less than 180 nm using a lamp.

[Crystalline cyclic olefin resin]
The crystalline cyclic olefin resin used in the present invention is a polymer obtained by polymerizing a cyclic olefin, and is a polymer having a melting point (hereinafter sometimes referred to as “polymer (α)”).
“Having a melting point” means that the melting point can be observed with a differential scanning calorimeter (DSC). In general, the cyclic olefin resin is a resin excellent in low water absorption and electrical characteristics, but in the present invention, since a crystalline cyclic olefin resin is used, in addition to these characteristics, it is excellent in heat resistance.

  Examples of the polymer (α) include dicyclopentadiene ring-opened polymer hydride having syndiotactic stereoregularity described in International Publication No. 2012/033076, and isotactic stereoregulation described in JP-A-2002-249553. Well known ones such as dicyclopentadiene ring-opening polymer hydride having the property, and norbornene ring-opening polymer hydride described in JP-A-2007-16102 can be used.

The melting point of the polymer (α) is higher than the glass transition temperature of the alicyclic structure-containing resin described later because the surface-modified film and the metal foil can be efficiently bonded when the laminate is produced. Is preferred. The melting point of the polymer (α) is preferably 180 to 350 ° C, more preferably 200 to 320 ° C, and particularly preferably 220 to 300 ° C.
When the melting point of the polymer (α) is within this range, the crystalline cyclic olefin resin has a good balance between moldability and heat resistance. In addition, as described above, the surface-modified film and the metal foil can be efficiently bonded.

  As the polymer (α), a target surface-modified film can be efficiently produced, and therefore a dicyclopentadiene ring-opened polymer hydride having syndiotactic stereoregularity (hereinafter referred to as “polymer (α1)”). Is preferred).

Although the degree of stereoregularity of a polymer ((alpha) 1) is not specifically limited, Since the surface-modified film excellent in heat resistance can be obtained efficiently, a thing with a higher degree of stereoregularity is preferable.
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, and more preferably 60% or more. 70% or more is particularly preferable.
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. Specifically, ¹³ C-NMR measurement was performed using ortho-dichlorobenzene-d ⁴ as a solvent and applying an inverse-gate decoupling method at 150 ° C., and the 127.5 ppm peak of ortho-dichlorobenzene-d ⁴ was shifted to the standard. As a result, the ratio of the racemo dyad can be determined from the intensity ratio of the 43.35 ppm signal derived from the meso dyad and the 43.43 ppm signal derived from the racemo dyad.

  The polymer (α1) undergoes ring-opening polymerization using dicyclopentadiene as a main monomer, and hydrogenates (hydrogenates) at least part of the carbon-carbon double bonds present in the resulting ring-opened polymer. Can be obtained.

  In dicyclopentadiene, there are stereoisomers of endo and exo, both of which can be used as monomers in the present invention. Moreover, only one isomer may be used alone, or an isomer mixture in which an endo isomer and an exo isomer are present in an arbitrary ratio may be used. In the present invention, the crystallinity of the polymer (α1) is increased, and a surface-modified film that is superior in heat resistance is easily obtained. Therefore, it is preferable to increase the ratio of one stereoisomer. For example, the ratio of endo-form or exo-form is preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more. In addition, since the synthesis | combination is easy, it is preferable that the ratio of an end body is high.

When synthesizing the polymer (α1), only dicyclopentadiene may be used as the monomer, or another monomer copolymerizable with dicyclopentadiene may be used. Examples of other monomers include norbornenes other than dicyclopentadiene, cyclic olefins, and dienes.
When other monomers are used, the amount used is preferably 10% by weight or less, more preferably 5% by weight or less, based on the total amount of monomers.

  The ring-opening polymerization catalyst used for synthesizing the polymer (α1) is not particularly limited as long as it allows ring-opening polymerization of dicyclopentadiene to obtain a ring-opening polymer having syndiotactic stereoregularity. Preferred examples of the ring-opening polymerization catalyst include those containing a metal compound represented by the following formula (1).

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

  M is a transition metal atom (chromium, molybdenum, tungsten) belonging to Group 6 of the periodic table, preferably molybdenum or tungsten, and more preferably tungsten.

The number of carbon atoms of the phenyl group which may have a substituent at at least ^one of the 3, 4, and 5 positions of R ¹ is not particularly limited, but is usually 6 to 20, preferably 6 to 15. .
Examples of the substituent include alkyl groups such as methyl group and ethyl group; halogen atoms such as fluorine atom, chlorine atom and bromine atom; alkoxy groups such as methoxy group, ethoxy group and isopropoxy group;
In addition, substituents present in at least two positions of the 3, 4, and 5 positions may be bonded to each other to form a ring structure.
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, a 3-methoxyphenyl group, 4- Monosubstituted phenyl groups such as cyclohexylphenyl group and 4-methoxyphenyl group; disubstituted groups such as 3,5-dimethylphenyl group, 3,5-dichlorophenyl group, 3,4-dimethylphenyl group and 3,5-dimethoxyphenyl group Phenyl group; trisubstituted phenyl group such as 3,4,5-trimethylphenyl group, 3,4,5-trichlorophenyl group; 2-naphthyl group, 3-methyl-2-naphthyl group, 4-methyl-2-naphthyl 2-naphthyl group which may have a substituent such as a group;

In the group represented by —CH ₂ R ³ in R ¹ , 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. Represents.
Although carbon number of the alkyl group which may have a substituent of R < ³ > is not specifically limited, Usually, 1-20, Preferably it is 1-10. This alkyl group may be linear or branched.
Examples of the substituent include a phenyl group optionally having a substituent such as a phenyl group and a 4-methylphenyl group; an alkoxyl group such as a methoxy group and an ethoxy group; and the like.
Examples of the alkyl group which may have a substituent for R ³ 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 neophyll groups.

Of R ^3, the carbon number of the aryl group which may have a substituent is not particularly limited, usually, 6 to 20, preferably 6 to 15.
Examples of the substituent include alkyl groups such as methyl group and ethyl group; halogen atoms such as fluorine atom, chlorine atom and bromine atom; alkoxy groups such as methoxy group, ethoxy group and isopropoxy group;
Examples of the aryl group of R ³ which may have a substituent include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 4-methylphenyl group, and a 2,6-dimethylphenyl group.

Among these, the group represented by R ³ is preferably an alkyl group having 1 to 20 carbon atoms.

Examples of the halogen atom for X include a chlorine atom, a bromine atom, and an iodine atom.
As the alkyl group which may have a substituent of X and the aryl group which may have a substituent, the alkyl group which may have a substituent and the substituent of R ³ respectively. The thing similar to what was shown as an aryl group which may have is mentioned.
Examples of the alkylsilyl group of X include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, and the like.
Moreover, when the metal compound shown by Formula (1) has two or more X, these may couple | bond together and may form the ring structure.

As the alkyl group which may have a substituent of R ² and the aryl group which may have a substituent, an alkyl group which may have a substituent and a substituent of R ³ respectively. The thing similar to what was shown as an aryl group which may have this is mentioned.

  Examples of the electron donating neutral ligand of L include an electron donating compound containing an atom 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, Amines such as lutidine; and the like. Among these, ethers are preferable.

As the metal compound represented by the formula (1), a tungsten compound having a phenylimide group (a compound in which M in the formula (1) is a tungsten atom and R ¹ is a phenyl group) is preferable, and tetrachlorotungsten phenylimide ( Tetrahydrofuran) complexes are more preferred.

The method for synthesizing the metal compound represented by the formula (1) is not particularly limited. For example, as described in JP-A-5-345817, an oxyhalide of a Group 6 transition metal and phenyl isocyanate that may have a substituent at at least one of the 3, 4, and 5 positions A target metal compound is obtained by mixing a naphthate or monosubstituted methyl isocyanate with an electron-donating neutral ligand (L) and, if necessary, an alcohol, a metal alkoxide, or a metal aryloxide. Can be synthesized.
After the synthesis of the metal compound, the reaction solution may be used as it is as a catalyst solution for the ring-opening polymerization reaction, or after isolation and purification of the metal compound by a known purification treatment such as crystallization, You may use for ring-opening polymerization reaction.

The ring-opening polymerization catalyst may be composed only of the metal compound represented by the formula (1), or may be a combination of the metal compound represented by the formula (1) and an organometallic reducing agent. By using a combination of the metal compound represented by the formula (1) and the organometallic reducing agent, the polymerization activity is improved.
Examples of the organometallic reducing agent include organometallic compounds belonging to Groups 1, 2, 12, 13 and 14 of the periodic table having a hydrocarbon group having 1 to 20 carbon atoms.
Examples of the organometallic compound include organic lithium such as methyl lithium, n-butyl lithium, and phenyl lithium; organic magnesium such as butyl ethyl magnesium, butyl octyl magnesium, dihexyl magnesium, ethyl magnesium chloride, n-butyl magnesium chloride, and allyl magnesium bromide. Organic zinc such as dimethyl zinc, diethyl zinc and diphenyl zinc; trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, diethyl aluminum chloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, diethyl aluminum ethoxide, diisobutyl aluminum isobutoxide, ethyl aluminum di Organic aluminum such as ethoxide, isobutylaluminum diisobutoxide Um; tetramethyl tin, tetra (n- butyl) tin, organic tin such as tetraphenyl tin; and the like.
Among these, organoaluminum or organotin is preferable.

The ring-opening polymerization reaction is usually performed in an organic solvent. The organic solvent used is not particularly limited as long as it can dissolve or disperse the ring-opening polymer or its hydride under predetermined conditions and does not inhibit the ring-opening polymerization reaction or the hydrogenation reaction. .
Examples of the organic solvent include aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane, hexa Alicyclic hydrocarbons such as hydroindene and cyclooctane; Aromatic hydrocarbons such as benzene, toluene and xylene; Halogenated aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; Chlorobenzene and dichlorobenzene Halogen-containing aromatic hydrocarbons such as: nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile; ethers such as diethyl ether and tetrahydrofuran; Solvent mixture; and the like.
Among these, as the organic solvent, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and ethers are preferable.

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 solution containing the metal compound represented by the formula (1) and the organometallic reducing agent may be added to and mixed with the solution containing the monomer, or the monomer containing the organometallic reducing agent may be added to the solution containing the organometallic reducing agent. And a solution containing the metal compound represented by the formula (1) may be added and mixed, or a solution containing the metal compound represented by the formula (1) may be added to the solution containing the monomer and the organometallic reducing agent. And may be mixed.
When adding each component, the whole quantity of each component may be added at once, and may be added in multiple times. Moreover, you may add continuously over a comparatively long time (for example, 1 minute or more).

  The concentration of the monomer at the start of the ring-opening polymerization reaction is not particularly limited, but is usually 1 to 50% by weight, preferably 2 to 45% by weight, and more preferably 3 to 40% by weight. If the concentration of the monomer is too low, the productivity may decrease. If it is too high, the solution viscosity after the ring-opening polymerization reaction is too high, and the subsequent hydrogenation reaction may be difficult.

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

  When using an organometallic reducing agent, the amount used is preferably 0.1 to 100 mol, more preferably 0.2 to 50 mol, relative to 1 mol of the metal compound represented by formula (1), 0.5 ˜20 mol is particularly preferred. If the amount of the organometallic reducing agent used is too small, the polymerization activity may not be sufficiently improved, and if it is too much, side reactions may easily occur.

An activity regulator may be added to the polymerization reaction system. By using the activity regulator, the ring-opening polymerization catalyst can be stabilized, the reaction rate of the ring-opening polymerization reaction and the molecular weight distribution of the polymer can be adjusted.
The activity regulator is not particularly limited as long as it is an organic compound having a functional group. Examples of the activity regulator include oxygen-containing compounds, nitrogen-containing compounds, and phosphorus-containing organic compounds.
Examples of the oxygen-containing compound include 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;
Nitrogen-containing compounds include nitriles such as acetonitrile and benzonitrile; amines such as triethylamine, triisopropylamine, quinuclidine and N, N-diethylaniline; pyridine, 2,4-lutidine, 2,6-lutidine, 2- pyridines such as t-butylpyridine; and the like.
Examples of the phosphorus-containing compound include phosphines such as triphenylphosphine, tricyclohexylphosphine, triphenylphosphate, and trimethylphosphate; phosphine oxides such as triphenylphosphine oxide; and the like.
An activity regulator can be used individually by 1 type or in combination of 2 or more types. The amount of the activity regulator to be added is not particularly limited, but is usually selected from 0.01 to 100 mol% with respect to the metal compound represented by the formula (1).

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, 2,5-dimethyl-1,5-hexadiene and other nonconjugated dienes; 1,3-butadiene, 2-methyl-1,3-butadiene, 2, 3-dimethyl-1,3-butadiene, 1,3-penta Ene, conjugated dienes such as 1,3-hexadiene; and the like.
A molecular weight regulator can be used individually by 1 type or in combination of 2 or more types. The amount of the molecular weight modifier to be added may be appropriately determined according to the target molecular weight, but is usually selected in the range of 0.1 to 50 mol% with respect to dicyclopentadiene.

  Although there is no restriction | limiting in particular in superposition | polymerization temperature, Usually, it is the range of -78- + 200 degreeC, Preferably it is the range of -30- + 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.

  The weight average molecular weight (Mw) of the dicyclopentadiene ring-opening polymer is not particularly limited, but is usually 1,000 to 1,000,000, preferably 2,000 to 500,000. By subjecting the ring-opening polymer having such a weight average molecular weight to a hydrogenation reaction, a polymer (α1) having an excellent balance between molding processability and heat resistance can be obtained. 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 (Mw / Mn) of the dicyclopentadiene ring-opening polymer is not particularly limited, but is usually 1.0 to 4.0, preferably 1.5 to 3.5. By subjecting the ring-opening polymer having such a molecular weight distribution to a hydrogenation reaction, a polymer (α1) excellent in 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 weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the dicyclopentadiene ring-opened polymer are polystyrene-converted values measured by gel permeation chromatography (GPC) using tetrahydrofuran as a developing solvent.

  By the ring-opening polymerization reaction, a dicyclopentadiene ring-opening polymer having syndiotactic stereoregularity can be obtained. In the hydrogenation reaction performed after the ring-opening polymerization reaction, if the reaction conditions are set appropriately, the tacticity of the ring-opening polymer does not usually change due to the hydrogenation reaction, and thus has this syndiotactic stereoregularity. The target polymer (α1) can be obtained by subjecting the dicyclopentadiene ring-opened polymer to a hydrogenation reaction. The degree of syndiotactic stereoregularity of the ring-opening polymer can be adjusted by selecting the type of ring-opening polymerization catalyst.

  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. As a hydrogenation catalyst, a well-known homogeneous catalyst and a heterogeneous catalyst can be used as a hydrogenation catalyst of an olefin compound.

  Homogeneous catalysts include transition metal compounds such as cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyllithium, tetrabutoxytitanate / dimethylmagnesium, etc. Catalyst comprising a combination of alkali metal compounds; dichlorobis (triphenylphosphine) palladium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, chlorohydridocarbonylbis (tricyclohexylphosphine) ruthenium, bis (tricyclohexylphosphine) benzilidineruthenium (IV ) Noble metal complex catalysts such as dichloride and chlorotris (triphenylphosphine) rhodium;

  As heterogeneous catalysts, metal catalysts such as nickel, palladium, platinum, rhodium, ruthenium; nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina, etc. And a solid catalyst in which the metal is supported on a carrier such as carbon, silica, diatomaceous earth, alumina, titanium oxide or the like.

The hydrogenation reaction is usually performed in an inert organic solvent. Examples of the inert organic solvent 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 may be the same as or different from the solvent used in the ring-opening polymerization reaction. Alternatively, the hydrogenation catalyst may be added as it is to the ring-opening polymerization reaction solution to carry out the hydrogenation reaction.

The reaction conditions for the hydrogenation reaction vary depending on the hydrogenation catalyst used, but the reaction temperature is usually -20 to + 250 ° C, preferably -10 to + 220 ° C, more preferably 0 to + 200 ° C. If the reaction temperature is too low, the reaction rate may be too slow, and if the reaction temperature 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 reaction rate may be too slow. If the hydrogen pressure is too high, a special device such as a high pressure reactor is required.
Although reaction time will not be specifically limited if a desired hydrogenation rate is achieved, Usually, it is 0.1 to 10 hours.
After the hydrogenation reaction, the target polymer (α1) may be recovered according to a conventional method.

  The hydrogenation rate in the hydrogenation reaction (the ratio of hydrogenated main chain double bonds) 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 obtained crystalline cyclic olefin resin.

[Crystalline resin film]
The crystalline resin film used for this invention has the said crystalline cyclic olefin resin as a main component.
“Crystalline resin film” refers to a film whose melting point can be observed when a differential scanning calorimeter (DSC) is measured using the film as a sample.
The “main component” means that the content is 50% by weight or more of the whole (the same applies hereinafter).

The crystalline resin film to be used may contain other components such as additives in addition to the crystalline cyclic olefin resin.
Other components include antioxidants, crystal nucleating agents, fillers, flame retardants, flame retardant aids, colorants, antistatic agents, plasticizers, ultraviolet absorbers, light stabilizers, near infrared absorbers, lubricants, etc. Is mentioned.
Although these content can be suitably determined according to the objective, it is less than 50 weight% with respect to a crystalline resin film, Preferably it is 40 weight% or less.

When the surface-modified film is used as a production material for a printed wiring board or the like, the crystalline resin film preferably contains an antioxidant.
Examples of the antioxidant include a phenolic antioxidant, a phosphorus antioxidant, and a sulfur antioxidant.

  Examples of phenolic antioxidants include 3,5-di-t-butyl-4-hydroxytoluene, dibutylhydroxytoluene, 2,2′-methylenebis (6-t-butyl-4-methylphenol), 4,4 ′. -Butylidenebis (3-t-butyl-3-methylphenol), 4,4'-thiobis (6-t-butyl-3-methylphenol), α-tocophenol, 2,2,4-trimethyl-6-hydroxy -7-t-butylchroman, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, and the like.

  Examples of phosphorus antioxidants include distearyl pentaerythritol diphosphite, bis (2,4-ditertiarybutylphenyl) pentaerythritol diphosphite, tris (2,4-ditertiarybutylphenyl) phosphite, tetrakis (2 , 4-ditertiary butylphenyl) 4,4′-biphenyl diphosphite, trinonylphenyl phosphite and the like.

Examples of sulfur-based antioxidants include distearyl thiodipropionate and dilauryl thiodipropionate.
Content of antioxidant is 0.001 to 5 weight% normally with respect to a crystalline resin film, Preferably it is 0.01 to 4 weight%, More preferably, it is 0.1 to 3 weight%.

The manufacturing method of a crystalline resin film is not specifically limited. For example, known methods such as injection molding, extrusion molding, press molding, inflation molding, blow molding, calendar molding, cast molding, compression molding, and cast molding can be appropriately employed.
The crystalline resin film is preferably subjected to stretching treatment or crystallization annealing treatment in order to increase its crystallinity.
Although the thickness of a crystalline resin film is not specifically limited, Usually, it is 10-150 micrometers, Preferably it is 15-100 micrometers.

[Method for producing surface-modified film]
In the method of the present invention, at least one surface of the resin film (hereinafter sometimes referred to as the resin film (1)) is irradiated with light having a central wavelength of less than 180 nm using an excimer lamp. The desired surface modified film is obtained.

The central wavelength of the irradiated light is less than 180 nm. When the center wavelength of light is less than 180 nm, the target modification treatment can be performed efficiently. There is no particular lower limit value for the center wavelength of light, but it is usually 100 nm or more.
In the present invention, the “center wavelength of light” refers to a wavelength that provides the maximum emission intensity in the emission spectrum.

  When performing the modification treatment, light of the target center wavelength can be irradiated by appropriately selecting the type of excimer lamp. For example, the central wavelength of light emitted from an Ar excimer lamp is 126 nm, the central wavelength of light emitted from a Kr excimer lamp is 146 nm, and the central wavelength of light emitted from an ArBr excimer lamp is 165 nm. The central wavelength of light emitted from the Xe excimer lamp is 172 nm, and the central wavelength of light emitted from the ArCl excimer lamp is 175 nm.

  The light irradiation time is usually 0.1 to 150 seconds, preferably 1 to 120 seconds, more preferably 5 to 90 seconds.

In the method of the present invention, it is preferable to install the excimer lamp close to the resin film (1). The distance between the excimer lamp and the resin film (1) is preferably 10 mm or less.
The light irradiation may be performed on only one surface of the resin film (1) or on both surfaces.
When the surface-modified film is continuously produced, the long resin film (1) is conveyed along a conveyance path with respect to the long resin film being conveyed while being conveyed in a certain direction by a roll-to-roll method. It is preferable to irradiate light from an excimer lamp installed.

By performing a modification treatment on the resin film (1) using an excimer lamp, hydrophilic functional groups such as a hydroxyl group, a carboxyl group, and a carbonyl group are generated on the surface of the resin film (1). For this reason, when the obtained surface modification film is adhere | attached with metal foil through an adhesive bond layer, the laminated body by which the surface modification film and metal foil were adhere | attached firmly can be obtained.
In addition, when the resin film (1) is modified using an excimer lamp, the flexibility is less likely to be lower than that when a modification process such as ultraviolet irradiation is performed, and a heat history is applied. Even later, it becomes difficult to yellow.
As described above, according to the method of the present invention, a surface-modified film useful as a material for a resin substrate used for a printed wiring board or the like can be efficiently produced.

[Reforming method of resin layer]
In the method for modifying a resin layer according to the present invention, the surface of a resin layer mainly composed of a crystalline cyclic olefin resin is irradiated with light having a wavelength of less than 180 nm using an excimer lamp. It is characterized by quality.

The modification method of the present invention is a resin layer mainly composed of a crystalline cyclic olefin resin instead of the crystalline resin film mainly composed of a crystalline cyclic olefin resin in the method for producing a surface modified film of the present invention. The method is the same as the method for producing a surface-modified film of the present invention except that light is irradiated on the surface.
According to the method for modifying a resin layer of the present invention, a modified resin layer having properties similar to those of the surface modified film can be efficiently formed.

2) Laminate and flexible printed circuit board The laminate of the present invention is a laminate in which a resin film and a metal foil are bonded via an adhesive layer, and the resin film is formed by the method of the present invention. The obtained surface-modified film having a modified surface on one side or both sides, wherein the adhesive layer is adjacent to the modified surface of the surface-modified film.

  By having the surface-modified film obtained by the method of the present invention, the obtained laminate is less likely to cause yellowing or a decrease in peel strength even after receiving a thermal history.

The kind of metal foil which comprises the laminated body of this invention is not specifically limited.
Examples of the metal foil include copper foil, gold foil, silver foil, stainless steel foil, aluminum foil, nickel foil, and chromium foil. Among these, a copper foil is preferable because a laminate useful as a production material for a printed wiring board or the like can be obtained.
What is necessary is just to select suitably the thickness and roughening state of metal foil according to the intended purpose. Further, the metal foil may be subjected to a surface treatment with a silane coupling agent, a titanate coupling agent, or the like as necessary for the purpose of further strengthening the adhesive force. In addition, when using what contains a carboxyl group or a carboxylic anhydride group as alicyclic structure containing resin mentioned later, the surface modification of metal foil is carried out by processing the surface of metal foil using an aminosilane coupling agent. The quality film can be bonded more firmly.

The adhesive layer which comprises the laminated body of this invention is a layer which adhere | attaches a surface modification film and metal foil. The adhesive used for forming the adhesive layer is not particularly limited. Examples thereof include urethane resin-based, polyvinyl butyral-based, melamine resin-based, urea resin-based, epoxy resin-based, and alicyclic structure-containing resin-based adhesives.
Among these, an epoxy resin-based adhesive or an alicyclic structure-containing resin-based adhesive is preferable because the surface-modified film and the metal foil can be firmly bonded.

Examples of the urethane resin adhesive include an adhesive made of a combination of a main agent such as a urethane prepolymer and a curing agent such as a polyol.
Examples of the polyvinyl butyral adhesive include an adhesive made of a combination of a main agent such as polyvinyl alcohol and a curing agent such as butyraldehyde.
Examples of the melamine resin-based adhesive include an adhesive composed of a combination of a main agent such as cyanuric amide and a curing agent such as formaldehyde.
Examples of the urea resin adhesive include an adhesive made of a combination of a main agent such as urea and a curing agent such as ammonium chloride.

  Epoxy resin adhesives include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, flexible epoxy resin, brominated epoxy resin, glycidyl ester type epoxy resin, high Examples thereof include an adhesive composed of a combination of a main component such as a molecular type epoxy resin and a biphenyl type epoxy resin and a curing agent such as amine, polyamide resin, imidazole, polymercaptan, boron trifluoride, and dicyandiamide.

The alicyclic structure-containing resin adhesive is an adhesive mainly composed of an alicyclic structure-containing resin (a resin having an alicyclic structure in the main chain and / or side chain).
The alicyclic structure-containing resin has a glass transition temperature lower than the melting point of the crystalline cyclic olefin resin [polymer (α)], and has an epoxy group, a carboxyl group, a carboxylic acid anhydride group, and an oxysilyl group. Having a functional group selected from the group consisting of [hereinafter sometimes referred to as polymer (β). ] Is preferable.

The polymer (β) has a glass transition temperature lower than the melting point of the polymer (α). When the glass transition temperature of the polymer (β) is lower than the melting point of the polymer (α), it is possible to obtain a laminate having a uniform thickness in which the adhesive layer is in close contact with other layers.
The glass transition temperature of the polymer (β) is preferably 80 to 250 ° C, more preferably 90 to 220 ° C, and particularly preferably 100 to 200 ° C.

The polymer (β) has a functional group selected from the group consisting of an epoxy group, a carboxyl group, a carboxylic anhydride group, and an oxysilyl group.
An oxysilyl group refers to a group having a silicon-oxygen bond. Examples thereof include an alkylsilyloxy group, an alkoxysilyl group, an alkylalkoxysilyl group, an arylsilyloxy group, an alkylarylsilyloxy group, an aryloxysilyl group, an arylalkoxysilyl group, a silanol group, and a siloxane group.

  The content ratio of the functional group in the polymer (β) (number of functional groups: number of repeating units of the alicyclic structure-containing resin) is preferably 0.1: 100 to 20: 100, more preferably 0.2. : 100 to 15: 100, more preferably 0.5: 100 to 5: 100.

When there is too little content of the functional group contained in a polymer ((beta)), there exists a possibility that the adhesive force of a surface modification film and metal foil may be insufficient. On the other hand, if the amount of the functional group is too large, the water absorption of the alicyclic structure-containing resin is increased or the electrical properties are deteriorated, so that the low water absorption and excellent electrical properties of the obtained laminate are impaired. There is a fear.
When the polymer (β) has an oxysilyl group, the content of the oxysilyl group is determined on the basis of the number of silicon atoms in the oxysilyl group.

The weight average molecular weight (Mw) of a polymer ((beta)) is 30,000-200,000 normally, Preferably it is 40,000-100,000, More preferably, it is 45,000-60,000.
The molecular weight distribution (Mw / Mn) of the polymer (β) is usually 3 or less, preferably 2 or less, more preferably 1.5 or less.
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer (β) are polystyrene conversion values measured by gel permeation chromatography (GPC) using tetrahydrofuran as a developing solvent.

  Polymer (β) undergoes a polymerization reaction using a monomer having a functional group and an alicyclic structure, or a copolymerization reaction using a monomer having a functional group and a monomer having an alicyclic structure Or the like. In addition, a polymer having an alicyclic structure in the main chain and / or side chain and not having a functional group [hereinafter sometimes referred to as a polymer (β1). ] Can be obtained by a method of subjecting it to a modification treatment or the like. Among these methods, a method of subjecting the polymer (β1) to modification treatment and the like is preferable because a polymer (β) having a desired substituent can be obtained efficiently.

Examples of the polymer (β1) include a ring-opening polymer of a monomer having a norbornene ring and a hydride thereof, an aromatic ring hydride of an aromatic ring-containing polymer, a monomer having a norbornene ring and an α-olefin. Examples include addition polymers, addition polymers of cyclic olefins and cyclic dienes, and hydrides thereof.
As the polymer (β1), ZEONEX (registered trademark), ZEONOR (registered trademark) manufactured by ZEON CORPORATION; APEL (registered trademark), APO (registered trademark) manufactured by Mitsui Chemicals; TOPAS manufactured by Polyplastics Co., Ltd. (Registered Trademark); and other commercially available products can also be used.

  As the polymer (β1), it is easy to obtain a laminate having excellent flexibility. Therefore, a copolymer of an aromatic vinyl monomer and a conjugated diene monomer (in the following description, “copolymer (β2) The polymer obtained by hydrogenating the aromatic ring and the unsaturated bond in the conjugated diene monomer unit of the copolymer (β2) may be referred to simply as “copolymer hydrogen”. Are sometimes referred to as “compounds”).

The aromatic vinyl monomer used for the synthesis of the copolymer (β2) is styrene; α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene. Alkyl group-substituted styrene such as 4-ethylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene; 2-chlorostyrene, 3 -Halogen-substituted styrene such as chlorostyrene, 4-chlorostyrene, 4-bromostyrene, 2,4-dibromostyrene; alkyl groups such as 2-methyl-4,6-dichlorostyrene and halogen-substituted styrene; vinylnaphthalene; Can be mentioned. Among these, styrene is preferable.
An aromatic vinyl monomer can be used individually by 1 type or in combination of 2 or more types.

Examples of the conjugated diene monomer used for the synthesis of the copolymer (β2) include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1, Examples include 3-pentadiene and 1,3-hexadiene. Among these, 1,3-butadiene and isoprene are preferable.
Conjugated diene monomers can be used singly or in combination of two or more.

  The content ratio of the aromatic vinyl monomer unit and the conjugated diene monomer unit in the copolymer (β2) is not particularly limited, but the weight ratio of the aromatic vinyl monomer unit to the conjugated diene monomer unit is not limited. And preferably 20:80 to 65:35, more preferably 30:70 to 60:40.

When the copolymer (β2) is synthesized, the copolymer (β2) may be copolymerized using a monomer other than the aromatic vinyl monomer and the conjugated diene monomer. 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 ester monomers and non-conjugated diene monomers.
The content of the monomer unit other than the aromatic vinyl monomer unit and the conjugated diene monomer unit in the copolymer (β2) is not particularly limited, but is preferably the total monomer unit. Is 10% by weight or less, more preferably 5% by weight or less, and still more preferably 1% by weight or less.

  The copolymerization mode of the copolymer (β2) is not particularly limited and may be any of random copolymerization, taper copolymerization, block copolymerization, graft copolymerization, and the like. From the viewpoint of improving the balance between flexibility and strength of the resulting copolymer hydride, at least one aromatic vinyl polymer block (a polymer having an aromatic vinyl monomer unit as a main constituent unit). Block) and at least one conjugated diene polymer block (a polymer block having a conjugated diene monomer unit as a main constituent unit) and preferably an aromatic vinyl-conjugated diene block copolymer. And an aromatic vinyl-conjugated diene block copolymer comprising at least two aromatic vinyl polymer blocks and at least one conjugated diene polymer block, wherein the aromatic vinyl polymer block occupies both ends of the polymer chain. More preferably, the aromatic vinyl polymer block is formed by bonding an aromatic vinyl polymer block to both ends of the conjugated diene polymer block. - particularly preferably conjugated di-entry block copolymer.

  When the copolymer (β2) 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 other monomer units and the content of other monomer units other than the conjugated diene monomer unit in the conjugated diene polymer block are not particularly limited, but are each 10% by weight or less. It is preferably 5% by weight or less, more preferably 1% by weight or less.

  The polymerization method for obtaining the copolymer (β2) is not particularly limited. For example, any of radical polymerization, anion polymerization method, cation polymerization method, coordination anion polymerization method, coordination cation polymerization method and the like can be used. Good. When the copolymer (β2) is a block copolymer, an anionic polymerization method is preferable, and a living anionic polymerization method is particularly preferable.

  When the living anion 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 , 4-dilithio-2-ethylcyclohexane, etc., can be used; monoorganolithium is preferred. The polymerization reaction temperature is not particularly limited, but is usually selected in the range of 0 to 100 ° C, preferably 10 to 80 ° C, particularly preferably 20 to 70 ° C.

The polymerization reaction form for obtaining the copolymer (β2) 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. is there.
Solvents used include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane, and isooctane; alicyclics such as cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, and decalin Hydrocarbons; 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 for the hydrogenation reaction described later and the solubility of the copolymer (β2) is good. These solvents can 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 (β2), Lewis polymer is used in the polymerization reaction system for the purpose of improving the reaction progress rate or controlling the microstructure of the copolymer (β2). A base compound can be added. Examples of Lewis base compounds to be used 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; third compounds such as tetramethylethylenediamine, trimethylamine, triethylamine, and pyridine. And the like, and the like, and the like, and the like, and the like, and the like. These Lewis base compounds can be used alone or in combination of two or more.

The method for hydrogenating the copolymer (β2) is not particularly limited, and may be performed according to a known hydrogenation method.
As the hydrogenation catalyst, either a heterogeneous catalyst or a homogeneous catalyst can be used. Specific examples thereof are the same as those shown above as catalysts for the hydrogenation reaction of the ring-opening polymer.
Among them, at least one metal selected from nickel, cobalt, rhodium, palladium, platinum and the like can be obtained because the hydrogenation rate of the unsaturated bond containing an aromatic ring can be increased and the polymer chain scission reaction can be suppressed. It is preferable to use a catalyst containing
A hydrogenation catalyst can be used individually by 1 type or in combination of 2 or more types. The amount of the hydrogenation catalyst used is usually 0.01 to 100 parts by weight, preferably 0.05 to 50 parts by weight, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the copolymer (β2). It is.

  The hydrogenation reaction is usually performed in an inert organic solvent. Examples of the inert organic solvent are the same as those previously shown as the inert organic solvent for the hydrogenation reaction of the ring-opening polymer.

Although hydrogenation reaction temperature is not specifically limited, Usually, 10-250 degreeC, Preferably it is 50-200 degreeC, More preferably, it is 80-180 degreeC. Also, the hydrogen pressure is not particularly limited, but is usually 0.1 to 30 MPa, preferably 1 to 20 MPa, and more preferably 2 to 10 MPa.
After the hydrogenation reaction, the desired copolymer hydride may be recovered according to a conventional method.

The hydrogenation rate in the hydrogenation reaction is not particularly limited as long as at least a part of the unsaturated bonds of both the aromatic ring and the conjugated diene monomer unit of the copolymer (β2) are hydrogenated. The ratio of hydrogenated unsaturated bonds among all unsaturated bonds in the copolymer (β2) is preferably 90% or more, more preferably 97% or more, and particularly preferably 99% or more. In addition, the hydrogenation rate of the copolymer (β2) for obtaining the copolymer hydride can be determined based on ¹ H-NMR measurement.

  A method for synthesizing the polymer (β) by introducing a functional group into the polymer (β1) is not particularly limited. For example, a compound having a target functional group and an ethylenically unsaturated bond in the molecule (hereinafter sometimes referred to as “functional group-containing unsaturated compound”) is polymerized in the presence of a peroxide (β1). The polymer (β) can be synthesized by reacting with.

Functional group-containing unsaturated compounds used include ethylenically unsaturated group-containing epoxy compounds such as allyl glycidyl ether, glycidyl acrylate, and glycidyl methacrylate; ethylene such as maleic acid, monomethyl maleate, acrylic acid, methacrylic acid, and 4-pentenoic acid. -Containing unsaturated group-containing carboxylic acid; maleic anhydride, itaconic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic anhydride Ethylenically unsaturated dicarboxylic acid anhydrides such as: vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, p-styryltrimethoxysilane, p-styryl Triet Ethylenically unsaturated silane compounds such Shishiran; and the like.
A functional group containing unsaturated compound can be used individually by 1 type or in combination of 2 or more types.
The usage-amount of a functional group containing unsaturated compound is 0.1-20 weight part normally with respect to 100 weight part of polymers ((beta) 1), Preferably it is 0.2-10 weight part, More preferably, it is 0.5-5. Parts by weight.

As the peroxide to be used, 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-butylperoxyisobutyrate, lauroyl peroxide, dipropionyl peroxide Organic peroxides such as p- menthane hydroperoxide and the like.
Peroxides can be used singly or in combination of two or more.
The amount of the peroxide used is not particularly limited, but is usually 0.01 to 2 parts by weight, preferably 0.05 to 1 part by weight, more preferably 0.1 to 100 parts by weight of the polymer (β1). -0.5 parts by weight.

When the functional group-containing unsaturated compound is reacted with the polymer (β1) in the presence of a peroxide, a heating kneader or a reactor can be used. For example, a mixture containing the polymer (β1), the functional group-containing unsaturated compound, and the peroxide is heated and melted at a temperature equal to or higher than the melting temperature of the polymer (β1) in a biaxial kneader and kneaded for a desired time. The reaction can be carried out.
The reaction temperature (the temperature of the polymer (β1)) at this time is not particularly limited, but is usually 180 to 240 ° C, preferably 190 to 230 ° C, and 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.

When the adhesive layer is mainly composed of the alicyclic structure-containing resin, the adhesive layer may contain other components such as additives in addition to the alicyclic structure-containing resin. .
Other components include antioxidants, crosslinking agents, antioxidants, flame retardants, flame retardant aids, colorants, antistatic agents, plasticizers, ultraviolet absorbers, light stabilizers, near infrared absorbers, lubricants, etc. Is mentioned.
These contents can be appropriately determined according to the purpose, but are usually less than 50% by weight, preferably 40% by weight or less based on the adhesive layer.

  In the laminate of the present invention, a surface modified film and a metal foil are bonded via an adhesive layer, and the adhesive layer is adjacent to the modified surface of the surface modified film. For this reason, the laminated body of this invention becomes the thing excellent in the adhesiveness of an adhesive bond layer and a surface modification film.

  The laminate of the present invention has a layer structure of metal foil / adhesive layer / surface modified film obtained by using a modified film having a modified surface only on one side as the surface modified film. Or having a layer structure of metal foil / adhesive layer / surface modified film / adhesive layer / metal foil obtained by using a modified film having modified surfaces on both sides. There may be.

  The laminate of the present invention is obtained by firmly bonding a surface-modified film excellent in heat resistance, low water absorption and electrical characteristics and a metal foil. Therefore, even after receiving a heat history, it is a laminate that hardly causes yellowing or a decrease in peel strength.

The flexible printed circuit board of the present invention uses the laminate of the present invention.
For this reason, the flexible printed circuit board of the present invention is excellent in heat resistance, low water absorption, and electrical characteristics, and is less likely to cause yellowing or a decrease in peel strength even after receiving a thermal history.

3. The manufacturing method of a laminated body The manufacturing method of the laminated body of this invention is the manufacturing method (A) which has the following process (aI)-(a-II), and the following process (bI)-(b-II). The manufacturing method (B) which has, or the manufacturing method (C) which has the following process (cI).

[Production method (A)]
The production method (A) includes the following steps (a-I) to (a-II).
Step (a-I): Step of forming an adhesive layer by applying an adhesive layer forming liquid on the modified surface of the surface modified film and drying the resulting coating film (a -II): A step of bonding the surface-modified film and the metal foil through the adhesive layer after the metal foil is overlaid on the adhesive layer formed in the step (a-I).

In the step (a-I), an adhesive layer is formed by applying an adhesive layer forming solution to the modified surface of the surface modified film and drying the obtained coating film.
As the adhesive layer forming liquid, the adhesive solution or dispersion shown for the adhesive layer can be used.
Solvents used for the preparation of the adhesive layer forming liquid include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as pentane and hexane; alicyclic hydrocarbons such as cyclohexane and decahydronaphthalene; And ethers such as tetrahydrofuran and ethylene glycol dimethyl ether; halogenated hydrocarbons such as cyclomethane; and the like.
The method for applying the adhesive layer forming liquid is not particularly limited. Examples thereof include a roll coating method, a reverse coating method, a roll brush method, a spray coating method, an air knife coating method, a gravure coating method, a dipping method, and a curtain coating method.

The coating amount of the adhesive layer forming liquid is not particularly limited, and can be appropriately determined according to the thickness of the target adhesive layer.
The thickness of the adhesive layer is preferably 1 to 50 μm, more preferably 2 to 20 μm after drying.

When drying the coating film obtained by applying the adhesive layer forming liquid, it can be performed according to a conventional method.
Although a drying temperature is not specifically limited, Usually, it is 50-180 degreeC, Preferably it is 80-160 degreeC.
The drying time is not particularly limited, but is usually 10 seconds to several hours.

In the step (a-II), the metal foil is overlaid on the adhesive layer formed in the step (a-I), and then the surface-modified film and the metal foil are bonded via the adhesive layer.
The bonding method is not particularly limited, and can be appropriately determined according to the adhesive to be used.
For example, in the case of an ultraviolet curable adhesive, the surface-modified film and the metal foil can be bonded by irradiating the adhesive layer with ultraviolet rays.
Moreover, if it is an adhesive agent which requires a heating, a surface modification film and metal foil can be adhere | attached by performing hot press on predetermined conditions.

[Production method (B)]
The production method (B) has the following steps (b-I) to (b-II).
Step (b-I): Step of forming an adhesive layer by applying an adhesive layer forming liquid on the metal foil and drying the obtained coating film (b-II): Step ( After the surface modified film is stacked on the adhesive layer formed in b-I) so that the modified surface faces the adhesive layer, the surface modified film and the metal foil are bonded. The process of bonding through the agent layer

In the step (b-I), an adhesive layer is formed by applying a liquid for forming an adhesive layer on a metal foil and drying the obtained coating film.
Step (b-I) is the same as step (a-I) except that in the step (a-I), a metal foil is used instead of the surface-modified film.

In the step (b-II), the surface-modified film is stacked on the adhesive layer formed in the step (b-I) so that the modified surface faces the adhesive layer. The surface modified film and the metal foil are bonded via an adhesive layer.
The step (b-II) is different from the step (a-II) except that the metal foil with an adhesive layer and the surface modified film are stacked instead of the surface modified film with the adhesive layer and the metal foil. The same operation as in step (a-II) is performed.

[Production method (C)]
The production method (C) includes the following step (c-I).
Step (c-I): The surface-modified film, the sheet-like adhesive, and the metal foil are arranged in this order, and the modified surface of the surface-modified film faces the sheet-like adhesive. The process of adhering the surface-modified film and the metal foil through the sheet adhesive after being stacked

  In the step (c-I), the surface modified film, the sheet adhesive, and the metal foil are arranged in this order, and the modified surface of the surface modified film faces the sheet adhesive. After superimposing, the surface-modified film and the metal foil are bonded via a sheet-like adhesive.

The sheet-like adhesive used in the step (c-1) can be obtained, for example, by applying an adhesive layer forming liquid on a release sheet and drying the obtained coating film. Alternatively, an adhesive resin (for example, the alicyclic structure-containing resin) can be obtained by melt extrusion using an extruder equipped with a T die.
Although the thickness of a sheet-like adhesive is not specifically limited, Usually, 5-100 micrometers, Preferably it is 10-50 micrometers.
In the step (c-I), when the surface-modified film and the metal foil are bonded via a sheet-like adhesive, the same method as in the step (a-II) can be used.

In the production methods (A) to (C), the adhesive layer or the sheet-like adhesive has a glass transition temperature lower than the melting point of the crystalline cyclic olefin resin, and an epoxy group, a carboxyl group, or a carboxylic acid When the main component is an alicyclic structure-containing resin having a functional group selected from the group consisting of an anhydride group and an oxysilyl group, the surface-modified film and the metal foil are bonded via a sheet-like adhesive. When adhering, the laminated body before the adhesion treatment having a layer structure of a surface modified film / adhesive layer or a sheet-like adhesive / metal foil is equal to or higher than the glass transition temperature of the alicyclic structure-containing resin, and It is preferable to heat to a temperature below the melting point of the crystalline cyclic olefin resin.
By heating on the said conditions, the laminated body to which each layer was adhere | attached more firmly can be obtained simply and efficiently.
When this heating is performed by hot pressing, the conditions are not particularly limited. For example, the heating can be performed under conditions of a temperature of 80 to 250 ° C., a pressure of pressure bonding of 1.0 to 5.0 MPa, and a pressure bonding time of 1 to 180 minutes.
Moreover, since the void at the time of bonding can be reduced, it is preferable to perform a hot press under reduced pressure using a vacuum laminator etc.
In the production methods (A) to (C), preferred crystalline cyclic olefin resins and preferred alicyclic structure-containing resins are the same as those described above in the description of the surface-modified film or laminate. Can be mentioned.

  According to the method of the present invention, a laminate useful as a flexible substrate material can be efficiently produced.

Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to the following examples. In the following examples and comparative examples, “parts” and “%” are based on weight unless otherwise specified.
The measurement in each example was performed by the following method.

[Glass transition temperature and melting point]
Using a differential scanning calorimeter (DSC), differential scanning calorimetry was carried out at a temperature rising rate of 10 ° C./min, and the glass transition temperature and melting point of the polymer were measured.

[Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)]
Gel permeation chromatography (GPC) was performed at 40 ° C. using tetrahydrofuran as a solvent, and the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) were determined as polystyrene equivalent values.
Measuring apparatus: Gel permeation chromatography (GPC) system “HLC-8220” (manufactured by Tosoh Corporation)
Column: “H type column” (manufactured by Tosoh Corporation)

[Hydrogenation rate of unsaturated bond]
^{Based on the 1} H-NMR measurement, the hydrogenation rate of the unsaturated bond in the polymer was determined.

[Functional group content]
^{Based on 1} H-NMR measurement, the content ratio of functional groups in the polymer (number of functional groups: number of repeating units of the polymer) was determined.

[Production Example 1] [Synthesis of dicyclopentadiene ring-opening polymer hydride]
In a metal pressure-resistant reaction vessel purged with nitrogen inside, 154.5 parts of cyclohexane, 42.8 parts of cyclohexane solution (concentration 70%) of dicyclopentadiene (end content 99% or more) (30 parts as dicyclopentadiene) 1-hexene 1.9 parts was added and the whole was heated to 53 ° C.
On the other hand, in a solution obtained by dissolving 0.014 part of tetrachlorotungstenphenylimide (tetrahydrofuran) complex in 0.70 part of toluene, 0.061 part of n-hexane solution of diethylaluminum ethoxide (concentration 19%). And stirred for 10 minutes to prepare a catalyst solution. This catalyst solution was added to the reactor and a ring-opening polymerization reaction was performed at 53 ° C. for 4 hours to obtain a solution containing a dicyclopentadiene ring-opening polymer.

To 200 parts of the solution containing the obtained dicyclopentadiene ring-opened polymer, 0.037 part of 1,2-ethanediol was added as a terminator and stirred at 60 ° C. for 1 hour to stop the polymerization reaction. Thereafter, 1 part of a hydrotalcite-like compound (product name “KYOWARD (registered trademark) 2000”, manufactured by Kyowa Chemical Industry Co., Ltd.) was added, heated to 60 ° C., and stirred for 1 hour. 0.4 parts of filter aid (product name “Radiolite (registered trademark) # 1500” manufactured by Showa Chemical Industry Co., Ltd.) is added, and PP pleated cartridge filter (product name “TCP-HX”, manufactured by ADVANTEC Toyo Co., Ltd.) is used. The adsorbent was filtered off to obtain a solution containing a dicyclopentadiene ring-opening polymer.
A part of this solution was used to measure the molecular weight of the dicyclopentadiene ring-opened polymer. The weight average molecular weight (Mw) was 28,100, the number average molecular weight (Mn) was 8,750, the molecular weight distribution (Mw / Mn) was 3.21.

100 parts cyclohexane and 0.0043 parts chlorohydridocarbonyltris (triphenylphosphine) ruthenium are added to 200 parts solution (polymer content 30 parts) containing dicyclopentadiene ring-opening polymer after purification treatment, and hydrogen Hydrogenation reaction was performed at 6 MPa and 180 ° C. for 4 hours. The reaction liquid was a slurry liquid in which a solid content was deposited.
The reaction solution was centrifuged to separate the solid and the solution, and the solid was dried under reduced pressure at 60 ° C. for 24 hours to obtain 28.5 parts of a dicyclopentadiene ring-opened polymer hydride.
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride was 99% or more, the glass transition temperature was 98 ° C., and the melting point was 262 ° C.

[Production Example 2] [Production of stretched film of crystalline cyclic olefin resin (resin film A1)]
To 100 parts of the dicyclopentadiene ring-opening polymer hydride obtained in Production Example 1, an antioxidant (tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] was added. After mixing 0.8 part of methane, product name “Irganox (registered trademark) 1010” (manufactured by BASF Japan), the mixture is put into a twin screw extruder (TEM-37B, manufactured by Toshiba Machine Co., Ltd.) and melted by heat. After obtaining a strand-like molded body by extrusion molding, this was chopped with a strand cutter to obtain pellets.
The operating conditions of the twin screw extruder are shown below.
-Barrel set temperature: 270-280 ° C
・ Die setting temperature: 250 ℃
・ Screw speed: 145rpm
・ Feeder rotation speed: 50 rpm

A 100 μm-thick film molded body was obtained from the obtained pellets with a hot melt extrusion film forming machine (product name “Measuring Extruder Type Me-20 / 2800V3”, manufactured by Optical Control Systems) equipped with a T-die.
The operating conditions of the film forming machine are shown below.
・ Barrel temperature setting: 280-290 ° C
-Die temperature: 270 ° C
-Screw rotation speed: 30rpm

After cutting out a part of the obtained film molded body, it was placed in a small stretching machine (product name “EX10-B type”, manufactured by Toyo Seiki Seisakusho Co., Ltd.) and stretched to obtain a stretched film. Next, the stretched film was fixed to an iron plate, and heat treatment was performed in an oven at 200 ° C. for 20 minutes to obtain a stretched film of a crystalline cyclic olefin resin having a thickness of 50 μm.
The operating conditions of the small stretcher are shown below.
-Stretching speed: 10,000 mm / min
-Stretching temperature: 100 ° C
-Stretch ratio: 2 times

[Production Example 3] [Production of crystalline cyclic olefin resin film (resin film A2)]
In the same manner as in Production Example 2, a 50 μm-thick film molded body was obtained using a hot melt extrusion film molding machine equipped with a T die.
Next, the obtained film molding was subjected to a crystallization annealing treatment at 200 ° C. to obtain a crystalline cyclic olefin resin film having a thickness of 50 μm.

[Production Example 4] (Synthesis of oxysilyl group-containing polymer)
550 parts of dehydrated cyclohexane, 25 parts of dehydrated styrene and 0.475 part of di-n-butyl ether were placed in a reactor equipped with a stirrer and purged with nitrogen. The whole volume of n-butyllithium was stirred at 60 ° C. with stirring. A polymerization reaction was started by adding 0.68 part of a cyclohexane solution (concentration 15%). While continuing the stirring, the reaction was conducted at 60 ° C. for 60 minutes, and then 50 parts of dehydrated isoprene was added and the reaction was continued for 30 minutes at 60 ° C. Further, 25 parts of dehydrated styrene was added and the reaction was continued for 30 minutes at 60 ° C. It was. Thereafter, 0.5 parts of isopropyl alcohol was added to stop the reaction.
The obtained styrene-isoprene-styrene triblock 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) 1 .5 parts and 50 parts of dehydrated cyclohexane were added and mixed. After replacing the inside of the reactor with hydrogen gas, hydrogen gas was supplied while stirring the entire volume, and a hydrogenation reaction was performed at a temperature of 170 ° C. and a pressure of 4.5 MPa for 6 hours.
The polymer was precipitated by pouring the reaction solution into a large amount of isopropyl alcohol. The polymer was collected by filtration, washed, and dried under reduced pressure at 60 ° C. for 24 hours.
The obtained polymer is a hydride of styrene-isoprene-styrene triblock copolymer, the weight average molecular weight (Mw) is 65,300, the molecular weight distribution (Mw / Mn) is 1.06, and all unsaturated. The hydrogenation rate of the bond was 99% or more.

  Next, 2.0 parts of vinyltrimethoxysilane and 0.2 part of di-t-butyl peroxide were added to and mixed with 100 parts of the resulting copolymer hydride. This mixture was 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 obtain an oxysilyl group-containing polymer. About this oxysilyl group-containing polymer, the content ratio of functional groups (trimethoxysilyl group) and the glass transition temperature were measured, and the content ratio of functional groups (number of functional groups: number of repeating units of alicyclic structure-containing resin) Was 1.4: 100 and the glass transition temperature was 122 ° C.

[Production Example 5] (Production of copper foil with adhesive layer)
Using a 30% toluene solution of the oxysilyl group-containing polymer obtained in Production Example 4 with a doctor blade with a gap of 25 μm, an electrolytic copper foil with a thickness of 18 μm (“F2-WS”, manufactured by Furukawa Electric Rz = 2.1 μm) ). This was heated in an oven at 150 ° C. for 5 minutes to dry toluene, thereby forming an adhesive layer (oxysilyl group-containing polymer layer) having a thickness of 5 μm, and a copper foil with an adhesive layer was obtained.

[Example 1]
Using an RF discharge excimer lamp (L11751, manufactured by Hamamatsu Photonics) on both sides of the resin film A1 obtained in Production Example 2, from the position where the distance between the lamp and the resin film A1 is 2 mm, excimer light ( The surface modified film 1 was obtained by irradiating with a wavelength of 172 nm for 30 seconds.

[Example 2]
A surface modified film 2 was obtained in the same manner as in Example 1 except that the resin film A2 obtained in Production Example 3 was used instead of the resin film A1.

Example 3
On the surface modified film 1 obtained in Example 1, a 30% toluene solution of the oxysilyl group-containing polymer obtained in Production Example 4 was applied using an applicator having a gap of 20 μm, and then this was applied at 150 ° C. By heating in an oven for 5 minutes, an adhesive layer (oxysilyl group-containing polymer layer) having a thickness of 5 μm was formed on one surface of the surface-modified film 1.
Next, an adhesive layer is formed in the same manner on the surface of the surface modified film 1 where the adhesive layer is not formed, and a laminate in which an adhesive layer having a thickness of 5 μm is formed on both surfaces of the surface modified film 1 A film was obtained.
Next, an electrolytic copper foil having a thickness of 18 μm was laminated on both surfaces of the laminated film so that the mat surface thereof was opposed to the adhesive layer of the laminated film. Next, after sandwiching the laminated body before the bonding treatment with a pair of SUS plates having a thickness of 1 mm, a manual hydraulic vacuum heating press (11FA, manufactured by Imoto Seisakusho Co., Ltd.) was used. The laminate was formed by pressing for 2 minutes, and copper foil was bonded to both surfaces of the surface-modified film 1 via an adhesive layer.

Example 4
On both surfaces of the surface modified film 1 obtained in Example 1, the copper foil with an adhesive layer obtained in Production Example 5 was overlapped so that the adhesive layer opposed to the surface modified film 1. Next, after sandwiching the laminate before the bonding treatment with a pair of 1 mm thick SUS plates, it was pressed using a manual hydraulic vacuum heating press at a temperature of 180 ° C. and a pressure of 1 MPa for 10 minutes to obtain a surface modified film. A laminate in which a copper foil was bonded to both sides of 1 via an adhesive layer was obtained.

Example 5
In Example 3, a laminate was obtained in the same manner as in Example 3 except that the surface modified film 2 obtained in Example 2 was used instead of the surface modified film 1.

Example 6
In Example 4, a laminate was obtained in the same manner as in Example 4 except that the surface modified film 2 obtained in Example 2 was used instead of the surface modified film 1.

Example 7
An epoxy resin adhesive (EPOX AH-333, manufactured by Printec Co., Ltd.) was applied onto the surface modified film 1 obtained in Example 1 using an applicator with a gap of 15 μm, and then applied to an oven at 150 ° C. By heating for 5 minutes, an adhesive layer having a thickness of 5 μm was formed on one surface of the surface-modified film 1.
Next, an adhesive layer is formed in the same manner on the surface of the surface modified film 1 where the adhesive layer is not formed, and a laminate in which an adhesive layer having a thickness of 5 μm is formed on both surfaces of the surface modified film 1 A film was obtained.
Next, an electrolytic copper foil having a thickness of 18 μm was laminated on both surfaces of the laminated film so that the mat surface thereof was opposed to the adhesive layer of the laminated film. Next, after sandwiching the laminated body before the bonding treatment with a pair of SUS plates having a thickness of 1 mm, a manual hydraulic vacuum heating press (11FA, manufactured by Imoto Seisakusho Co., Ltd.) was used. The laminate was formed by pressing for 2 minutes, and copper foil was bonded to both surfaces of the surface-modified film 1 via an adhesive layer.

Example 8
In Example 7, a laminate was obtained in the same manner as in Example 7 except that the surface modified film 2 obtained in Example 2 was used instead of the surface modified film 1.

[Comparative Example 1]
In Example 1, a surface-modified film was obtained in the same manner as in Example 1, except that an amorphous cyclic olefin resin film (ZF14, manufactured by Nippon Zeon Co., Ltd., thickness 50 μm) was used instead of the resin film A1. 3 was obtained.
Next, in Example 3, a laminate was obtained in the same manner as in Example 3 except that the surface modified film 3 was used instead of the surface modified film 1.

[Reference Example 1]
Using a small ultraviolet surface treatment apparatus (KOL1-300, manufactured by Koto Electric Co., Ltd.) on both surfaces of the resin film A2 obtained in Production Example 3, ultraviolet rays (center wavelength: 254 nm) from a low-pressure mercury lamp in the air at an irradiation distance of 10 mm Was irradiated for 30 seconds to obtain a surface-modified film 4.
In Example 7, it replaced with the surface modification film 1, and except having used the surface modification film 4, it carried out similarly to Example 7, and obtained the laminated body.

[Reference Example 2]
Using a small ultraviolet surface treatment device, both surfaces of the resin film A2 obtained in Production Example 3 were irradiated with ultraviolet light (center wavelength: 254 nm) from a low-pressure mercury lamp for 120 seconds in an air at an irradiation distance of 10 mm, and the surface modified film 5 was obtained.
In Example 7, it replaced with the surface modification film 1, and except having used the surface modification film 5, it carried out similarly to Example 7, and obtained the laminated body.

[Reference Example 3]
On both surfaces of the resin film A2 obtained in Production Example 3, a corona surface treatment apparatus (manufactured by Wedge Corporation) using a switchback automatic traveling type corona discharge treatment is performed once at a conveying speed of 1 m / min, and the surface modification is performed. A quality film 6 was obtained.
In Example 7, a laminate was obtained in the same manner as in Example 7 except that the surface modified film 6 was used instead of the surface modified film 1.

[Reference Example 4]
On both surfaces of the resin film A2 obtained in Production Example 3, plasma treatment is performed once at a conveying speed of 3 m / min and a nitrogen flow rate of 400 l / min using an atmospheric pressure plasma processing apparatus (manufactured by eSquare). A quality film 7 was obtained.
In Example 7, a laminate was obtained in the same manner as in Example 7 except that the surface modified film 7 was used instead of the surface modified film 1.

[Reference Example 5]
In Example 7, instead of the surface-modified film 1, an attempt was made to produce a laminate using the resin film A2 obtained in Production Example 3 as it was without undergoing a modification treatment, but an epoxy adhesive was applied. As a result, the resin film A2 repels the adhesive, and the adhesive layer could not be formed.

  The initial peel strength and the peel strength after the heat resistance test of the laminate obtained in each example were measured by the following methods. Moreover, the evaluation board | substrate with which the through-hole daisy chain was formed was produced using the obtained laminated body, and the thermal shock test was done. These results are shown in Table 1.

[Initial peel strength]
In accordance with JIS K6471 standard, peel strength was measured as follows.
The laminates obtained in Examples, Comparative Examples, and Reference Examples were cut into a size of 25 mm × 100 mm and used as test pieces. A 10 mm × 100 mm strip-shaped cut was made in the copper foil at the center of the test piece with a cutter. After peeling off the end of the cut copper foil, the test piece was attached to a 3 mm thick FR-4 substrate with a double-sided adhesive tape. This was fixed to a tensile tester (Autograph AGS-5kNG, manufactured by Shimadzu Corporation) with a dedicated 90 ° peel test jig, and then the peel strength of the copper foil was measured at a speed of 50 mm / min.

[Peel strength after heat test]
The laminates obtained in the examples, comparative examples, and reference examples were cut into a size of 25 mm × 100 mm, and then heated in an oven at 150 ° C. for 168 hours to obtain a test piece.
Next, peel strength was measured by the same method as described above.

(Cool thermal shock test)
The laminates obtained in the examples, comparative examples, and reference examples were cut out to a size of 40 mm × 80 mm, and then 10 × 4 rows of through holes having a drill diameter of 0.30 mm were provided. Next, after performing desmear treatment and reduction treatment on this, electroless copper plating and electrolytic copper plating were performed to form a conductor layer having a thickness of about 15 μm on the side wall of the through hole, and a through hole plated substrate was obtained. .
A dry film resist (RY3215 manufactured by Hitachi Chemical Co., Ltd.) is thermally laminated on both sides of the obtained substrate with a roll laminator, and a film mask printed with a predetermined conductor circuit pattern is disposed on both sides of the substrate, and then a double-sided printer. The exposure was performed. Furthermore, after developing the exposed resist with a 1% aqueous sodium carbonate solution, opening a predetermined portion, etching with ferric chloride, and immersing in a 5% aqueous sodium hydroxide solution to remove the resist, Four daisy chain circuits consisting of 10 through holes were produced.
After connecting the cables of the connection reliability evaluation system (MLR21, manufactured by Enomoto Kasei Co., Ltd.) to the four daisy chain circuits, the test pieces are put into the air tank type thermal shock tester (WINTECH NT1200W, Enomoto Kasei Co., Ltd.). Then, the thermal shock test was conducted up to 1000 cycles under the conditions of a low temperature bath of -45 ° C, a high temperature bath of 125 ° C, and an exposure time of 15 minutes. Evaluation was performed according to the following criteria.

A: There is no disconnection up to 1000 cycles.
○: There was no disconnection up to 500 cycles, and disconnection occurred between 501 and 1000 cycles.
Δ: Disconnection occurred up to 500 cycles.
X: All four daisy chain circuits were disconnected by 500 cycles.

As can be seen from Table 1, the laminate of the present invention has a high initial peel strength, and even when exposed to high temperature conditions for a long time, there is little decrease in peel strength. In addition, a thermal shock test in a low temperature bath of −45 ° C. and a high temperature bath of 125 ° C. was performed on a test substrate on which a through-hole daisy chain was formed, but there was little disconnection.
Therefore, it can be seen that according to the present invention, it is possible to provide a flexible printed wiring board that is superior in connection reliability compared to a conventional flexible printed circuit board material made from a cycloolefin polymer.

Claims (13)

Modifying the crystalline resin film by irradiating at least one surface of the crystalline resin film mainly composed of the crystalline cyclic olefin resin with light having a center wavelength of less than 180 nm using an excimer lamp. A method for producing a surface-modified film, characterized in that:   A resin layer characterized by modifying the resin layer by irradiating the surface of the resin layer mainly composed of a crystalline cyclic olefin resin with light having a center wavelength of less than 180 nm using an excimer lamp. Reforming method. A resin film and a metal foil are laminated bodies formed by bonding via an adhesive layer,
The resin film is a surface modified film obtained by the method according to claim 1 and having a modified surface on one side or both sides,
The laminate is characterized in that the adhesive layer is adjacent to the modified surface of the surface-modified film.   The laminate according to claim 3, wherein the metal foil is a copper foil.   The adhesive layer has a glass transition temperature lower than the melting point of the crystalline cyclic olefin resin, and a functional group selected from the group consisting of an epoxy group, a carboxyl group, a carboxylic acid anhydride group, and an oxysilyl group The laminated body of Claim 3 or 4 which has an alicyclic structure containing resin which has as a main component.   The content ratio (the number of functional groups: the number of repeating units of the alicyclic structure-containing resin) of the functional group in the alicyclic structure-containing resin is 0.1: 100 to 20: 100. Laminated body. The surface modified film is a film having modified surfaces on both sides,
The laminate according to any one of claims 3 to 6, wherein the laminate has a layer structure of metal foil / adhesive layer / surface modified film / adhesive layer / metal foil.   The flexible printed circuit board which uses the laminated body in any one of Claims 3-7. The manufacturing method of the laminated body in any one of Claims 3-7 which has the following process (aI)-(a-II).
Step (a-I): Step of forming an adhesive layer by applying an adhesive layer forming liquid on the modified surface of the surface modified film and drying the resulting coating film (a -II): A step of bonding the surface-modified film and the metal foil through the adhesive layer after the metal foil is overlaid on the adhesive layer formed in the step (a-I). The manufacturing method of the laminated body in any one of Claims 3-7 which has the following process (bI)-(b-II).
Step (b-I): Step of forming an adhesive layer by applying an adhesive layer forming liquid on the metal foil and drying the obtained coating film (b-II): Step ( After the surface modified film is stacked on the adhesive layer formed in b-I) so that the modified surface faces the adhesive layer, the surface modified film and the metal foil are bonded. The process of bonding through the agent layer The manufacturing method of the laminated body in any one of Claims 3-7 which has the following process (c-I).
Step (c-I): The surface-modified film, the sheet-like adhesive, and the metal foil are arranged in this order, and the modified surface of the surface-modified film faces the sheet-like adhesive. The process of adhering the surface-modified film and the metal foil through the sheet adhesive after being stacked The adhesive layer or the sheet-like adhesive has a glass transition temperature lower than the melting point of the crystalline cyclic olefin resin, and from the group consisting of an epoxy group, a carboxyl group, a carboxylic anhydride group, and an oxysilyl group The main component is an alicyclic structure-containing resin having a selected functional group,
The operation of bonding the surface-modified film and the metal foil through the adhesive layer or the sheet-like adhesive is
The laminated body before the adhesion treatment having a layer structure of surface modified film / adhesive layer or sheet-like adhesive / metal foil is equal to or higher than the glass transition temperature of the alicyclic structure-containing resin and the crystalline cyclic olefin resin. The manufacturing method of the laminated body in any one of Claims 9-11 which is what heats to the temperature below melting | fusing point.   The content ratio of the functional group in the alicyclic structure-containing resin (the number of functional groups: the number of repeating units of the alicyclic structure-containing resin) is 0.1: 100 to 20: 100. The manufacturing method of the laminated body.