JP2009298063A - Laminate and wiring substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate and a wiring substrate, wherein the laminate comprises a resin substrate, a rubber layer and a conductive layer joined firmly by molecular adhesion and the wiring substrate has a smooth surface metal wiring superior in insulating characteristics and transmits electric signal of even a high-frequency current. <P>SOLUTION: A laminate 10A has: a resin layer formed of an alicyclic olefin polymer, an adhesive layer (I) 2a of a specific alkoxysilane compound (A) formed on one side of the resin layer, a rubber layer 3 formed on the opposite side to the resin layer in the adhesive layer (I), an adhesive layer (II) 2b of the specific alkoxysilane compound (A) formed on the opposite side to the adhesive layer (I) in the rubber layer and a conductive layer 4 formed on the opposite side to the rubber layer in the adhesive layer (II). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a laminate and a wiring board in which a resin substrate, a rubber layer, and a conductive layer are firmly bonded by molecular bonding.

  With the recent demand for higher functionality and smaller electronic devices, electronic components have been increasingly densely integrated and densely mounted, and high-speed transmission of electrical signals has been demanded. However, as the density of electronic components has increased, the speed has been increased to such a state that electrical performance such as delay of electrical signals cannot be ensured. Therefore, degradation of electrical signals becomes a problem for high speed transmission. ing.

  The deterioration of the electric signal is the sum of the loss of the electric signal from the conductor and the loss of the electric signal from the dielectric. In particular, the loss of the electric signal from the dielectric due to the interlayer insulating material increases remarkably with an increase in the frequency of the electric signal, and is a main factor for deterioration of the electric signal at a frequency of 1 GHz band. .

  For this reason, generally used epoxy resin, polyimide resin, etc. as interlayer insulation materials for electronic devices such as multilayer wiring boards have insufficient electrical properties such as dielectric constant and dielectric loss tangent, and can support high-speed transmission of electrical signals. May be difficult to do.

  Examples of the resin having a low dielectric constant and excellent electrical characteristics include polynorbornene, which is an alicyclic cycloolefin polymer (Non-Patent Document 1). However, this polynorbornene has insufficient photosensitivity / developability and adhesion to the substrate.

In connection with the present invention, Patent Document 1 discloses a printed wiring board in which a conductive metal wiring layer is formed on a resin substrate using a molecular adhesive made of a triazine dithiol metal salt, and the multilayered structure is bonded together. A multilayer printed circuit board is described.
Patent Document 2 discloses an adhesive composite product of resin and rubber using a molecular adhesive composed of a triazine dithiol metal salt.
However, these documents do not describe an alicyclic olefin polymer as a resin substrate material to be used.
NiCOLE R.M. GROVE et al. Journal of Polymer Science: part B, Polymer Physics, Vol. 37, 3003-3010 (1999) JP 2007-17921 A JP 2007-119752 A

  The present invention has been made in view of the above-described prior art, and is excellent in a laminated body in which a resin substrate, a rubber layer, and a conductive layer are firmly bonded to each other by molecular bonding, and an insulating signal. It is an object of the present invention to provide a wiring board having a smooth-surface metal wiring through which water is propagated.

  As a result of diligent research to solve the above problems, the present inventors have used a resin substrate made of an alicyclic olefin polymer as a resin substrate, introduced an OH group on the surface of the resin substrate, and then a specific thiol reaction. The alkoxysilane compound is reacted to form a monomolecular film of the alkoxysilane compound, a rubber layer is laminated on the surface of the monomolecular film, and a conductive layer is formed on the rubber layer surface via the monomolecular film of the alkoxysilane compound. It was found that a laminated body in which the resin substrate, the rubber layer and the conductive layer are firmly bonded can be obtained by laminating. In addition, this laminate has excellent insulating properties and has smooth surface metal wiring through which an electric signal is propagated even with high-frequency current. Therefore, it has been found that the laminate is suitable as a wiring board, and the present invention has been completed. It was.

Thus, according to the first aspect of the present invention, the following laminates (1) to (9) are provided.
(1) a resin layer formed from an alicyclic olefin polymer;
On one side of the resin layer, an adhesive layer (I) formed from a thiol-reactive alkoxysilane compound represented by the following formula (A);
A rubber layer formed on the surface of the adhesive layer (I) opposite to the resin layer;
An adhesive layer (II) formed from a thiol-reactive alkoxysilane compound represented by the following formula (A) on the surface of the rubber layer opposite to the adhesive layer (I), and the adhesive layer The laminated body which has a conductive layer formed in the surface on the opposite side to the said rubber layer in (II).

(In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an optionally substituted phenyl group, or a cycloalkyl having 3 to 10 carbon atoms. Represents a group.
R ² represents an alkylene group having 1 to 20 carbon atoms. In the alkylene chain, the alkylene group is an oxygen atom, a sulfur atom, a group represented by the formula: NR ³ (R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms), —C (= A group represented by O) NH—CH ₂ CH ₂ — or a group represented by —O—C (═O) NH— may be contained.
X represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
Y represents an alkoxy group having 1 to 10 carbon atoms.
n represents an integer of 1 to 3.
M represents an alkali metal atom. )

(2) The adhesive layer (I) reacts the OH group provided on the surface of the alicyclic olefin polymer with the alkoxy group of the thiol-reactive alkoxysilane compound represented by the formula (A). The laminated body as described in (1) which is formed by this.
(3) The rubber layer is a surface of the adhesive layer (I), or a part or all of the surface of the adhesive layer (I) subjected to an adhesion reactivity control process for controlling adhesion reactivity with rubber. On the surface,
The laminate according to (1) or (2), which is formed by bringing an unvulcanized rubber or a vulcanized rubber into contact with each other and thermocompression bonding.
(4) The adhesive layer (II) is formed by reacting an OH group provided on the surface of the rubber layer with an alkoxy group of the thiol-reactive alkoxysilane compound represented by the formula (A). The laminate according to any one of (1) to (3).

(5) The conductive layer irradiates the surface of the adhesive layer (II) with ultraviolet rays having a wavelength of 200 to 400 nm through a mask pattern, thereby forming a reactive and non-reactive finely patterned rubber adhesive. Obtaining step (i),
A step (ii) of obtaining a catalyst-supported rubber adhesive by immersing the obtained reactive and non-reactive fine patterned rubber adhesive in a reducing metal salt solution; and
The laminate according to any one of (1) to (4), which is formed by the step (iii) of electroless plating the obtained catalyst-carrying rubber adhesive.
(6) The laminate according to any one of (1) to (4), wherein the conductive layer is formed on the surface of the adhesive layer (II) by a step (iii) of electroless plating.
(7) The laminate according to any one of (1) to (4), wherein the conductive layer is a metal foil attached to the surface of the adhesive layer (II).

(8) The resin layer formed from the alicyclic olefin polymer is formed from the thiol-reactive alkoxysilane compound represented by the formula (A) on the other surface which is the surface opposite to the one surface. The other adhesive layer (I) made,
The other side rubber layer formed on the surface opposite to the resin layer in the other side adhesive layer (I), and the surface opposite to the other side adhesive layer (I) in the other side rubber layer The other side adhesive layer (II) formed from the thiol-reactive alkoxysilane compound represented by the formula (A), and the other side rubber layer in the other side adhesive layer (II) opposite to the other side rubber layer A laminate according to any one of (1) to (7), comprising: the other conductive layer formed on the other surface.
(9) The laminate according to any one of (1) to (8), which is a wiring board.

According to a second aspect of the present invention, there is provided the following multilayer wiring board (10).
(10) The laminate according to any one of (1) to (9) and the laminate or the resin substrate according to any one of (1) to (9) are represented by the formula (A). The multilayer wiring board laminated | stacked through the adhesive bond layer formed by making the thiol reactive alkoxysilane compound shown react.

  According to the present invention, a laminated body in which a resin substrate, a rubber layer, and a conductive layer are firmly bonded by molecular bonding, and a smooth surface metal wiring that has an excellent insulating property and propagates an electric signal even at a high frequency current. A wiring board is provided.

Hereinafter, the present invention will be described in detail.
1) Laminate The laminate of the present invention is formed of a resin layer formed from an alicyclic olefin polymer and a thiol-reactive alkoxysilane compound represented by the following formula (A) on one surface of the resin layer. Adhesive layer (I), a rubber layer formed on the surface of the adhesive layer (I) opposite to the resin layer, and a side of the rubber layer opposite to the adhesive layer (I) The adhesive layer (II) formed from the thiol-reactive alkoxysilane compound represented by the following formula (A) is formed on the surface of the adhesive layer (II), and formed on the surface opposite to the rubber layer in the adhesive layer (II). A conductive layer.

(1) Resin layer The resin layer of the laminate of the present invention is formed from an alicyclic olefin polymer.
By using an alicyclic olefin polymer as a material for forming the resin layer, it is possible to obtain a laminate having low hygroscopicity and excellent insulating properties and high frequency properties.

  An alicyclic olefin polymer is a polymer having a repeating unit containing an alicyclic structure. Examples of the alicyclic structure include a saturated cyclic hydrocarbon (cycloalkane) structure and an unsaturated cyclic hydrocarbon (cycloalkene) structure. From the viewpoint of mechanical strength and heat resistance, the cycloalkane structure and the cycloalkene structure are exemplified. A structure is preferable, and a cycloalkane structure is most preferable among them. The alicyclic structure may be in the main chain or in the side chain, but those containing an alicyclic structure in the main chain are preferred from the viewpoint of mechanical strength, heat resistance and the like. The number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually 4 to 30, preferably 5 to 20, more preferably 5 to 15 in the mechanical strength, Properties such as heat resistance and moldability of the resin layer are highly balanced. The proportion of the repeating unit containing the alicyclic structure may be appropriately selected according to the purpose of use, but is preferably 50% by weight or more, more preferably 70% by weight or more, and particularly preferably 90% by weight. That's it. When the ratio of the repeating unit containing the alicyclic structure in the alicyclic structure-containing polymer is within this range, it is preferable from the viewpoint of the transparency and heat resistance of the resin layer.

As described above, alicyclic olefin polymers include homopolymers and copolymers of alicyclic olefins and derivatives thereof (hydrogenated products, etc.), as well as polymers having structures equivalent to these. It is. The polymerization mode may be addition polymerization or ring-opening polymerization.
Specifically, a ring-opening polymer of a monomer having a norbornene ring (hereinafter referred to as a norbornene monomer) and a hydrogenated product thereof, an addition polymer of a norbornene monomer, a norbornene monomer and a vinyl compound Examples thereof include addition copolymers, monocyclic cycloalkene addition polymers, alicyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrogenated products thereof. Furthermore, the polymer in which an alicyclic structure is formed by hydrogenation after polymerization, such as an aromatic olefin hydrogenated product of an aromatic olefin polymer, has reached a structure equivalent to the alicyclic olefin polymer. . Among these, a ring-opening polymer of a norbornene monomer and a hydrogenated product thereof, an addition polymer of a norbornene monomer, an addition copolymer of a norbornene monomer and a vinyl compound, an aromatic ring of an aromatic olefin polymer A hydrogenated product is preferable, and a hydrogenated product of a ring-opening polymer of a norbornene monomer is particularly preferable. The polymerization method of alicyclic olefin or aromatic olefin, and the hydrogenation method performed as necessary are not particularly limited and can be performed according to a known method.
Moreover, in addition to the case where it consists only of an alicyclic olefin polymer, the composition which mixed the alicyclic olefin polymer and the other polymer is also contained in the said alicyclic olefin polymer. In this case, the ratio of the alicyclic olefin polymer is not particularly limited. As said other polymer, an epoxy resin, a urethane resin, an acrylic resin etc. can be mentioned, for example.

  Moreover, what has a polar group is also contained in an alicyclic olefin polymer. Examples of the polar group include a hydroxyl group, a carboxyl group, an alkoxyl group, an epoxy group, a glycidyl group, an oxycarbonyl group, a carbonyl group, an amino group, an ester group, and a carboxylic acid anhydride group. An anhydride group is preferred. The method for obtaining the alicyclic olefin polymer having a polar group is not particularly limited. For example, (i) an alicyclic olefin monomer containing a polar group is homopolymerized, or with other monomers. A method of copolymerizing; (ii) a carbon-carbon unsaturated bond-containing compound having a polar group is grafted to an alicyclic olefin polymer not containing a polar group, for example, in the presence of a radical initiator, A method of introducing a group; and the like.

As an alicyclic olefin monomer containing a polar group used in the method (i), 8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ] dodec-3-ene, 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene , 5-carboxymethyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 8-methyl-8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-carboxymethyl-8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 5-exo-6-endo-dihydroxycarbonylbicyclo [2.2.1] hept-2-ene, 8-exo-9-endo-dihydroxycarbonyltetracyclo [4. 4.0.1 ^2,5 . Carboxyl group-containing alicyclic olefin monomers such as ^{17, 10} ] dodec-3-ene; bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride, tetracyclo [4. 4.0.1 ^2,5 . 1 ^7,10 ] dodec- ³ -ene-8,9-dicarboxylic anhydride, hexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] heptadec-4-ene-11,12-acid anhydride such as a dicarboxylic acid anhydride group-containing alicyclic olefin monomer; and the like.

Specific examples of the monomer used to obtain the alicyclic olefin polymer containing no polar group used in the method (ii) include bicyclo [2.2.1] hept-2-ene (common name: Norbornene), 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1]. ] Hept-2-ene, 5-methylidene-bicyclo [2.2.1] hept-2-ene, 5-vinyl-bicyclo [2.2.1] hept-2-ene, tricyclo [4.3.0] .1 ^2,5] deca-3,7-diene (common name: dicyclopentadiene), tetracyclo ^{[8.4.0.1 11,14.} 0 ^2,8 ] tetradeca-3,5,7,12,11-tetraene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dec-3-ene (common name: tetracyclododecene), 8-methyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-vinyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-3,10-diene, pentacyclo [7.4.0.1 ^3,6. 1 ^10,13 . 0 ^2,7 ] pentadeca-4,11-diene, cyclopentene, cyclopentadiene, 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene, 8-phenyl-tetracyclo [4.4. 0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like.

 The carbon-carbon unsaturated bond-containing compound having a polar group used in the method (ii) includes acrylic acid, methacrylic acid, α-ethylacrylic acid, 2-hydroxyethyl (meth) acrylic acid, maleic acid. , Fumaric acid, itaconic acid, endocis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid, methyl-endocis-bicyclo [2.2.1] hept-5-ene-2, And unsaturated carboxylic acid compounds such as 3-dicarboxylic acid; unsaturated carboxylic acid anhydrides such as maleic anhydride, chloromaleic anhydride, butenyl succinic anhydride, tetrahydrophthalic anhydride, and citraconic anhydride;

  The alicyclic olefin resin may contain a curing agent. As the curing agent, general ones such as an ionic curing agent, a radical curing agent or a curing agent having both ionic and radical properties can be used, and in particular, bisphenol A bis (propylene glycol glycidyl ether) ether. Polyhydric epoxy compounds such as glycidyl ether type epoxy compounds, alicyclic epoxy compounds, and glycidyl ester type epoxy compounds can be suitably used. In addition to epoxy compounds, non-epoxy curing that has a carbon-carbon double bond such as 1,3-diallyl-5- [2-hydroxy-3-phenyloxypropyl] isocyanurate and contributes to crosslinking reaction An agent can also be used. Moreover, the said hardening | curing agent may contain a hardening accelerator and a hardening adjuvant further.

  In addition, the alicyclic olefin resin includes a flame retardant, a soft polymer, a heat stabilizer, a weather stabilizer, an anti-aging agent, a leveling agent, an antistatic agent, a slip agent, an antiblocking agent, an antifogging agent, a lubricant, Also included are those containing additives such as dyes, pigments, natural oils, synthetic oils, waxes, emulsifiers, fillers, and UV absorbers.

  The alicyclic olefin polymer suitable for the present invention has a molecular weight of polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using cyclohexane or toluene as an organic solvent. The range is preferably 1,000 to 1,000,000, more preferably 5,000 to 500,000, and particularly preferably 10,000 to 250,000. When the weight average molecular weight (Mw) of the alicyclic olefin polymer is in this range, the moldability, the processing strength, etc. are highly balanced, which is preferable.

  In the alicyclic olefin polymer suitable for the present invention, the molecular weight distribution is a ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by GPC, preferably 5 Hereinafter, it is more preferably 4 or less, particularly preferably 3 or less.

  As long as the alicyclic olefin polymer used in the present invention does not impair the purpose of the present invention, fillers such as carbon, calcium carbonate, talc, clay, kaolin, glass, wet and dry silica, rayon, nylon, polyester, It may contain additives such as vinylon, steel, Kevlar (trade name of DuPont), carbon fiber, glass fiber and the like, and cloth. The additive amount of these additives is 0 to 100 parts by weight, preferably 10 to 60 parts by weight. Rigidity can be obtained as the amount of the other additive is increased, but if 60 parts by weight or more is added, the workability is remarkably lowered. In addition, if it is 10 parts by weight or less, the expected rigidity may not be obtained.

  The resin layer of the laminate of the present invention is a film-like product, a sheet-like resin composition prepared by blending an alicyclic olefin polymer or a resin composition containing an alicyclic olefin polymer and other additives as required. It can be obtained by forming a sheet or plate.

  Examples of the molding method include injection molding, injection compression molding, press molding, extrusion molding, blow molding, and vacuum molding. In the case of forming into a film, an extrusion molding method using a T-die, a calendar molding method, an inflation molding method, or a solution casting method can also be used.

  The resin layer used in the present invention preferably has an OH group (hydroxyl group, carboxyl group) on the surface. As a method for obtaining a resin layer having an OH group on its surface, a method for producing a resin substrate using an alicyclic olefin polymer having an OH group, an adhesive layer for a resin substrate having no OH group on its surface The method of surface-treating the surface side surface which forms (I) is mentioned.

  Examples of the surface treatment method include corona discharge, atmospheric pressure plasma irradiation, and UV irradiation treatment.

  The corona discharge treatment on the resin surface is performed using, for example, a known corona surface reformer, power source: AC 100 V, output voltage: 0 to 20 kV, oscillation frequency: 0 to 40 kHz, 0.1 to 60 seconds, temperature 0 to 60 It can be performed under the condition of ° C.

  The atmospheric pressure plasma treatment of the resin surface is performed using, for example, a known atmospheric pressure plasma generator, plasma treatment speed of 10 to 100 mm / s, power source: AC 200 or 220 V (30 A), compressed air: 0.5 MPa (1 NL / min), high frequency: 10 kHz / 300 W to 5 GHz, power: 100 to 400 W, irradiation time: 0.1 to 60 seconds.

The UV irradiation of the resin surface is performed using, for example, a known UV-LED irradiation device, wavelength: 200 to 400 nm, power source: AC 100 V, light source peak illuminance: 400 to 3000 mW / cm ² , irradiation time: 1 to 60 seconds Can be done.

  In any case, since the optimum processing conditions vary greatly depending on the type and history of the resin, the type and amount of the resin additive, the type and amount of the filler, etc., the range cannot be specified uniquely. However, it is important that the resin surface exhibits extended wetting (surface tension: 55 kN / m or more) with respect to the treated water and that the operating conditions are set so that the irradiation time is in the range of 1 to 60 seconds. .

(2) Adhesive layer (I)
The laminate of the present invention is formed on one surface of the resin layer from a thiol-reactive alkoxysilane compound represented by the formula (A) (hereinafter sometimes referred to as “alkoxysilane compound (A)”). Having an adhesive layer (I) formed. The adhesive layer (I) serves to firmly bond the resin layer and the rubber layer.

In formula (A), R ¹ represents a hydrogen atom; a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, C1-C10 alkyl groups such as n-hexyl group and n-octyl group; C2-C10 alkenyl groups such as vinyl group, allyl group, crotyl group; phenyl group, 2-chlorophenyl group, 4-methyl A phenyl group optionally having a substituent such as a phenyl group, 2,4-dimethylphenyl group, 2,4,6-trimethylphenyl group; or a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclo group A cycloalkyl group having 3 to 10 carbon atoms such as an octyl group;
Among these, as R ¹ , a hydrogen atom or a methyl group is preferable, and a hydrogen atom is particularly preferable.

R ² represents an alkylene group having 1 to 20 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, a propylene group, or a tetramethylene group.

In the alkylene chain, the alkylene group includes an oxygen atom, a sulfur atom, a group represented by the formula: NR ³ (R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms), —C ( A group represented by ═O) NH—CH ₂ CH ₂ — or a group represented by —O—C (═O) NH— may be contained.

Preferable specific examples of R ² include —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH (CH ₃ ) —, —CH ₂ CH ₂ CH ₂ CH ₂ —, —CH ₂ CH. ₂ CH ₂ CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ SCH ₂ CH ₂ —, —CH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ —, — (CH ₂ CH ₂ ) ₂ N—CH ₂ CH ₂ CH _{2 -, - CH 2 CH 2} OCONHCH 2 CH 2 CH 2 -, - CH 2 CH 2 NHCONHCH 2 CH 2 CH 2 -, - (CH 2 CH 2) 2 CHOCONHCH 2 CH 2 CH 2 - and the like. Of these, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, and —CH ₂ CH (CH ₃ ) — are preferable.

X is a hydrogen atom; or methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, represents an alkyl group having 1 to 10 carbon atoms such as an n-octyl group.
n represents an integer of 1 to 3, and 2 or 3 is preferable.
M represents an alkali metal atom such as a lithium atom, a sodium atom, a potassium atom, or a cesium atom.

The adhesive layer (I) can be formed, for example, as follows.
First, an adhesive layer forming solution is prepared. The adhesive layer forming solution contains an alkoxylane compound (A) in an appropriate solvent, and the content thereof is usually 0.001 to 10% by weight (hereinafter referred to as “wt%”), preferably 0.01 to. It can be prepared by dissolving to 2 wt%.

  When the content of the alkoxylane compound (A) is 0.01 wt% or less, a case where sufficient peel strength cannot be obtained tends to occur. Even when the content is 2 wt% or more, in addition to the monomolecular film layer, a multi-molecular film layer may be generated, and sufficient peel strength may not be obtained.

  As a solvent to be used, water; alcohol solvents such as methanol, ethanol and isopropanol; glycol solvents such as diethylene glycol, ethylene glycol monoethyl ether and ethylene glycol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; n -Aliphatic hydrocarbon solvents such as pentane and n-hexane; ester solvents such as ethyl acetate and isopropyl acetate; and mixed solvents composed of two or more of these solvents.

  Next, the resin substrate is immersed in the adhesive layer forming solution. This resin substrate constitutes the resin layer of the laminate of the present invention.

  The soaking conditions are governed by the temperature, time and concentration of the solution, so they are not uniquely determined, but at a constant concentration, the time tends to be long when the temperature is low and the time is short when the temperature is high. it can. The temperature at the time of immersion is usually within a temperature range of 0 ° C. to 100 ° C., and the immersion time is usually from 1 second to 60 minutes.

  Next, the immersed resin substrate is dried by heating at 40 to 200 ° C. for 1 to 30 minutes, or the substrate surface is washed with the solvent used for the immersion. Thereby, a resin substrate (hereinafter, also referred to as “resin substrate with an adhesive layer (I)”) having the adhesive layer (I) formed on the surface thereof is obtained.

  The obtained adhesive layer (I) of the resin substrate with the adhesive layer (I) is an alkoxy formed by a condensation reaction between an OH group provided on the surface of the resin substrate and an alkoxy group of the alkoxysilane compound (A). It can consist of a monomolecular film of a silane compound (A). And SH group and SS group mentioned later exist in the surface of the monomolecular film.

  In the present invention, the rubber layer can be formed on the adhesive layer (I) using the resin substrate with the adhesive layer (I) obtained as it is, but as described below, the adhesive agent A step of controlling adhesion reactivity with rubber is provided for a part or all of the surface of the resin substrate with the layer (I), and for a part or all of the surface of the resin substrate with the adhesive layer (I). The adhesion reactivity with rubber can also be controlled.

  The reason for providing this step is, for example, to control the reactivity of the thiol group on the resin surface because the reactivity of the unvulcanized rubber blend described later varies depending on the characteristics of the vulcanized compounding agent. For example, in halogen-containing rubber, if an acid acceptor such as MgO or ZnO is added, the thiol group of triazinedithiol easily reacts in the temperature range of 130 ° C. to 200 ° C. Adhesion reaction occurs. When it is desired to promote the adhesion reaction, the object can be achieved by immersing the resin in an alkaline aqueous solution.

  The method for controlling the adhesion reactivity is not particularly limited. For example, the control methods listed in the following (a) to (f) can be appropriately employed.

(A) Ultraviolet irradiation A mask is put on the surface of the resin substrate to irradiate with ultraviolet rays. In this case, a part or all of the surface of the surface reactive resin is irradiated with 200 to 400 nm ultraviolet rays. As a result, the resin substrate to which the reactive SH group is bonded is covered with a mask, and when this is irradiated with ultraviolet light, the ultraviolet irradiated portion changes to a disulfide group (SS group), and the SH group remains in the unirradiated portion. In this way, the resin surface can be separated into parts having different reactivity by ultraviolet irradiation.

  As an ultraviolet light source, a mercury lamp (wavelength: 254, 303, 313, 365 nm) or a metal halide lamp (200-450 nm) can be used. Further, when a benzophenone-based sensitizer is adsorbed, a hypermetal halide lamp (400 to 450 nm) can be used.

  The conditions of ultraviolet irradiation can achieve the purpose at 0 to 100 ° C. and 1 second to 100 minutes, preferably 20 to 50 ° C. and 20 seconds to 180 seconds. Under these conditions below, the UV irradiation part may not be completely converted to SS groups and SH groups may remain. Moreover, since the ultraviolet irradiation part may decompose | disassemble on conditions more than these, it may be unpreferable. In general, 100% SS group conversion is achieved in a long time when the temperature is low, and in a short time when the temperature is high.

(B) Immersion in aqueous metal salt solution The resin substrate with the adhesive layer (I) is immersed in an aqueous metal salt solution prepared in a concentration range of 0.001-1 mol / L for 1 second to 60 minutes, preferably 20 to 50 ° C. Soak for 20 to 180 seconds. Thereby, the SH group can be activated or inactivated.
Examples of the metal salt to be used include Li, Na, K, Ce, Mg, Ca, Ba, Ni, Fe, Co, Zn, Cd, Al, Au, Pt, Pd, Sn, Cu, Ag, etc., hydrochloride, sulfuric acid Examples thereof include salts, nitrates, and carbonates.

(C) Metalization The surface reactive resin after irradiation with ultraviolet rays is immersed in a metal reduction catalyst solution and is immersed in an electroless plating solution. That is, a resin product having SH groups and SS groups on the surface as described above is obtained by using a Pd-Sn salt composed of PdCl ₂ and SnCl ₂ .7H ₂ O prepared in a concentration range of 0.001-1 mol / L. After immersing in an aqueous solution for 1 second to 60 minutes, preferably at 20 to 50 ° C. for 20 to 180 seconds, it is immersed in an electroless plating bath at 0 to 100 ° C. for 1 to 300 minutes. Thereby, the SH base portion is metalized.

  The electroless plating bath is mainly composed of a metal salt and a reducing agent, and supplemental components such as a pH adjusting agent, a buffering agent, a complexing agent, an accelerator, a stabilizer and an improving agent are added thereto.

  Examples of metals that can be electrolessly plated include gold, silver, copper, nickel, cobalt, iron, palladium, platinum, brass, molybdenum, tungsten, permalloy, and steel, and these metal salts are used.

Specific examples of the metal salt include AuCN, Ag (NH ₃ ) ₂ NO ₃ , AgCN, CuSO ₄ .5H ₂ O, CuEDTA, NiSO ₄ .7H ₂ O, NiCl ₂ , Ni (OCOCH ₃ ) _2, CoSO ₄ , Examples thereof include CoCl ₂ , SnCl ₂ .7H ₂ O, PdCl _{2 and the} like. These metal salts are used in a concentration range of 0.001-1 mol / L.

The reducing agent has an action of reducing the above metal salt to produce a metal. Examples include KBH ₄ , NaBH ₄ , NaH ₂ PO ₂ , (CH ₃ ) ₂ NH · BH ₃ , CH ₂ O, NH ₂ NH ₂ , hydroxylamine salt, N, N-ethylglycine and the like. The reducing agent is used in a concentration range of 0.001-1 mol / L.

  An auxiliary component can be added to the above main components for the purpose of extending the life of the electroless plating bath or increasing the reduction efficiency. Adjuvants include basic compounds, inorganic salts, organic acid salts, citrates, acetates, borates, carbonates, ammonia hydroxide, EDTA, diaminoethylene, sodium tartrate, ethylene glycol, thiourea, triazine thiol And triethanolamine. The adjuvant is used in a concentration range of 0.001-0.1 mol / L.

  The temperature and immersion time of electroless plating vary depending on the type of bath and the purpose of plating, and it is difficult to specify the range clearly. However, the temperature range is approximately 0 to 98 ° C., and the immersion time is 1 minute to 300. Minutes.

(D) Immersion in an organic halogen compound solution A resin substrate with an adhesive layer (I) is added to an organic halide solution prepared in a concentration range of 0.001-1 mol / L at 0 to 100 ° C for 1 to 300 minutes. Preferably, by immersing at 30 to 70 ° C. for 10 to 60 minutes, the SH group portion can be blocked with an organic substance and inactivated.

The organic halide solution to be used can be prepared by dissolving the organic halide and alkali in a suitable solvent.
Organic halides include X′CH ₂ COONa, X′CH ₂ COOCH ₃ , C ₆ H ₅ CH ₂ X ′, CH ₂ ═CHCH ₂ X ′ (X ′ represents a halogen atom of Cl, Br and I) Etc.).
Examples of the alkali include NaOH, KOH, triethylamine, dibutylamine, dicyclohexylamine, dimethylaniline and the like.

  Solvents used include alcohols such as water, methanol, ethanol and isopropanol; glycols such as diethylene glycol and ethylene glycol monoethyl ether; ketones such as acetone, methyl ethyl ketone and cyclohexanone; esters such as ethyl acetate and isopropyl acetate; n -Aliphatic hydrocarbons such as pentane and n-hexane; mixed solvents thereof.

(E) Immersion in an organic sulfur compound solution A resin substrate with an adhesive layer (I) is placed in an organic sulfur compound solution prepared in a concentration range of 0.001-1 mol / L at 0 to 100 ° C for 1 to 300 minutes. Preferably, by immersing at 30 to 70 ° C. for 1 to 60 minutes, the SH group portion and the organic sulfur compound react to generate an active functional group with respect to the unsaturated rubber.

  Examples of the organic sulfur compound to be used include dibenzothiazoyl disulfide, 4-morpholinodithiothiobenzothiazol, N-cyclohexyl-2-benzothiazoylsulfenamide, Nt-butyl-2-benzothiazoylsulfenamide, N-oxydiethylene-2-benzothiazoylsulfenamide, N-diisopropyl-2-benzothiazoylsulfenamide, N-dicyclohexyl-2-benzothiazoylsulfenamide, tetramethylturum disulfide, tetraethylturum disulfide Tetrabutylturum disulfide, tetraoctylturum disulfide and the like.

  The organic sulfur compound solution is obtained by mixing the organic sulfur compound with alcohols such as methanol, ethanol and isopropanol; glycols such as diethylene glycol and ethylene glycol monoethyl ether; ketones such as acetone, methyl ethyl ketone and cyclohexanone; ethyl acetate and isopropyl acetate It can be obtained by dissolving it in an aliphatic hydrocarbon such as n-pentane or n-hexane; a mixed solvent thereof.

(F) Immersion in an organic peroxide solution A resin substrate with an adhesive layer (I) is added to an organic peroxide solution prepared in a concentration range of 0.001-1 mol / L at 0 to 100 ° C. at 1 to 300. By immersing for 1 minute, preferably at 10 to 50 ° C. for 1 to 60 minutes, the SH group portion and the organic peroxide can react to generate an active functional group with respect to the unsaturated rubber.

  Examples of the organic peroxide used include benzoyl peroxide, t-butyl perbenzoate, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, Examples include 5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, di (t-butylperoxyisopropyl) benzene and the like.

  The organic oxide solution is prepared by dissolving the organic oxide in methanol, ethanol, isopropanol, diethylene glycol, ethylene glycol monoethyl ether, ethylene glycol, acetone, hexane, methyl ethyl ketone, hexanone, ethyl acetate, or a mixed solvent thereof. Can be obtained.

(3) Rubber layer The multilayer substrate of this invention has the rubber layer formed in the surface on the opposite side to the said resin layer in the said adhesive bond layer (I).
The rubber layer can be formed by bringing an unvulcanized rubber or a vulcanized rubber into contact with each other and thermocompression bonding.

  Unvulcanized rubber contains elastomers, fillers, vulcanizing agents, vulcanization accelerators, metal activators, and other essential components. In addition to these, stabilizers, anti-aging agents, UV inhibitors, softeners, colorants, retarders Etc. can be added.

  Elastomers include polyvinyl chloride, chlorinated polyethylene, chlorosulfonated polyethylene, alkylated chlorosulfonated polyethylene, chloroprene rubber, chlorinated acrylic rubber, brominated acrylic rubber, fluororubber, epichlorohydrin and its copolymer rubber, and chlorinated ethylene. Propylene rubber, chlorinated butyl rubber, brominated butyl rubber, natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, butyl rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, acrylic rubber, ethylene-acrylic rubber , Silicon rubber, urethane rubber and the like.

  The filler is added for the purpose of increasing the strength of the rubber or increasing the amount. Examples of the filler include carbon black, silica, nippil, talc, calcium silicate, calcium carbonate, carbon fiber, Kevlar fiber (trade name of DuPont), polyester fiber, and glass fiber.

  The amount of the filler used is usually in the range of 1 to 200 parts by weight, preferably in the range of 20 to 80 parts by weight with respect to 100 parts by weight of the elastomer.

Vulcanizing agents are added to vulcanize the elastomer.
Examples of the vulcanizing agent include triazine trithiol, 2-dibutylamino-1,3,5-triazine-4,6-dithiol, ethylenethiourea, bisphenol A, sulfur, colloidal sulfur, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, di (t-butylperoxyisopropyl) benzene, etc. Peroxides, benzoquinone dioxime, sarigen, dimethylol / phenol, and the like.

  The addition amount of the vulcanizing agent is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight. If the amount is 0.5 parts by weight or less, crosslinking is incomplete, so that a sufficient elastic body is not obtained. On the other hand, when the amount is 5 parts by weight or more, the degree of cross-linking is too high, resulting in a hard elastic body, and airtightness and sealing properties may not be exhibited.

A vulcanization accelerator is added to accelerate the above vulcanization.
Vulcanization accelerators include azole vulcanization accelerators such as dibenzothiazoyl disulfide and 4-morpholinodithiobenzothiazole; N-cyclohexyl-2-benzothiazoylsulfenamide, Nt-butyl-2-benzothia Sulfenamides such as zoylsulfenamide, N-oxydiethylene-2-benzothiazoylsulfenamide, N-diisopropyl-2-benzothiazoylsulfenamide, N-dicyclohexyl-2-benzothiazoylsulfenamide Vulcanization accelerators; and turam vulcanization accelerators such as tetramethylturum disulfide, tetraethylturum disulfide, tetrabutylturum disulfide, tetraoctylturum disulfide; and the like. The addition amount of the vulcanization accelerator is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight.
If the amount is 0.5 parts by weight or less, crosslinking is incomplete, so that a sufficient elastic body is not obtained. On the other hand, when the amount is 5 parts by weight or more, the degree of cross-linking is too high and the elastic body becomes hard and the airtightness and sealing properties are not exhibited.

  The metal activator is added for the purpose of adjusting the crosslinking rate or accepting acid. Examples of metal activators include zinc oxide, magnesium oxide, calcium oxide, barium oxide, aluminum oxide, tin oxide, iron oxide, calcium hydroxide, calcium carbonate, magnesium carbonate, fatty acid sodium, calcium octylate, potassium isooctylate, and potassium bromide. Toxides, cesium octylate, potassium isostearate and the like can be mentioned.

The addition amount of the metal activator is usually 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight.
If the amount is 1 part by weight or less, the object may not be achieved. On the other hand, if it exceeds 10 parts by weight, the properties of the rubber may change, which is not preferable.

The vulcanized rubber can be obtained by heating the unvulcanized rubber.
In the present invention, unvulcanized rubber or vulcanized rubber can be used singly or in combination of two or more.

  The rubber layer can be formed by bringing the adhesive layer (I) into contact with the unvulcanized rubber or vulcanized rubber, pressurizing as desired, and heating at 80 ° C. to 200 ° C. for 1 to 60 minutes.

It is preferable to introduce an OH group into the surface of the rubber layer formed as described above on the surface side where the adhesive layer (II) is to be formed.
Examples of the surface treatment include corona discharge, atmospheric pressure plasma irradiation, and UV irradiation treatment as described above.

(4) Adhesive layer (II)
The laminated body of this invention has the adhesive bond layer (II) formed from the alkoxysilane compound (A) in the surface on the opposite side to the said adhesive bond layer (I) in a rubber layer.
The adhesive layer (II) serves to firmly bond the rubber layer and the conductive layer.

  The adhesive layer (II) can be formed in the same manner as the adhesive layer (I). Of course, the alkoxysilane compound (A) used for forming the adhesive layer (II) is the same as or different from the alkoxysilane compound (A) used for forming the adhesive layer (I). May be.

(5) Conductive layer The laminated body of this invention has the conductive layer formed in the surface on the opposite side to the said rubber layer in adhesive bond layer (II).

  The conductive material used for forming the conductive layer is not particularly limited, and those used in the general electronics field are used. As a suitable material, a metal having high conductivity, low temperature dependency, no migration, withstands a heat cycle, and can be soldered on the outermost layer surface is used.

  Examples of the metal material include Ag, Au, Cu, Ni, Al, and W, and Cu is usually used from the viewpoint of cost.

  Although the thickness of a conductive layer is suitably selected according to the intended purpose, it is about 1-10 micrometers normally, Preferably it is about 4-6 micrometers. The wiring width is about 100 μm for copper paste or silver paste printing, and about 40 to 60 μm for copper electroless plating.

  For the purpose of improving the adhesion of the conductive layer to the substrate, it is preferable to perform a base treatment such as chromium vapor deposition. In order to improve the adhesion between the conductive layer and the solder, it is preferable to deposit chromium or Ni on the conductive layer.

  For applications requiring a high-density wiring pitch such as MCM (multi-chip module), it is preferable to reduce the wiring width to 10 to 20 μm and conversely to increase the film thickness to about 15 μm.

  As a method for forming the conductive layer, methods such as a dry process technique and a wet process technique are used.

As the dry film forming process technique, for example, methods such as physical vapor deposition (PVD) and chemical vapor deposition (CVD) are used.
(I) Physical vapor deposition method:
Physical vapor deposition methods include vacuum vapor deposition (normal vacuum vapor deposition, flash vapor deposition, gas scattering vapor deposition, electric field vapor deposition, reactive vapor deposition, etc.), ion plating vapor deposition (DC ion plating, high frequency ion plating, ion beam vapor deposition, HCD). Method, arc discharge ion plating, etc.), sputtering (DC sputtering, high frequency sputtering, magnetron sputtering, ion beam sputtering, etc.) and the like.

(Ii) Chemical vapor deposition:
Chemical vapor deposition methods include thermal CVD (thermal CVD, MOCVD), plasma CVD (direct current plasma CVD, high frequency CVD, microwave plasma CVD), optical CVD (excimer laser excitation, mercury lamp excitation, CO ₂ laser excitation), plasma polymerization. (DC discharge excitation, microwave excitation, high frequency excitation) and the like.

  Examples of the wet film forming process technique include methods such as an electroplating technique and an electroless plating technique. Examples of the thick film forming method include a printing method typified by a screen printing method and a drawing method.

  In the conductive layer laminated on the adhesive layer (II), a wiring pattern is usually formed. As a method for forming a wiring pattern of a conductive layer, (α) a subtractive method in which unnecessary portions are removed from a metal layer applied over the entire surface while leaving unnecessary portions, or (β) a wiring pattern. There is an additive method in which the layer is formed later by electroless plating, electrolytic plating, or the like.

(Α) In the subtractive method, a metal film is formed on the entire surface of the adhesive layer (II) by vacuum deposition, sputtering, electroless plating, or the like. Next, an etching resist film is applied to a portion to be left as a wiring circuit pattern. After removing unnecessary portions of the metal film using an etching solution, the resist film is peeled off to form a wiring pattern.

(Β) In the additive method, a plating resist film is applied using a dry film resist or the like on a portion of the adhesive layer on which no metal film is deposited, on which a wiring pattern is not desired to be formed. Next, after forming a metal film using an electroless plating method or the like, the resist film is peeled off to form a wiring pattern.

  When constituting the laminate of the present invention, the surface of the adhesive layer (II) is irradiated with ultraviolet rays having a wavelength of 200 to 400 nm through a mask pattern, thereby allowing reactive and non-reactive fine patterned rubber adhesion. (Step i), and the resulting reactive and non-reactive fine patterned rubber adhesive is immersed in a reducing metal salt solution to obtain a catalyst-supported rubber adhesive (Step ii). It is preferable to form the conductive layer by electroless plating the support rubber adhesive (step iii). According to this method, it is possible to easily obtain a laminate in which a metal wiring through which an electric signal is reliably propagated even with a high-frequency current is formed on the rubber layer surface with high adhesive force.

  The laminate of the present invention is a laminate in which a resin substrate, a rubber layer, and a conductive layer are firmly bonded by molecular adhesion, and has excellent insulating properties and a smooth surface metal that can propagate an electric signal even at high frequency current. Since it has wiring, it is particularly useful as a wiring board.

  The laminate of the present invention is the other side formed from the alkoxysilane compound (A) on the other side which is the side opposite to the one side in the resin layer formed from the alicyclic olefin polymer. An adhesive layer (I), the other side rubber layer formed on the opposite side of the resin layer in the other side adhesive layer (I), and the other side adhesive layer in the other side rubber layer ( On the surface opposite to I), the other side adhesive layer (II) formed from the alkoxysilane compound (A) and the other side adhesive layer (II) opposite to the other side rubber layer. It may have the other side conductive layer formed in the field. This is useful as a double-sided wiring board (two-layer wiring board).

  The other side adhesive layer (I), the other side rubber layer, and the other side adhesive layer (II) have a rubber layer on one side of the above-described resin substrate via the adhesive layers (I) and (II). It can be formed in the same manner as in the production of a laminate. Even in this case, effects such as adhesion can be sufficiently obtained as in the case of manufacturing a laminate having a rubber layer on one side of the resin substrate via the adhesive layers (I) and (II).

  In addition, the other side conductive layer irradiates the surface of the other side adhesive layer (II) with ultraviolet rays having a wavelength of 200 to 400 nm through a mask pattern, thereby forming a reactive and non-reactive fine patterned rubber adhesive. Obtaining (step i), immersing the obtained reactive and non-reactive fine patterned rubber adhesive in a reducing metal salt solution to obtain a catalyst-carrying rubber adhesive (step ii), and obtaining the catalyst-carrying rubber By electrolessly plating the adhesive (step iii), the surface of the other adhesive layer (II) is irradiated with ultraviolet rays having a wavelength of 200 to 400 nm via a mask pattern, and then the steps (ii) and (iii) ) By repeating the above operation.

  1 and 2 are structural cross-sectional views of the laminate of the present invention. In FIG. 1, 1 is a resin layer (resin substrate), 2a is an adhesive layer (I), 3 is a rubber layer, 2b is an adhesive layer (II), and 4 is a conductive layer. A laminated body 10A shown in FIG. 1 has a structure in which a rubber layer 3 and a conductive layer 4 are laminated on one surface of a resin layer 1 via adhesive layers (I) and (II).

  In FIG. 2, 1a is a resin layer (resin substrate), 2c and 2e are adhesive layers (I), 3a and 3b are rubber layers, 2d and 2f are adhesive layers (II), 4a and 4b are conductive layers, respectively. Show. A laminate 10B shown in FIG. 2 has a structure in which rubber layers 3a and 3b and conductive layers 4a and 4b are laminated on both surfaces of a resin substrate 1a via adhesive layers (I) and (II).

2) Multilayer wiring board The second aspect of the present invention is the reaction of the laminate of the present invention with the laminate or resin substrate of the present invention with the thiol-reactive alkoxysilane compound represented by the formula (A). It is a multilayer wiring board laminated | stacked through the adhesive bond layer formed by (1).

  For example, through holes are made in the resin substrate in advance to connect the layers, or through holes after UV irradiation, catalyst support, electroless plating and electroplating are performed on both the front and back surfaces of the resin substrate. A two-layer printed wiring board can be obtained.

  Further, after performing the adhesive activation treatment on the metal surface and the resin surface of the 1- and 2-layer printed resin substrates, the adhesive-treated 1- and 2-layer printed resin substrates and untreated resin substrates are alternately combined, for example, 100 A multilayer printed wiring board can be obtained by heat-pressing at a pressure of 100 MPa for 1 to 180 minutes at an overheating temperature of ˜200 ° C.

As a method for performing an adhesion activation treatment on the metal surface and the resin surface of the 1- and 2-layer printed resin substrates, for example, (i) the 1-layer and 2-layer printed resin substrates are converted into KBH ₄ , NaBH ₄ , NaH ₂ PO ₂ , (CH _{3) 2 NH · BH 3,} CH 2 O, NH 2 NH 2, hydroxylamine salt, N, in a reducing solution such as N- ethyl-glycine, by soaking at 0 to 80 ° C. 1 to 100 minutes, the resin substrate A method of reducing the upper SS group to an SH group to impart adhesiveness to the resin surface; and (ii) 1 and 2 layer printed resin substrate of 1 to 100 mmol / dm ³ of triazine trithiol monosodium and triethanol A method of imparting adhesiveness to the surface of the wiring metal by immersing it in an aqueous amine mixture at 20 to 80 ° C. for 1 to 200 seconds can be mentioned.

  Furthermore, a three-dimensional resin surface obtained by injection molding or the like is covered with a three-dimensional mask and irradiated with ultraviolet rays, whereby a wiring pattern composed of an SH group portion and an SS group portion is drawn on the three-dimensional resin surface. By immersing in the electrolytic bath, the metal wiring can be formed three-dimensionally.

  Hereinafter, although an Example demonstrates in detail, this invention is not limited by a following example.

Example 1
A plate (30 mm × 50 mm) of an alicyclic olefin polymer (manufactured by Nippon Zeon Co., Ltd., Zeonex 480) was immersed in acetone, subjected to ultrasonic cleaning, and then dried with warm air with a dryer. Next, the surface of the resin plate was subjected to corona treatment using a corona discharge irradiation device (manufactured by Shinko Electric Instrumentation Co., Ltd., Corona Master).

  The surface of the corona-treated resin plate was washed with distilled water, and then [6- (3-triethoxysilylpropyl) amino-1,3,5-triazine-2,4-dithiol monosodium salt [Sodium 6]. -(Triethoxysilylpropylamino) -1,3,5triazine-2,4-dithiolate] After dipping in an aqueous solution (TES solution) for 10 minutes, it was dried by heating in an oven at 120 ° C. for 15 minutes (TES treatment).

Next, a 100 μm-thick silicon rubber (SE 6721 A & B, manufactured by Toray Dow Corning Co., Ltd.) was attached to the surface of the TES-treated resin plate, and heated and vulcanized at 120 ° C. for 360 minutes with a hot press.

  The surface of the silicon rubber affixed to the surface of the resin plate was subjected to corona treatment again, then the surface was washed with distilled water, immersed in a TES solution having a concentration of 2 mM for 10 minutes, and then heated and dried in an oven at 120 ° C. for 15 minutes. .

Next, a resin plate having a silicon rubber surface whose surface is TES-treated is placed in a catalyst bath for metal plating containing tin and palladium maintained at 52 ° C. (cataposit 44 manufactured by Rohm and Haas Electronic Materials Co., Ltd.). After dipping for 5 minutes, the resin plate having the silicon rubber surface was taken out of the catalyst bath for plating and washed with ion-exchanged water.

  Next, the resin plate was immersed in a room temperature accelerator solution (Accelerator 19E, manufactured by Rohm and Haas Electronic Materials Co., Ltd.) for 7 minutes, then taken out of the accelerator solution and the resin plate surface was washed with ion-exchanged water.

  The resin plate having the silicon rubber surface on which the catalyst for plating thus obtained was supported was immersed in an aqueous copper sulfate solution (concentration: 47 mM) at room temperature for 12 minutes, washed with ion-exchanged water and alcohol, and then a dryer. And dried.

  A resin plate having an electrolessly plated silicon rubber surface was electroplated in an aqueous copper sulfate solution to obtain a resin plate having a copper foil having a copper foil thickness of 25 μm on the silicon rubber surface.

  The peel strength of the copper foil formed on the silicon rubber surface on the resin plate thus obtained was measured by the method described in JIS-C6481, and the copper foil was cut. At that time, the strength was 3.0 kN / m. Met.

(Example 2)
In Example 1, except that the alicyclic olefin polymer was changed from (Nippon ZEON Co., Ltd., ZEONEX 480) to (Nippon Zeon Co., Ltd., RS420), copper having a thickness of 25 μm was obtained in the same manner as in Example 1. A resin plate having a foil and having a thin silicon rubber layer between the copper thin film and the resin substrate was obtained.

  The peel strength of the copper foil of the substrate obtained by laminating the thin rubber layer and the copper foil on the obtained resin plate was 3 kN / m as measured by the method described in JIS-C6481.

(Reference Example 1)
A plate (30 mm × 50 mm) of an alicyclic olefin polymer (manufactured by Nippon Zeon Co., Ltd., ZEONEX 480) was immersed in acetone, subjected to ultrasonic cleaning, and then dried with warm air with a dryer.
Next, the surface of the resin plate was subjected to corona treatment using a corona discharge irradiation device (manufactured by Shinko Electric Instrumentation Co., Ltd., Corona Master).
The surface of the corona-treated resin plate was washed with distilled water, immersed in a TES solution having a concentration of 2 mM for 10 minutes, and then heated and dried in an oven at 120 ° C. for 15 minutes.

Next, the resin plate whose surface was treated with TES was immersed for 5 minutes in a metal plating catalyst (Rohm & Haas Electronic Materials, Cataposit 44) containing tin and palladium maintained at 52 ° C., and then the resin. The plate was removed from the plating catalyst bath and washed with ion exchange water.

  The obtained resin plate was immersed in an accelerator solution (Accelerator 19E, manufactured by Rohm and Haas Electronic Materials Co., Ltd.) for 7 minutes at room temperature, then taken out from the accelerator solution, and the resin plate surface was washed with ion-exchanged water.

The obtained resin plate having the surface on which the plating catalyst was supported was immersed in an aqueous copper sulfate solution (concentration: 47 mM) for 12 minutes at room temperature, washed with ion-exchanged water and alcohol, and then dried with a dryer.
The electroless plated resin plate was electroplated in an aqueous copper sulfate solution to obtain a resin plate having a copper foil with a thickness of 25 μm.

The peel strength of the copper foil formed on the resin plate thus obtained was 0.2 kN / m as measured by the method described in JIS-C6481.
Compared to Example 1, it can be seen that when there is no rubber layer on the resin substrate, the peel strength decreases.

(Reference Example 2)
In Reference Example 1, copper having a thickness of 25 μm was obtained in the same manner as Reference Example 1, except that the alicyclic olefin polymer was changed from (ZEONEX 480 manufactured by Nippon Zeon Co., Ltd.) to RS420 manufactured by Nippon Zeon Co., Ltd. A resin plate with a foil was obtained.
The peel strength of the copper foil laminated on the obtained resin plate was 0.7 kN / m as measured by the method described in JIS-C6481.
Compared to Example 2, it can be seen that when there is no rubber layer on the resin substrate, the peel strength decreases.

(Example 3)
Next, a plate (30 mm × 50 mm) of an alicyclic olefin polymer (manufactured by Nippon Zeon Co., Ltd., ZEONEX 480) is immersed in acetone, subjected to ultrasonic cleaning, and then dried with warm air with a dryer.
Next, the surface of the resin plate is subjected to corona treatment using a corona discharge irradiation device (manufactured by Shinko Electric Instrument Co., Ltd., corona master).
After washing the surface of the corona-treated resin plate with distilled water, TES ((6- (3-triethoxysilylpropyl) amino-1,3,5-triazine-2,4-dithiol monosodium salt) with a concentration of 2 mM ) After dipping in the solution for 10 minutes, heat-dry in a 120 ° C. oven for 15 minutes
Next, a thin rubber (about 100 μm) silicon rubber (SE6721A & B, manufactured by Toray Dow Corning Co., Ltd.) is applied to the surface of the TES-treated resin plate, and heated and vulcanized at 120 ° C. for 120 minutes with a hot press. Further, heat vulcanization is performed at 120 ° C. for 240 minutes.
Next, after the surface of the resin plate is dried with warm air using a dryer, a mask made of, for example, an alicyclic olefin polymer is placed on the resin plate and irradiated with ultraviolet rays using a low-pressure mercury lamp.
The resin surface after UV irradiation was washed with distilled water, and then immersed for 15 seconds in a metal plating catalyst bath (Rohm and Haas Electronic Materials, Cataposit 44) maintained at 52 ° C. Wash with ion exchange water.

Next, after immersing the resin plate in a room temperature accelerator solution (Accelerator 19E, manufactured by Rohm and Haas Electronic Materials) for 7 minutes, the resin plate is washed with ion-exchanged water.
The resin plate having the surface on which the catalyst for plating thus obtained is supported is immersed in an aqueous copper sulfate solution (concentration: 47 mM) for 12 minutes at room temperature, washed with ion-exchanged water and alcohol, and then dried with a dryer. Thus, a substrate having a copper pattern drawn on the surface of the resin plate is obtained.

(Example 4)
In Example 3, except that the alicyclic olefin polymer was changed to RS420 manufactured by Nippon Zeon Co., Ltd., the copper foil pattern was applied to the substrate in which the thin silicon rubber layer was laminated on the resin plate surface in the same manner as in Example 3. A drawn substrate is obtained.

It is sectional structure sectional drawing of the laminated body of this invention. It is sectional structure sectional drawing of the laminated body of this invention.

Explanation of symbols

1. Resin layer (resin substrate)
2a, 2c, 2e ... adhesive layer (I)
3, 3a, 3b ... rubber layer 2b, 2d, 2f ... adhesive layer (II)
4, 4a, 4b ... conductive layer 10A, 10B ... laminate

Claims (10)

A resin layer formed from an alicyclic olefin polymer;
On one side of the resin layer, an adhesive layer (I) formed from a thiol-reactive alkoxysilane compound represented by the following formula (A);
A rubber layer formed on the surface of the adhesive layer (I) opposite to the resin layer;
An adhesive layer (II) formed from a thiol-reactive alkoxysilane compound represented by the following formula (A) on the surface of the rubber layer opposite to the adhesive layer (I);
A conductive layer formed on the surface of the adhesive layer (II) opposite to the rubber layer;
A laminate having

(In the formula, R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an optionally substituted phenyl group, or a cycloalkyl having 3 to 10 carbon atoms. Represents a group.
R ² represents an alkylene group having 1 to 20 carbon atoms. In the alkylene chain, the alkylene group is an oxygen atom, a sulfur atom, a group represented by the formula: NR ³ (R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms), —C (= A group represented by O) NH—CH ₂ CH ₂ — or a group represented by —O—C (═O) NH— may be contained.
X represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
Y represents an alkoxy group having 1 to 10 carbon atoms.
n represents an integer of 1 to 3.
M represents an alkali metal atom. )   The adhesive layer (I) is formed by reacting the OH group provided on the surface of the alicyclic olefin polymer with the alkoxy group of the thiol-reactive alkoxysilane compound represented by the formula (A). The laminate according to claim 1, which has been obtained. The rubber layer is formed on the surface of the adhesive layer (I), or on the surface of the adhesive layer (I) on which a part or all of the surface has been subjected to adhesion reactivity control processing for controlling adhesion reactivity with rubber.
The laminate according to claim 1 or 2, which is formed by bringing an unvulcanized rubber or a vulcanized rubber into contact with each other and thermocompression bonding.   The adhesive layer (II) is formed by reacting an OH group provided on the surface of the rubber layer with an alkoxy group of the thiol-reactive alkoxysilane compound represented by the formula (A). The laminate according to any one of claims 1 to 3. The conductive layer irradiates the surface of the adhesive layer (II) with ultraviolet rays having a wavelength of 200 to 400 nm through a mask pattern, thereby obtaining a reactive and non-reactive finely patterned rubber adhesive ( i),
A step (ii) of obtaining a catalyst-supported rubber adhesive by immersing the obtained reactive and non-reactive fine patterned rubber adhesive in a reducing metal salt solution; and
The laminate according to any one of claims 1 to 4, which is formed by the step (iii) of electroless plating of the obtained catalyst-carrying rubber adhesive. The laminate according to any one of claims 1 to 4, wherein the conductive layer is formed on the surface of the adhesive layer (II) by an electroless plating step (iii). The laminate according to any one of claims 1 to 4, wherein the conductive layer is a metal foil attached to the surface of the adhesive layer (II). The other side formed from the thiol-reactive alkoxysilane compound represented by the formula (A) on the other side of the resin layer formed from the alicyclic olefin polymer, which is the side opposite to the one side. Side adhesive layer (I);
The other-side rubber layer formed on the surface opposite to the resin layer in the other-side adhesive layer (I);
The other side adhesive layer (II) formed from the thiol-reactive alkoxysilane compound represented by the formula (A) on the opposite side of the other side adhesive layer (I) in the other side rubber layer When,
The other side conductive layer formed on the opposite side of the other side rubber layer in the other side adhesive layer (II);
The laminate according to any one of claims 1 to 7.   It is a wiring board, The laminated body in any one of Claims 1-8.   The laminate according to any one of claims 1 to 9 and the laminate or the resin substrate according to any one of claims 1 to 9, wherein the thiol-reactive alkoxysilane compound represented by the formula (A) is used. A multilayer wiring board formed by laminating through an adhesive layer formed by reacting.

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