CN118250890A

CN118250890A - Laminate, method for producing same, and electronic component having laminate

Info

Publication number: CN118250890A
Application number: CN202311776480.6A
Authority: CN
Inventors: 田村礼; 富士川亘
Original assignee: DIC Corp
Current assignee: DIC Corp
Priority date: 2022-12-22
Filing date: 2023-12-22
Publication date: 2024-06-25
Also published as: JP2024089906A

Abstract

The invention provides a laminate, a method for producing the laminate, and an electronic component having the laminate. The invention provides a metal circuit board which is inexpensive, simple and highly reliable, and which suppresses cracking of a support by suppressing stress differences caused by thermal contraction of the support and copper wiring on the support made of an inorganic compound or ceramic containing silicon. The discovery is as follows: the laminate is characterized in that a stress-relaxing layer (B) containing an organic resin component, a plating base layer (C) and a metal plating layer (D) are laminated in this order on a support (A) composed of an inorganic compound or ceramic containing silicon.

Description

Laminate, method for producing same, and electronic component having laminate

Technical Field

The present invention relates to a method for manufacturing a printed wiring board, a printed wiring board for high-frequency transmission, a rigid printed wiring board, a package substrate, an interposer, an antenna, a semiconductor chip, and the like.

Background

With the miniaturization and high speed of electronic devices, there is a demand for higher density and higher performance of printed wiring boards, and in order to meet this demand, a support body having a smooth surface and low dielectric loss is required. Among them, an electronic circuit board using an inorganic substrate such as a glass substrate, which is made of an inorganic compound containing silicon or ceramic, as a support for a wiring board has been attracting attention.

As a conventional wiring board material, an organic material typified by a glass epoxy resin is generally used, but in recent years, with the progress of a wiring formation technology and a hole forming technology on a support made of an inorganic compound or ceramic containing silicon, a small-diameter through hole of 100 μm or less and a fine wiring of 2 μm can be formed, and thus a wiring board using an inorganic base material as a support has been attracting attention.

As an example of the support made of an inorganic compound containing silicon or ceramic, a glass substrate is given. The support has low dielectric loss in a circuit board using a glass substrate as a support, and has excellent performance as a support for high-frequency transmission. Further, since the flatness is excellent, the conductor loss of the wiring can be reduced. Further, applications to electronic circuit boards that effectively use characteristics of transparency, chemical stability, rigidity, and low cost have been studied, and the production of printed boards for semiconductors, transparent antennas, wiring boards for LED displays, and the like has been desired. Further, development of wiring boards for foldable smartphones, wiring boards for rollable displays, and the like has been actively conducted by using an extremely thin film glass substrate having a thickness of 50 μm.

Further, since an inorganic substrate such as a silicon wafer has a higher flatness than glass, it is used as a substrate material for CPUs, memories, transistors, and the like which require fine wiring. In recent years, siC wafers excellent in constant temperature resistance, high voltage resistance, and high current resistance as power semiconductors have been developed by adding carbon.

Conventionally, as a method for forming a metal film on such an inorganic substrate, sputtering or vapor deposition, which is a drying process, is used to form a conductive metal wiring by continuously forming a metal adhesion layer and a plating base layer and then plating the metal adhesion layer and the plating base layer.

However, the thermal load during film formation and the thermal load during manufacturing are affected by the difference in thermal expansion between the substrate and the metal wiring, and the stress concentration at the contact portion between the inorganic substrate and the metal wiring tends to cause a decrease in adhesion, and cracks in the inorganic substrate tend to occur, which results in a problem of a decrease in wiring reliability. Therefore, in order to suppress cracks between the metal wiring and the inorganic substrate, a thin film metal wiring and a thick film inorganic substrate have to be used, and the substrate design is limited.

Further, since deposition or sputtering is used for forming a metal thin film by a drying process, a large-scale vacuum apparatus is required, and there is a problem that the size of a substrate is limited in the apparatus. In addition, when the substrate is broken with the crack of the substrate and the metal wiring as a starting point at the time of manufacturing, there is a disadvantage that the yield is lowered and the production cost is increased because the vacuum is again pulled after the atmosphere is opened.

As a method for suppressing the cracks, a multilayer wiring board is proposed in which a metal layer of a circuit board is formed on an insulating substrate and laminated with a thermoplastic adhesive layer interposed therebetween. On the other hand, as a method for suppressing cracking of a single-layer circuit board, there has been proposed a glass circuit board having high electrical reliability, in which a stress relaxation layer of an inorganic substance is formed through a glass base material and a metal wiring layer by a drying process, and cracking, or warpage of the glass base material is suppressed, but there is a disadvantage in that the production cost is increased due to film formation by the drying process.

Therefore, there is a need for a method of manufacturing an inorganic substrate, which is inexpensive, simple, and stable in quality, without limiting the thickness of the inorganic substrate and the thickness of the metal wiring, improves the adhesion between the inorganic substrate and the metal wiring, suppresses cracking of the inorganic substrate, has sufficient wiring reliability, and does not require a large-scale vacuum apparatus at the time of forming the metal layer.

Prior art literature

Patent literature

Patent document 1: japanese patent application laid-open No. 2019-204921

Patent document 2: japanese patent application laid-open No. 2022-135962

Disclosure of Invention

Problems to be solved by the invention

The present invention aims to provide a metal circuit board with high reliability by suppressing cracking of a support body by suppressing stress difference caused by thermal shrinkage of the support body and copper wiring with respect to the support body composed of an inorganic compound or ceramic containing silicon, and by an inexpensive and simple method.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above problems, and as a result, found that: the present invention has been accomplished in view of the above problems, and it is an object of the present invention to provide a laminate comprising a support made of an inorganic compound containing silicon or ceramic, a stress relaxation layer containing an organic resin component, and a plating base layer and a metal plating layer laminated in this order on the stress relaxation layer.

Specifically, the present invention provides a laminate comprising a support (A) made of an inorganic compound or ceramic containing silicon, a stress relaxation layer (B) containing an organic resin component, a plating base layer (C), and a metal plating layer (D) laminated in this order, and a printed wiring board, a package substrate, and an interposer using the laminate.

That is, specifically, the present invention provides:

1. A laminate is characterized in that a stress relaxation layer (B), a plating base layer (C) and a metal plating layer (D) are provided in this order on at least one surface of a support (A) composed of an inorganic compound or ceramic containing silicon.

2. A laminate is characterized in that a stress relaxation layer (B), a plating base layer (C) and a temporary support (E) are provided in this order on at least one surface of a support (A) composed of an inorganic compound or ceramic containing silicon.

3. The laminate according to 1 or 2, further comprising a silane coupling layer (F) between the support (a) composed of an inorganic compound containing silicon or ceramic and the stress relaxation layer (B).

4. The laminate according to any one of claims 1 to 3, wherein the thickness of the support (A) made of an inorganic compound or ceramic containing silicon is 1 to 10,000 μm.

5. The laminate according to any one of 1 to 4, wherein the stress relaxation layer (B) has a thickness of 0.01 to 100. Mu.m.

6. The laminate according to any one of claims 1 to 5, wherein the stress relaxation layer (B) is at least selected from the group consisting of a urethane resin, an acrylic resin, a core-shell type composite resin having a urethane resin as a shell and an acrylic resin as a core, an epoxy resin, a phenoxy resin, an imide resin, an amide resin, a melamine resin, a phenol resin, a urea formaldehyde resin, a blocked isocyanate obtained by reacting a blocking agent such as phenol with a polyisocyanate, a polyvinyl alcohol, and a polyvinylpyrrolidone.

7. The laminate according to any one of claims 1 to 6, wherein the stress relaxation layer (B) is one or more layers.

8. The laminate according to any one of claims 1 to 7, wherein the thickness of the plating base layer (C) is 1 to 10,000mg/m ².

9. The laminate according to claim 1, wherein the thickness of the metal plating layer (D) is 0.05 to 100. Mu.m.

10. The laminate according to claim 3, wherein the silane coupling layer (F) has a thickness of 0.1 to 100nm.

The method for producing a laminate according to any one of claims 11.1, 3 to 10, comprising the steps of:

Step 1 of forming the stress relaxation layer (B) on at least one surface of a support (a) composed of an inorganic compound or ceramic containing silicon;

A step 2 of forming the plating base layer (C) on the surface of the stress relaxation layer (B);

and step 3, forming a metal plating layer (D) on the surface of the plating base layer (C).

The method for producing a laminate according to any one of claims 2 to 10, comprising the steps of:

step 1, manufacturing a transfer laminate in which a plating base layer (C) and a stress relaxation layer (B) are sequentially formed on a temporary support (E);

a step 2 of bonding a surface of the transfer laminate on which the stress relaxing layer (B) is formed to at least one surface of a support (a) made of an inorganic compound containing silicon or ceramic;

Step 3 of peeling off the temporary support (E) of the transfer laminate bonded to the support (a) made of an inorganic compound or ceramic containing silicon, and forming the stress relaxing layer (B) and the plating underlayer (C) on at least one surface of the support (a) made of an inorganic compound or ceramic containing silicon;

and step 4, forming a metal plating layer (D) on the surface of the plating base layer (C).

13. The method according to claim 11 or 12, comprising the following step 1: a silane coupling layer (F) is formed on at least one surface of a support (A) composed of an inorganic compound containing silicon or a ceramic.

14. A printed wiring board, a package substrate, an interposer, a wiring substrate for an LED electrode, and a photo fusion device, comprising the laminate of any one of 1 to 10.

Effects of the invention

The laminate of the present invention has the following characteristics: compared with the conventional method of forming a metal plating layer by vapor deposition or sputtering, the method is inexpensive and simple, and the adhesion between a support made of an inorganic compound or ceramic containing silicon and the metal plating layer is excellent, so that the thermal expansion difference between the support and wiring can be suppressed by the stress relaxation layer, and cracking of the support can be suppressed. Accordingly, the laminate of the present invention can be suitably used as an electronic component such as a printed wiring board, a rigid printed wiring board, a flexible printed wiring board, a package substrate, a metal mesh for a touch panel, an organic solar cell, an organic EL element, a wiring substrate for an LED electrode, an organic transistor, an RFID such as a noncontact IC card, an electromagnetic wave shield, an LED lighting substrate, a digital signage, a photofusion device, an interposer, or the like.

Drawings

Fig. 1 is a cross-sectional view of a laminate of the present invention in which a stress relaxing layer, a plating base layer, and a metal plating layer are formed in this order on one surface of a support made of an inorganic compound containing silicon or ceramic.

Fig. 2 is a cross-sectional view of a laminate of the present invention in which a surface of a transfer laminate having a plating base layer and a stress relaxation layer formed thereon is bonded to a surface of a support made of an inorganic compound or ceramic containing silicon.

Fig. 3 is a cross-sectional view of a laminate of the present invention in which a silane coupling layer, a stress relaxing layer, a plating base layer, and a metal plating layer are formed in this order on one surface of a support made of an inorganic compound containing silicon or ceramic.

Fig. 4 is a cross-sectional view of a laminate of the present invention in which a surface of a laminate for transfer having a plating base layer and a stress relaxation layer formed thereon and a surface of a support having silicon formed thereon and a surface of a support having a silane coupling layer formed thereon are bonded to each other, the surface being formed on one side of the support being composed of an inorganic compound or ceramic having silicon.

Fig. 5 is a cross-sectional view of a wiring board of the present invention in which a stress relaxing layer, a plating base layer, and a metal plating layer are sequentially formed and patterned on one surface of a support made of an inorganic compound containing silicon or ceramic.

Fig. 6 is a cross-sectional view of a wiring board of the present invention in which a silane coupling layer, a stress relaxing layer, a plating base layer, and a metal plating layer are sequentially formed and patterned on one surface of a support made of an inorganic compound containing silicon or ceramic.

Symbol description

1: Metal plating

2: Plating base layer

3: Stress relaxation layer

4: Support (A) composed of inorganic compound or ceramic containing silicon

5: Temporary support

6: And a silane coupling layer.

Detailed Description

The laminate of the present invention is a laminate having the following characteristics: the support (A) is provided with a stress relaxation layer (B), a plating base layer (C) and a metal plating layer (D) on at least one surface of the support (A) composed of an inorganic compound or ceramic containing silicon.

The laminate of the present invention may be a laminate in which the stress relaxation layers (B) and the like are laminated in this order on one surface of the support (a) composed of the inorganic compound or the ceramic containing silicon, or a laminate in which the stress relaxation layers (B) and the like are laminated in this order on both surfaces of the support (a) composed of the inorganic compound or the ceramic containing silicon.

The laminate of the present invention is a laminate obtained by bonding a transfer laminate in which the plating base layer (C) and the stress relaxation layer (B) are sequentially formed on the temporary support (E) to at least one surface of the support (a) composed of an inorganic compound or ceramic containing silicon.

Further, the laminate of the present invention is a laminate having the following characteristics: at least one surface of a support (A) composed of an inorganic compound or ceramic containing silicon is provided with a silane coupling layer (F), the stress relaxing layer (B), and the plating base layer (C).

Examples of the support (a) made of an inorganic compound containing silicon include alkali-free glass, alkali glass, borosilicate glass, quartz glass, sapphire glass, photosensitive glass, silicon wafer, silicon carbide wafer, and the like.

Examples of the support (a) made of ceramics include alumina, zirconia, magnesia, titania, ceria, zinc oxide, tin oxide, uranium oxide, silicon carbide, titanium carbide, tungsten carbide, boron carbide, titanium boride, zirconium boride, lanthanum boride, molybdenum silicide, iron silicide, barium silicide, aluminum nitride, silicon nitride, forsterite, talc, cordierite, sialon (Sialon), machinable ceramics (machinable ceramic), barium titanate, lead zirconate titanate, ferrite, mullite, hydroxyapatite, carbonate, zinc oxide, YAG, barium ferrite, graphite, diamond, gallium nitride, and the like.

When the shape of the support (a) made of the inorganic compound or ceramic containing silicon is a film or a sheet, the thickness of the support (a) made of the inorganic compound or ceramic containing silicon is preferably a film from the viewpoint of downsizing of the electronic device, but the more likely the film is, the more unstable the quality is, and therefore, is preferably in the range of 1 to 10,000 μm, more preferably in the range of 10 to 1,000 μm, and even more preferably in the range of 30 to 700 μm.

In the prior art, an organic resin layer imparting adhesion and releasability to a metal plating layer is formed on an organic film substrate, but in the support (a) composed of an inorganic compound or ceramic containing silicon of the film of the present invention, there is a problem that cracks and warpage occur in the support peculiar to a hard substrate of the film. In the present invention, stress relaxation properties are imparted by the stress relaxation layer (B) described later, so that adhesion between the inorganic substrate and the metal wiring is improved, cracking of the inorganic substrate is suppressed, and sufficient wiring reliability is provided.

In addition, in order to improve the adhesion between the support (a) made of the inorganic compound or ceramic containing silicon and the stress relaxation layer (B) described later, the surface of the support (a) made of the inorganic compound or ceramic containing silicon may be subjected to surface treatment for forming fine irregularities, cleaning dirt adhering to the surface, introducing functional groups such as hydroxyl groups, carbonyl groups, carboxyl groups, and the like. Specifically, a dry treatment such as a plasma discharge treatment such as a corona discharge treatment, an ultraviolet treatment, or a wet treatment using water, an aqueous solution such as an acid or an alkali, an organic solvent, or the like may be performed.

The use of the thermoplastic resin for the stress relaxation layer (B) can suppress curing shrinkage generated during the curing reaction in the step of curing the stress relaxation layer (B), and therefore can reduce stress applied to the interface between the support (a) made of the inorganic compound containing silicon or ceramic and the stress relaxation layer (B), and improve adhesion.

The stress relaxation layer (B) is formed by heat shrinkage due to a heat load during the production of the circuit board, and the stress relaxation layer (B) is formed by following a plating base layer (C) and a metal plating layer (D) described later. As a result, the stress generated in the stress relaxing layer (B) and the plating base layer (C) and the metal plating layer (D) described later is suppressed, and cracks generated in the laminate are suppressed.

The stress relaxation layer (B) can be formed by coating a resin solution on a part or the whole of the surface of the support (a) composed of an inorganic compound or ceramic containing silicon, and removing a solvent such as an aqueous medium or an organic solvent contained in the resin solution.

Examples of the method of applying the stress relaxing layer (B) to the surface of the support (a) made of an inorganic compound or ceramic containing silicon include gravure method, coating method, screen method, roll method, rotary method, and spray method.

In order to further improve the adhesion with the plating base layer (C) described later, the surface of the stress relaxation layer (B) is preferably subjected to surface treatment by, for example, a plasma discharge treatment method such as a corona discharge treatment method, a dry treatment method such as an ultraviolet treatment method, or a wet treatment method using water, an acidic or basic chemical agent, an organic solvent, or the like.

As a method of removing the solvent contained in the coating layer after the stress relaxation layer (B) is applied to the surface of the support (a) composed of the inorganic compound containing silicon or ceramic, for example, a method of drying the support using a dryer to volatilize the solvent is generally used. The drying temperature may be set to a temperature in a range that allows the solvent to volatilize and does not adversely affect the support (a) made of the inorganic compound containing silicon or the ceramic, such as thermal deformation.

The film thickness of the stress relaxation layer (B) varies depending on the application in which the laminate of the present invention is used, but is preferably in a range that further improves the adhesion between the support (a) made of an inorganic compound or ceramic containing silicon and a plating base layer (C) described later, and that does not deteriorate the stress relaxation property, and the film thickness of the stress relaxation layer (B) is preferably in a range of 0.01 μm to 100 μm, preferably in a range of 0.05 μm to 50 μm, more preferably in a range of 0.1 μm to 30 μm, and even more preferably in a range of 0.2 μm to 5 μm.

As the resin composition (B) of the stress relaxation layer used for forming the stress relaxation layer (B), a resin composition containing various resins and solvents can be used.

Examples of the resin (b) include urethane resins, acrylic resins, core-shell type composite resins having a urethane resin as a shell and an acrylic resin as a core, epoxy resins, phenoxy resins, imide resins, amide resins, melamine resins, phenol resins, urea formaldehyde resins, blocked isocyanate polyvinyl alcohols obtained by reacting a blocking agent such as phenol with a polyisocyanate, and polyvinylpyrrolidone. The core-shell type composite resin having a urethane resin as a shell and an acrylic resin as a core is obtained, for example, by polymerizing an acrylic monomer in the presence of the urethane resin. In addition, one kind of these resins may be used or two or more kinds may be used in combination.

The aminotriazine modified novolak resin is a novolak resin in which an aminotriazine ring structure and a phenol structure are bonded via a methylene group. The aminotriazine-modified novolak resin is obtained, for example, by subjecting an aminotriazine compound such as melamine, benzoguanamine, acetoguanamine, etc. to a co-condensation reaction with phenol compounds such as phenol, cresol, butylphenol, bisphenol a, phenylphenol, naphthol, resorcinol, etc. and formaldehyde in the presence or absence of a weakly basic catalyst such as alkylamine, etc. in the vicinity of neutrality, or by reacting an alkyl etherate of an aminotriazine compound such as methyl etherified melamine, etc. with the phenol compounds.

The aminotriazine modified novolak resin preferably has substantially no hydroxymethyl group. The aminotriazine-modified novolak resin is not particularly limited, even if it contains a molecule having only an aminotriazine structure bound thereto via a methylene group, a molecule having only a phenol structure bound thereto via a methylene group, or the like, which is produced as a by-product during production thereof. Further, a certain amount of unreacted raw materials may be contained.

Examples of the phenol structure include phenol residues, cresol residues, butylphenol residues, bisphenol a residues, phenylphenol residues, naphthol residues, resorcinol residues, and the like. In addition, the residue herein refers to a structure in which at least one of hydrogen atoms bonded to carbon of an aromatic ring is removed. For example, in the case of phenol, it refers to hydroxyphenyl.

Examples of the triazine structure include structures derived from aminotriazine compounds such as melamine, benzoguanamine and acetoguanamine.

The above phenol structure and the above triazine structure may each be used singly or in combination. In addition, from the viewpoint of further improving adhesion, the phenol structure is preferably a phenol residue, and the triazine structure is preferably a melamine-derived structure.

The hydroxyl value of the aminotriazine modified novolak resin is preferably in the range of 50 to 200mgKOH/g, more preferably in the range of 80 to 180mgKOH/g, and even more preferably in the range of 100 to 150mgKOH/g, from the viewpoint of further improving the adhesion.

The aminotriazine-modified novolak resin may be used singly or in combination.

In addition, as the amino triazine ring compound, in the use of amino triazine modified novolak resin, preferably used in combination with epoxy resin.

Examples of the epoxy resin include bisphenol a type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy resin, bisphenol a novolak type epoxy resin, alcohol ether type epoxy resin, tetrabromobisphenol a type epoxy resin, naphthalene type epoxy resin, phosphorus-containing epoxy compound having a structure derived from 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, epoxy resin having a structure derived from dicyclopentadiene derivative, epoxy compound of oil or fat such as epoxidized soybean oil, and the like. One kind of these epoxy resins may be used, or two or more kinds may be used in combination.

Among the above epoxy resins, bisphenol a type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, cresol novolac type epoxy resins, phenol novolac type epoxy resins, bisphenol a novolac type epoxy resins are preferable, and bisphenol a type epoxy resins are particularly preferable, since stress relaxation properties can be further improved. The epoxy group of the epoxy resin reacts with the basic nitrogen atom-containing group contained in the plating base layer (C) described later to form a covalent bond, so that the adhesion of the interface between the plating base layer (C) described later and the stress relaxation layer (B) is improved.

The epoxy equivalent of the epoxy resin is preferably in the range of 100 to 300 g/equivalent, more preferably in the range of 120 to 250 g/equivalent, and even more preferably in the range of 150 to 200 g/equivalent, from the viewpoint of further improving the adhesion.

When the stress relaxation layer (B) is a layer containing an aminotriazine modified novolak resin and an epoxy resin, the molar ratio [ (x)/(y) ] of the phenolic hydroxyl group in the aminotriazine modified novolak resin to the epoxy group in the epoxy resin is preferably in the range of 0.1 to 5, more preferably in the range of 0.2 to 3, and even more preferably in the range of 0.3 to 2, from the viewpoint that the adhesion can be further improved.

In order to promote the reaction between the aminotriazine modified novolak resin and the epoxy resin, a curing accelerator may be used in combination. Examples of the curing accelerator include amine compounds having a primary amino group, a secondary amino group, or a tertiary amino group. As the amine compound, any of aliphatic, alicyclic, and aromatic amine compounds may be used. As the curing accelerator, use may be made of thiols, anhydrides, boron trifluoride, boric acid esters, organic acid hydrazides, lewis acids, organometallic compounds,Salts, cationic compounds, and the like.

In addition, a compound containing a phenoxy resin is preferably used. The stress relaxation layer (B) has a function of improving the stress relaxation property of the support (a) made of an inorganic compound or ceramic containing silicon and the plating base layer (C). In the present invention, a resin having a weight average molecular weight in the range of 10,000 ～ 100,000 is preferably used as the phenoxy resin. By using a phenoxy resin having a high molecular weight for the stress relaxation layer (B), the elongation of the polymer can be improved, and the stress relaxation property can be further improved.

The phenoxy resin is a polyhydroxy polyether obtained by reacting a bivalent phenol compound with epichlorohydrin or a bivalent epoxy compound with a bivalent phenol compound. As the bivalent phenol compound, bisphenols are exemplified. Examples of the phenoxy resin include a phenoxy resin having a bisphenol a structure (skeleton), a phenoxy resin having a bisphenol F structure, a phenoxy resin having a bisphenol S structure, a phenoxy resin having a bisphenol M structure, a phenoxy resin having a bisphenol P structure, and a phenoxy resin having a bisphenol Z structure. Examples of the resin include phenoxy resins having a skeleton structure such as a novolac structure, an anthracene structure, a fluorene structure, a dicyclopentadiene structure, a norbornene structure, a naphthalene structure, a biphenyl structure, and an adamantane structure. These phenoxy resins may be used singly or in combination of two or more. Among these, a phenoxy resin having a bisphenol structure is preferable, and a bisphenol a skeleton, a bisphenol F skeleton, and a bisphenol S skeleton are more preferable. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

In the present invention, the weight average molecular weight of the phenoxy resin used is preferably in the range of 10,000 ～ 100,000. If the molecular weight is 10,000 or more, the plating adhesion after the long-term heat resistance test becomes high, and if the molecular weight is 100,000 or less, the solubility in an organic solvent is improved, and the viscosity of the coating liquid at the time of forming the stress relaxation layer (B) becomes appropriate, so that the treatment becomes good. The phenoxy resin preferably has a weight average molecular weight of 20,000 ～ 80,000, more preferably 22,000 ～ 50,000. The weight average molecular weight of the phenoxy resin can be adjusted by the molar ratio of the epoxy resin to the novolak resin and the reaction time in the above reaction. In the present specification, the weight average molecular weight is a value in terms of standard polystyrene measured by Gel Permeation Chromatography (GPC) described later. In the measurement of GPC, a high-speed GPC apparatus (HLC-8420 GPC, manufactured by Tosoh Co., ltd.) was used as a measuring apparatus, and a column was used by connecting TSKgelG 5000: 5000HxL/G4000HxL/G3000HxL/G2000HxL (manufactured by Tosoh Co., ltd.) in series, tetrahydrofuran was used as an eluent, and the measurement was performed using an RI detector. In addition, the phenoxy resin generally refers to a high molecular weight epoxy resin, but the "epoxy resin" in the present specification refers to a resin having a weight average molecular weight of less than 10,000, which is different from the above phenoxy resin.

As the phenoxy resin, commercially available resins may be used, and examples thereof include 1256 and 4250 (all of which are phenoxy resins having bisphenol A skeleton, made by Mitsubishi chemical Co., ltd.), 4275 (bisphenol A/bisphenol F mixture), YL6794, YL7213, YL7290, YL7482, YL7553, YX8100 (phenoxy resins having bisphenol S skeleton), X6954 (phenoxy resins having bisphenol acetophenone skeleton, YX7200 (phenoxy resins having cyclohexane skeleton), YP-70 (bisphenol F type phenoxy resins made by Nitro chemical & materials Co., ltd.), ZX356-2 (phenoxy resins having bisphenol A and bisphenol F skeleton), YPB-40 PWM 40 (phenoxy resins having bromine), ERF-001M30 (phenoxy resins having phosphorus), FX-280, FX-293, FX-310 (phenoxy resins having fluorene skeleton), gabriel Phenoxies +, PKHC, PKHH, PKHJ, PKFE, etc.

In the present invention, the stress relaxation layer (B) preferably contains an epoxy resin used in combination with the phenoxy resin. By using a combination of a phenoxy resin and an epoxy resin, the adhesion to a metal plating layer (D) described later and the stress relaxation property are further improved in a normal state and after a long-term heat resistance test.

Examples of the epoxy resin include bisphenol a type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy resin, bisphenol a novolak type epoxy resin, alcohol ether type epoxy resin, tetrabromobisphenol a type epoxy resin, naphthalene type epoxy resin, phosphorus-containing epoxy compound having a structure derived from 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, epoxy resin having a structure derived from dicyclopentadiene derivative, epoxy of oil and fat such as epoxidized soybean oil, and the like. These epoxy resins may be used singly or in combination of two or more.

The epoxy resin used in combination with the phenoxy resin is preferably an aromatic epoxy resin such as bisphenol a type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol a novolac type epoxy resin, or the like, more preferably a liquid epoxy resin, and particularly preferably a bisphenol a type epoxy resin, from the viewpoint of further improving the adhesion of the metal plating layer (D) described later.

The epoxy equivalent of the epoxy resin is preferably 100 to 5,000 g/equivalent, more preferably 120 to 2,000 g/equivalent, and even more preferably 120 to 250 g/equivalent, from the viewpoint of further improving the adhesion.

When the stress relaxation layer (B) further contains an epoxy resin in addition to a phenoxy resin, the blending ratio of the phenoxy resin to the epoxy resin is preferably 90 on a mass basis: 10-10: 90, more preferably 85: 15-15: 85.

In the present invention, when a phenoxy resin is used for the stress relaxation layer (B), the epoxy group at the end of the phenoxy resin reacts with a basic nitrogen atom-containing group contained in a plating base layer (C) described later, and thus the adhesion of the interface between the stress relaxation layer (B) and the plating base layer (C) described later is improved. The phenoxy resin may be used in combination with other resins.

The stress relaxation layer (B) is preferably composed of a thermoplastic resin which is excellent in heat resistance and can follow the metal plating layer (D) described later when the metal plating layer (D) is deformed by a load such as heat, and as an example, a phenoxy resin, a polyurethane resin, an acrylic resin, a core-shell type composite resin having a polyurethane resin as a shell and an acrylic resin as a core, a polyimide resin, a polyphenylene ether resin, an aromatic polyamide resin, a polycarbonate resin, a polyacetal resin, a polybutylene terephthalate resin, a polyphenylene sulfide resin, a polysulfone resin, a polyetherimide resin, a polyethersulfone resin, a polyamideimide resin, a polyether ether ketone resin, and a polytetrafluoroethylene resin are preferably used.

The stress relaxation layer (B) may be one layer or two or more layers. When two or more stress relaxation layers (B) are formed, for example, adhesion between a layer close to a plating base layer (C) described later and the plating base layer (C) described later can be improved, and on the other hand, stress relaxation between the stress relaxation layer (B) close to the support (a) composed of the inorganic compound or ceramic containing silicon and the support (a) composed of the inorganic compound or ceramic containing silicon can be improved. The stress relaxation layer (B) of the first layer adjacent to the plating base layer (C) described later is a layer adjacent to the plating base layer (C) described later and the metal plating layer (D) described later, and is a portion adjacent to the copper wiring when the conductive pattern is formed, and therefore, the stress relaxation layer (B) may be formed by selecting a resin composition for improving insulation reliability.

Further, since the coating material of the stress relaxation layer (B) is applied to the surface of the support (a) composed of an inorganic compound containing silicon or ceramic, an organic solvent is preferably blended so as to have a viscosity that facilitates application. Examples of the organic solvent include ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isopropyl alcohol, diacetone alcohol, ethylene glycol, toluene, and the like. These solvents may be used singly or in combination.

In the coating material of the stress relaxation layer (B), known additives such as a film forming aid, a leveling agent, a thickener, a water repellent, an antifoaming agent, and an antioxidant may be added as necessary.

Examples of the method of applying the coating material of the stress relaxation layer (B) include gravure type, coating type, screen type, roll type, rotary type, spray type, capillary type, doctor roll type, and the like.

As a method of forming the coating material of the stress relaxation layer (B) on the surface of the support (a) composed of the inorganic compound containing silicon or ceramic, and then removing the organic solvent contained in the coating layer, for example, a method of drying the support (a) using a dryer to volatilize the organic solvent is generally used.

The drying temperature of the stress relaxation layer (B) is preferably in the range of 50 to 400 ℃, more preferably in the range of 80 to 340 ℃, still more preferably in the range of 120 to 280 ℃, and even more preferably in the range of 150 to 200 ℃.

The plating base layer (C) is a layer formed on the stress relaxation layer (B), and examples of the metal constituting the plating base layer (C) include transition metals and compounds thereof, and among these, ionic transition metals are preferable. Examples of the ionic transition metal include copper, silver, gold, nickel, palladium, platinum, cobalt, and the like. Among these ionic transition metals, copper, silver, and gold are preferable because conductive patterns having low resistance and high corrosion are obtained. The plating base layer (C) is preferably a porous layer, and in this case, the layer has voids therein.

The method for producing the laminate of the present invention includes the following methods: first, the stress relaxation layer (B) is formed on the support (a) composed of an inorganic compound or ceramic containing silicon, then a fluid containing nano-sized metal nanoparticles (C) is applied, an organic solvent or the like contained in the fluid is removed by drying, thereby forming the plating base layer (C), and then a metal plating layer (D) to be described later is formed by electroplating or electroless plating. In the formation of the plating base layer (C), the fluid containing the metal nanoparticles (C) is applied to the stress relaxation layer (B) and dried to form a plating base layer (C '), and then the plating base layer (C ') is baked to remove the organic compound containing the dispersant in the plating base layer (C ') and form voids, thereby forming the porous plating base layer (C), and the adhesion to the metal plating layer (D) described later is preferably improved.

The shape of the metal nanoparticles (C) used for forming the plating base layer (C) is preferably a particle shape or a fiber shape. In addition, when the metal nanoparticles (c) are in the form of particles, the average particle diameter is preferably in the range of 1 to 100nm, more preferably in the range of 1 to 50nm, in order to form a fine network-like conductive pattern. The "average particle diameter" is a volume average value measured by a dynamic light scattering method by diluting the conductive material with a good dispersion solvent. As the measurement, nanotrac UPA-150 "manufactured by Microtrac, inc. can be used.

On the other hand, in the case where the metal nanoparticles (c) are fibrous in shape, the diameter of the fibers is preferably in the range of 5 to 100nm, more preferably in the range of 5 to 50nm, in order to form a fine network-like conductive pattern and to further reduce the resistance value. The length of the fibers is preferably in the range of 0.1 to 100. Mu.m, more preferably in the range of 0.1 to 30. Mu.m.

The content of the metal nanoparticles (c) in the fluid is preferably in the range of 1 to 90% by mass, more preferably in the range of 1 to 60% by mass, and even more preferably in the range of 1 to 10% by mass.

Examples of the components that can be blended in the fluid include a dispersant for dispersing the metal nanoparticles (c) in a solvent, and if necessary, a surfactant, a leveling agent, a viscosity regulator, a film-forming auxiliary agent, an antifoaming agent, a preservative, and the like, which will be described later.

In order to disperse the metal nanoparticles (c) in a solvent, a low-molecular-weight or high-molecular-weight dispersant is preferably used. Examples of the dispersant include dodecyl mercaptan, 1-octanethiol, triphenylphosphine, dodecylamine, polyethylene glycol, polyvinylpyrrolidone, polyethyleneimine, and polyvinylpyrrolidone; fatty acids such as myristic acid, caprylic acid, and stearic acid; and polycyclic hydrocarbon compounds having a carboxyl group such as cholic acid, glycyrrhizic acid and abietic acid. Among them, a polymer dispersant is preferable in that the adhesion between the plating base layer (C) and the metal plating layer (D) to be described later can be improved by forming the plating base layer (C) into a porous shape, and examples of the polymer dispersant include polyalkyleneimines such as polyethyleneimine and polypropyleneimine, a compound obtained by adding a polyoxyalkylene to the polyalkyleneimine, a urethane resin, an acrylic resin, a compound containing a phosphate group in the urethane resin and the acrylic resin, and the like.

As described above, by using a polymer dispersant as the dispersant, the dispersant in the plating base layer (C) can be removed to form a porous shape, and the void size can be increased, so that voids having a size of nano-scale to submicron-scale can be formed, as compared with a low-molecular dispersant. The voids are easily filled with a metal constituting a metal plating layer (D) described later, and the filled metal serves as an anchor agent, so that the adhesion between the plating base layer (C) and the metal plating layer (D) described later can be greatly improved.

The amount of the dispersant to be used for dispersing the metal nanoparticles (c) is preferably 0.01 to 50 parts by mass, more preferably 0.01 to 10 parts by mass, based on 100 parts by mass of the metal nanoparticles (c).

In order to further improve the adhesion between the plating base layer (C) and the metal plating layer (D) described later, the amount of the dispersant to be removed by firing is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the nano-sized metal powder, in the case where the porous plating base layer (C) is formed by removing the dispersant.

As the solvent used in the fluid, an aqueous medium or an organic solvent can be used. Examples of the aqueous medium include distilled water, ion-exchanged water, pure water, and ultrapure water. Examples of the organic solvent include alcohol compounds, ether compounds, ester compounds, and ketone compounds.

Examples of the alcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, heptanol, hexanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, stearyl alcohol, allyl alcohol, cyclohexanol, terpineol, dihydroterpineol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, and the like.

In addition to the metal powder and the solvent, ethylene glycol, diethylene glycol, 1, 3-butanediol, isopentane diol, and the like may be used as needed.

The surfactant may be any conventional surfactant, and examples thereof include di-2-ethylhexyl sulfosuccinate, dodecylbenzene sulfonate, alkyldiphenyl ether disulfonate, alkylnaphthalene sulfonate, and hexametaphosphate.

As the leveling agent, a general leveling agent can be used, and examples thereof include an organosilicon compound, an acetylene glycol compound, and a fluorine compound.

Examples of the viscosity modifier include an acrylic polymer which is thickened by being alkaline, a synthetic rubber latex, a polyurethane resin which is thickened by molecular association, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, polyvinyl alcohol, hydrogenated castor oil, amide wax, oxidized polyethylene, metallic soap, dibenzylidene sorbitol, and the like.

Examples of the film-forming auxiliary include anionic surfactants (dioctyl sulfosuccinate sodium salt, etc.), hydrophobic nonionic surfactants (sorbitan monooleate, etc.), polyether-modified silicones, silicone oils, etc.

As the defoaming agent, a general defoaming agent can be used, and examples thereof include silicone-based defoaming agents, nonionic surfactants, polyethers, higher alcohols, and polymer-based surfactants.

As the preservative, a general preservative may be used, and examples thereof include isothiazoline-based preservatives, triazine-based preservatives, imidazole-based preservatives, pyridine-based preservatives, azole-based preservatives, iodine-based preservatives, and pyrithione-based preservatives.

The viscosity of the fluid (measured at 25 ℃ C. Using a B-type viscometer) is preferably in the range of 0.1 to 500,000 mPas, more preferably in the range of 0.5 to 10,000 mPas. When the fluid is applied (printed) by a method such as an inkjet printing method or a relief reverse printing method, which will be described later, the viscosity is preferably in the range of 5 to 20mpa·s.

Examples of the method of applying and printing the fluid on the stress relaxation layer (B) include an inkjet printing method, a reverse printing method, a screen printing method, an offset printing method, a spin coating method, a spray coating method, a bar coating method, a die coating method, a slit coating method, a roll coating method, a dip coating method, a pad printing method, a gravure printing method, and a flexographic printing method.

Among these coating methods, when the patterned plating base layer (C) is formed in a fine line shape of about 0.01 to 100 μm, which is required for achieving high density of electronic circuits and the like, an inkjet printing method and a reverse printing method are preferably used.

As the inkjet printing method, an inkjet printing method called an inkjet printer can be generally used. Specifically, kenicamada EB100, XY100 (manufactured by Kenicamada IJ Co., ltd.), dimatix MATERIALS PRINTER DMP-3000, dimatix MATERIALS PRINTER DMP-2831 (manufactured by Fuji film Co., ltd.) and the like are exemplified.

As the reverse printing method, a relief reverse printing method and a gravure reverse printing method are known, and examples thereof include the following methods: the fluid is applied to the surface of each of the rubberized fabrics, the non-painted portion is brought into contact with the protruding plate, the fluid corresponding to the non-painted portion is selectively transferred to the surface of the plate, thereby forming the pattern on the surface of the rubberized fabric or the like, and then the pattern is transferred to the support (a) (surface) composed of the inorganic compound or ceramic containing silicon.

In addition, a pad printing method is known for printing a pattern when the support (a) made of an inorganic compound containing silicon or ceramic is a molded article. The following methods may be mentioned: the ink was placed on the intaglio plate, recorded with a doctor blade, and the ink was uniformly filled in the concave portion, and a pad made of silicone rubber or urethane rubber was pressed against the plate on which the ink was placed, and the pattern was transferred onto the pad, and then onto the molded article.

The drying temperature after the application and printing of the fluid is preferably in the range of 50 to 400 ℃, more preferably in the range of 80 to 340 ℃, still more preferably in the range of 120 to 320 ℃, still more preferably in the range of 150 to 300 ℃, and still more preferably in the range of 180 to 280 ℃.

The mass per unit area of the plating base layer (C) is preferably in the range of 1 to 10,000mg/m ², preferably in the range of 1 to 5,000mg/m ². In the case of electroless plating of the plating base layer (C), the thickness of the plating base layer (C) may be relatively small, and specifically, it is preferably 1 to 5,000mg/m ², preferably 10 to 1,000mg/m ², preferably 10 to 500mg/m ², more preferably 50 to 500mg/m ², because the plating base layer (C) is used as a catalyst. On the other hand, in the case of applying electroplating to the plating base layer (C), since the plating base layer (C) has conductivity and preferably low resistance, the film thickness may be relatively thick, preferably 100 to 10,000mg/m ², preferably 300 to 5,000mg/m ², and the plating base layer (C) is made thinner and made lower in cost, more preferably 500 to 2,000mg/m ², for the adhesion of the metal plating layer (D) to the plating base layer (C) to be described later.

The surface resistance of the plating base layer (C) when electroplating is performed on the plating base layer (C) is preferably low in order to form electroplating uniformly. The surface resistance is preferably in the range of 0.1 to 10,000 Ω/∈s, more preferably in the range of 0.15 to 1,000 Ω/∈s, more preferably in the range of 0.15 to 500 Ω/∈s, more preferably in the range of 0.2 to 100 Ω/∈s, more preferably in the range of 0.2 to 10 Ω/∈s, and even more preferably in the range of 0.2 to 5 Ω/∈s.

The method for forming the stress relaxation layer (B) and the plating base layer (C) on the support (a) made of an inorganic compound containing silicon or ceramic includes the following methods: a transfer laminate is produced by sequentially laminating the plating base layer (C) and the stress relaxation layer (B) on a temporary support (E), and the surface of the stress relaxation layer (B) of the transfer laminate is bonded to at least one surface of the support (A) made of an inorganic compound or ceramic containing silicon.

The method of bonding by transfer is a simple method in which the stress relaxing layer (B) and the plating base layer (C) can be formed simultaneously by thermocompression bonding on the support (a) composed of the inorganic compound or ceramic containing silicon, and therefore productivity is excellent and manufacturing cost can be suppressed, as compared with a method of applying by a known dry process or a wet process on the support (a) composed of the inorganic compound or ceramic containing silicon. Further, it is preferable to embed the plating base layer (C) in the stress relaxation layer (B) by applying pressure thereto by thermocompression bonding, so as to strengthen the adhesion force at the interface between the stress relaxation layer (B) and the plating base layer (C).

As the temporary support (E), a final peeling is required after the lamination of the transfer laminate, and therefore, a temporary support that can be easily peeled off at the interface between the temporary support (E) and the plating base layer (C) is preferably selected. For example, as the polymer film, aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate (PBT), polyethylene naphthalate, and polybutylene naphthalate; fluorine-based resins such as polytetrafluoroethylene, tetrafluoroethylene perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, vinylidene fluoride resin, chlorotrifluoroethylene-ethylene copolymer, tetrafluoroethylene-perfluorodioxole copolymer, vinyl fluoride resin, polyvinylidene fluoride and the like; olefin resins such as polymethylpentene (TPX), polypropylene (PP) [ including biaxially oriented polypropylene (OPP), non-axioriented polypropylene (CPP) ] and Polyethylene (PE) [ including High Density Polyethylene (HDPE), low Density Polyethylene (LDPE), linear Low Density Polyethylene (LLDPE) ]; polystyrene (PS); polyimide resins such as polyvinyl chloride (PVC), polyimide, and transparent polyimide; polyamide resins such as polyamideimide and polyamide; polycarbonates, acrylonitrile-butadiene-styrene (ABS) resins, polymer alloys of ABS and polycarbonate, acrylic resins such as polymethyl (meth) acrylate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polycarbonates, polyethylene, polypropylene, polyurethane, liquid Crystal Polymers (LCP), polyetheretherketone (PEEK), polyphenylene sulfide (PPS), polyphenylsulfone (PPSU), epoxy resins, and the like. Among them, aromatic polyesters, polyethylenes, olefin resins, fluorine resins, polyimide resins, LCPs, polyphenylene sulfides, and polystyrenes are preferably used as the temporary support (E).

As the temporary support (E), a metal may be used, and copper, aluminum alloy, titanium, stainless steel, beryllium copper, phosphor bronze, nickel, nichrome, nickel alloy, tin, zinc, lead, gold, tantalum, molybdenum, niobium, iron, silver may be used. The inorganic substrate may be used as the temporary support (E) made of silicon, ceramic, glass, or the like.

The shape of the temporary support (E) is not particularly limited, but is easy to handle in the case of a film or sheet. The film thickness of the temporary support (E) is usually preferably in the range of 1 to 5,000. Mu.m, more preferably in the range of 1 to 300. Mu.m, still more preferably in the range of 1 to 200. Mu.m, still more preferably in the range of 1 to 100. Mu.m, and still more preferably in the range of 1 to 50. Mu.m. The temporary support (E) is preferably a film in order not to lose workability because it is unnecessary to laminate the plating base layer (C) and the stress relaxation layer (B) on the support (a) made of the inorganic compound or the ceramic containing silicon after the plating base layer (C) and the stress relaxation layer (B) are transferred to each other.

In order to facilitate transfer of the plating base layer (C) and the stress relaxation layer (B) from the transfer laminate, the surface of the temporary support (E) is preferably smooth. Specifically, the surface roughness (maximum height Sz) when measured by a laser microscope is preferably in the range of 0.001 to 30 μm, more preferably in the range of 0.01 to 20 μm, and even more preferably in the range of 0.05 to 10 μm. The surface roughness (maximum height Sz) is a value measured by the evaluation method described in ISO 25178, and indicates a distance from the highest point to the lowest point of the surface.

Further, a temporary support having a release layer formed on the surface of the temporary support (E) may be used. The release layer may be formed by coating a silicone release agent and a non-silicone release agent on the temporary support (E). As the non-silicone release agent, alkyd resin, melamine resin, acrylic resin, cellulose resin, urea resin, polyolefin, paraffin wax, silica composite acrylic resin, silica composite melamine resin, silica composite polyurethane resin, silica composite epoxy resin, silica composite phenolic resin, silica composite polyvinyl alcohol resin, silica composite polystyrene resin, silica composite polyvinyl acetate resin, silica composite polyimide resin, silica composite polyamide imide resin can be used. The release layer of the silicone resin prevents adhesion between the plating base layer (C) and the metal plating layer (D) when the silicone resin is transferred to the surface of the plating base layer (C) and the metal plating layer (D) is formed on the plating base layer (C) when the temporary support (E) of the transfer laminate is peeled off. Therefore, as the release layer, a non-silicone release agent is preferably used, and polyolefin, acrylic resin, melamine resin, polyurethane resin, silica composite acrylic resin, silica composite melamine resin, silica composite polyurethane resin, silica composite epoxy resin, silica composite phenolic resin, silica composite polyvinyl alcohol resin, silica composite polystyrene resin, silica composite polyvinyl acetate resin, silica composite polyimide resin, silica composite polyamide imide resin are preferably used.

The thickness of the release layer is not particularly limited as long as the releasability can be ensured, but a thin film is preferable in order to prevent the release layer from adhering to the surface of the plating base layer (C). Specifically, the particle size is preferably 0.01 to 50. Mu.m, more preferably 0.01 to 10. Mu.m, still more preferably 0.01 to 1. Mu.m.

As the temporary support (E), a metal is preferably used. When the plating base layer (C) using metal nanoparticles is formed on the surface of the temporary support (E) described later, if a metal is used, the plating base layer can be dried at a higher temperature than in the case of using a polymer film, and the conductivity of the plating base layer itself can be improved by reducing the surface resistance of the plating base layer (C). In the step of forming the conductive pattern, when a through hole penetrating both surfaces from the surface of the temporary support (E) or a non-through hole extending to the conductive pattern of the inner layer is formed after bonding the surface of the stress relaxation layer (B) of the transfer laminate to the support (a) made of an inorganic compound or ceramic containing silicon, which will be described later, a hole is formed by using a drill or a laser, but when a polymer film is used as the temporary support (a), a stain of the polymer occurs during the hole forming process, and a plating deposition defect may occur in the step of conducting the through hole or the non-through hole. On the other hand, if a metal is used, conventional methods of drilling a hole in a printed board using a drill or a laser can be applied, and copper or aluminum is preferably used as the temporary support (E).

When the plating base layer (C) is coated on the temporary support (E) described later, the surface of the temporary support (E) may be subjected to a surface treatment as needed to facilitate wetting of the coating material. Specifically, methods such as a dry treatment such as a plasma discharge treatment such as a corona discharge treatment, an ultraviolet treatment, and a wet treatment using water, an aqueous solution such as an acid or alkali, an organic solvent, or the like can be mentioned. If the temporary support (E) is excessively surface-treated, the interface between the temporary support (E) and the plating base layer (C), which will be described later, is less likely to be peeled off, and therefore, it is preferable to appropriately perform the surface treatment.

Examples of the method for coating and printing the plating base layer (C) on the temporary support (E) include an inkjet printing method, a reverse printing method, a screen printing method, an offset printing method, a gravure printing method, a flexographic printing method, a pad printing method, a spin coating method, a spray coating method, a bar coating method, a die coating method, a slit coating method, a roll coating method, a dip coating method, a spin coating method, a capillary coating method, a micro gravure coating method, a doctor roll method, and the like.

When the plating base layer (C) is coated on the temporary support (E), the drying temperature after coating and printing is preferably in the range of 50 to 400 ℃, more preferably in the range of 80 to 340 ℃, still more preferably in the range of 120 to 320 ℃, still more preferably in the range of 150 to 300 ℃, and still more preferably in the range of 180 to 280 ℃.

The stress relaxation layer (B) can be formed by coating a part or the whole of the plating base layer (C) formed on the surface of the temporary support (E) with the stress relaxation layer (B), and removing an organic solvent contained in the coating material of the stress relaxation layer (B).

As a method of applying the coating material of the stress relaxation layer (B) to the surface of the plating base layer (C) formed on the surface of the temporary support (E), the organic solvent contained in the coating layer is removed, and for example, a method of drying the coating material using a dryer to volatilize the organic solvent is generally used. The drying temperature needs to be set to a temperature in a range where the organic solvent used can be volatilized.

Next, a method of transferring the transfer laminate to the support (a) made of an inorganic compound containing silicon or ceramic will be described.

As the transfer method, a method of bonding the surface of the stress relaxation layer (B) of the transfer laminate to the support (a) composed of the inorganic compound containing silicon or ceramic by heat and pressure can be used. The method is not particularly limited, and for example, a thermal lamination method, a solvent-free lamination method, an extrusion lamination method, a wet lamination method, a thermal roll transfer method, an in-mold transfer method, a pressing method, a vacuum pressing method, a hydraulic transfer method, and the like can be used.

In the case where the support (a) made of an inorganic compound containing silicon or ceramic is a flexible material and is a roll film, a thermal lamination method, a solvent-free lamination method, an extrusion lamination method, or a wet lamination method is preferably used. In particular, the thermal lamination method is more preferable in terms of easy handling. On the other hand, in the case where the support (a) made of an inorganic compound containing silicon or ceramic is a rigid material, since the thermocompression bonding is often performed in a single piece, a pressing method or a vacuum pressing method is preferably used.

The thermal compression bonding conditions are preferably 50 to 400 ℃, more preferably 80 to 350 ℃, still more preferably 80 to 280 ℃, still more preferably 100 to 200 ℃, still more preferably 120 to 180 ℃. The pressure condition is preferably in the range of 0.05MPa to 35MPa, more preferably in the range of 0.3MPa to 20 MPa.

As a treatment time for the thermocompression bonding, in the case of the thermocompression bonding, the thermocompression bonding is performed by the wire pressure of the roller while being conveyed, and thus the treatment is performed within 1 second. On the other hand, in the case of pressing or vacuum pressing, the treatment is preferably performed in the range of 1 to 120 minutes, preferably in the range of 30 to 60 minutes, more preferably in the range of 30 to 15 minutes, and from the viewpoint of productivity, the treatment is preferably performed in the range of 1 to 5 minutes.

In the case of thermocompression bonding, air may enter between the transfer laminate and the support (a) made of the inorganic compound or ceramic containing silicon, or a gas generated from the support (a) made of the inorganic compound or ceramic containing silicon or the transfer laminate may exist between the transfer laminate and the support (a) made of the inorganic compound or ceramic containing silicon in a gas volume, so that a transfer rate may be reduced. The vacuum condition is preferably 100hPa or less, more preferably 50hPa or less, and still more preferably 13hPa or less. The heating conditions and the pressure conditions are preferably the same as those described above.

Next, a method of bonding the surface of the stress relaxation layer (B) of the transfer laminate to the support (a) composed of an inorganic compound or ceramic containing silicon and peeling off the temporary support (E) will be described.

The method of peeling the temporary support (E) is not particularly limited, and when the adhesion between the support (a) made of an inorganic compound or ceramic containing silicon and the stress relaxation layer (B) is low during the thermocompression bonding (temporary adhesion state), the stress relaxation layer (B) and the plating underlayer (C) cannot be sufficiently transferred to the support (a) made of an inorganic compound or ceramic containing silicon, and a part of the support (a) may remain on the transfer laminate side, so that the peeling direction and speed of the temporary support (E) during peeling are important. Specifically, the support (a) made of the inorganic compound containing silicon or ceramic is preferably peeled off in a direction of 90 to 180 degrees, preferably 120 to 180 degrees, and preferably 150 to 180 degrees. In the peeling, it is preferable that the temporary support (E) side is peeled at the angle not on the support (a) side made of the inorganic compound containing silicon or ceramic. The peeling rate is preferably in the range of 0.01 m/min to 20 m/min, more preferably in the range of 0.05 to 10 m/min, and even more preferably in the range of 0.5 to 5 m/min.

Next, a post-treatment of the laminate after the temporary support (E) of the transfer laminate is peeled off will be described, after the surface of the stress relaxing layer (B) of the transfer laminate is bonded to the support (a) made of an inorganic compound or ceramic containing silicon.

In order to further improve the adhesion between the support (a) made of an inorganic compound containing silicon or ceramic and the stress relaxation layer (B), heat treatment may be performed. The heat treatment conditions are preferably in the range of 80 to 400 ℃, more preferably in the range of 100 to 350 ℃, still more preferably in the range of 120 to 325 ℃, and still more preferably in the range of 150 to 300 ℃. The heat treatment time is preferably in the range of 1 second to 168 hours, more preferably in the range of 30 seconds to 72 hours, and even more preferably in the range of 1 minute to 30 minutes from the viewpoint of productivity.

In the next step, in order to form a metal plating layer (D) and a pattern resist, which will be described later, on the surface of the plating base layer (C), a cleaning treatment is preferably performed to clean the components that reduce the adhesion of the metal plating layer (D) and the pattern resist. As a component for reducing the adhesion, for example, when the temporary support (E) is a resin film, an oligomer component that is present in the film and oozes out on the film surface, and when the release layer is formed on the temporary support (E), a component of the release agent component is transferred to the plating base layer (C), and when the temporary support (E) is a metal, a film of a metal oxide on the temporary support is formed. Examples of the cleaning treatment include a method of performing oxidative decomposition by heating, a plasma discharge treatment such as a corona discharge treatment, a dry treatment such as an ultraviolet treatment, a wet treatment using water, an aqueous solution such as an acid or alkali, water containing ozone (ozone nanobubbles), an organic solvent, or the like on the organic matter present on the surface of the plating base layer (C).

In addition, there are the following methods: a silane coupling layer (F), the stress relaxing layer (B) and the plating base layer (C) are laminated on at least one surface of the support (A) composed of an inorganic compound containing silicon or ceramic.

In the method for forming the silane coupling layer (F), the support (a) composed of the inorganic compound or ceramic containing silicon reacts with the stress relaxation layer (B) to form a covalent bond, so that the adhesion between the interface between the support (a) composed of the inorganic compound or ceramic containing silicon and the silane coupling layer (F) and the interface between the stress relaxation layer (B) and the silane coupling layer (F) can be further improved.

Examples of the silane coupling layer (F) include aminosilane compounds, epoxysilane compounds, (meth) acrylic silane compounds, vinylsilane compounds, mercaptosilane compounds, and acrylic silane compounds. In particular, aminosilane compounds are preferred from the viewpoint of improving the long-term reliability of plating adhesion and the long-term reliability of substrate adhesion.

The thickness of the silane coupling layer (F) is preferably a single-layer film formed on the solid surface during the chemisorption of the organic molecule, more preferably in the range of 0.1 to 100nm, still more preferably in the range of 0.2 to 3nm, and still more preferably in the range of 1 to 2nm, from the viewpoint of adhesion.

Examples of the method of applying the silane coupling layer (F) to the surface of the support (a) composed of the inorganic compound containing silicon or ceramic include gravure method, coating method, screen method, roll method, rotary method, dipping method, and spray method.

In order to further improve the adhesion with the stress relaxation layer (B), the surface of the silane coupling layer (F) is preferably subjected to surface treatment by, for example, a plasma discharge treatment method such as a corona discharge treatment method, a dry treatment method such as an ultraviolet treatment method, or a wet treatment method using water, an acidic or alkaline chemical agent, an organic solvent, or the like.

As a method of coating the silane coupling layer (F) on the surface of the support (a) composed of an inorganic compound or ceramic containing silicon, and then removing the solvent contained in the coating layer, for example, a method of drying the support using a dryer to volatilize the solvent is generally used. The drying temperature may be set to a temperature in a range that allows the solvent to volatilize and does not adversely affect the support (a) made of the inorganic compound containing silicon or the ceramic, such as thermal deformation.

Further, as a method of sequentially stacking the stress relaxation layer (B) and the plating base layer (C) on the silane coupling layer (F), there is a method as follows: a method of sequentially laminating the stress relaxing layer (B) and the plating base layer (C) by the coating; and a method in which the stress relaxing layer (B) and the plating base layer (C) are laminated in this order on the temporary support (E) to produce a transfer laminate, and the surface of the stress relaxing layer (B) of the transfer laminate is bonded to the silane coupling layer (F).

The method of bonding by the transfer method is preferable from the viewpoint of excellent long-term reliability of plating adhesion because the silane coupling layer (F) is not exposed to the solvent of the stress relaxation layer (B) as compared with the coating method.

When the laminate of the present invention is used as a metal wiring described later, there are the following methods: the plating base layer (C), the metal plating layer (D), and the like are removed by etching described later, and a pattern of metal wiring is formed to produce metal wiring.

The metal plating layer (D) constituting the laminate of the present invention is a layer provided for the purpose of forming a highly reliable wiring pattern capable of maintaining good electrical conduction without causing disconnection or the like for a long period of time, for example, when the laminate is used for a conductive pattern or the like.

Examples of the metal constituting the metal plating layer (D) include copper, nickel, chromium, cobalt, tin, and the like. Among them, copper is preferable in that a conductive pattern having low resistance and high corrosion is obtained.

In the laminate of the present invention, it is preferable that the metal constituting the metal plating layer (D) is filled in the voids existing in the plating base layer (C), and the metal constituting the metal plating layer (D) is filled up to the voids existing in the plating base layer (C) in the vicinity of the interface between the support (a) made of an inorganic compound containing silicon or a ceramic and the plating base layer (C), and it is preferable that the adhesion between the plating base layer (C) and the metal plating layer (D) is further improved.

The metal plating layer (D) is a layer formed on the plating base layer (C), and a method of forming the metal plating layer (D) is preferably a method of forming the metal plating layer by plating. Examples of the plating treatment include wet plating methods such as electroplating and electroless plating, and dry plating methods such as sputtering and vacuum evaporation. In addition, the metal plating layer (D) may be formed by combining two or more of these plating methods.

The electroless plating method is, for example, the following method: by bringing the electroless plating solution into contact with the metal constituting the plating base layer (C), a metal such as copper contained in the electroless plating solution is precipitated, and an electroless plating layer (film) composed of a metal film is formed.

Examples of the electroless plating solution include electroless plating solutions containing metals such as copper, nickel, chromium, cobalt, and tin, a reducing agent, an aqueous medium, and a solvent such as an organic solvent.

Examples of the reducing agent include dimethylaminoborane, hypophosphorous acid, sodium hypophosphite, dimethylaminoborane, hydrazine, formaldehyde, sodium borohydride, phenol, and the like.

Further, as the electroless plating solution, a monocarboxylic acid such as acetic acid or formic acid may be used as required; dicarboxylic acid compounds such as malonic acid, succinic acid, adipic acid, maleic acid, and fumaric acid; hydroxycarboxylic acid compounds such as malic acid, lactic acid, glycolic acid, gluconic acid, and citric acid; amino acid compounds such as glycine, alanine, iminodiacetic acid, arginine, aspartic acid, and glutamic acid; organic acids such as aminopolycarboxylic acid compounds such as iminodiacetic acid, nitrilotriacetic acid, ethylenediamine diacetic acid, ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, etc., or complexing agents such as soluble salts (sodium salts, potassium salts, ammonium salts, etc.) of these organic acids, amine compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, etc.

The electroless plating solution is preferably used at a temperature of 20 to 98 ℃.

The above-mentioned electroplating method is, for example, the following method: and (C) applying an electric current in a state in which the plating solution is brought into contact with the surface of the metal constituting the plating base layer (C) or the electroless plating layer (coating) formed by the chemical treatment, thereby depositing the metal such as copper contained in the plating solution on the surface of the conductive material constituting the plating base layer (C) or the electroless plating layer (coating) formed by the chemical treatment provided on the cathode to form a plated layer (metal coating).

Examples of the plating solution include plating solutions containing sulfides of metals such as copper, nickel, chromium, cobalt, and tin, sulfuric acid, and an aqueous medium. Specifically, a plating solution containing copper sulfate, sulfuric acid and an aqueous medium is exemplified.

The plating solution is preferably used at a temperature of 20 to 98 ℃.

In the above-mentioned plating method, since a highly toxic substance is not used and workability is good, it is preferable to form the metal plating layer (D) made of copper by the plating method.

As the dry plating treatment step, a sputtering method, a vacuum evaporation method, or the like can be used. The sputtering method is as follows: introducing an inert gas (mainly argon) in a vacuum, applying negative ions to the metal plating layer (D) forming material to generate glow discharge, then ionizing the inert gas atoms to cause gas ions to strongly strike the surface of the metal plating layer (D) forming material at a high speed, ejecting atoms and molecules constituting the metal plating layer (D) forming material and strongly adhering to the surface of the plating base layer (C) to form a metal plating layer (D).

Examples of the material for forming the metal plating layer (D) by sputtering include chromium, copper, titanium, silver, platinum, gold, nickel-chromium alloy, stainless steel, copper-zinc alloy, indium Tin Oxide (ITO), silica, titania, niobium oxide, and zinc oxide.

In the case of performing the plating treatment by the sputtering method, for example, a magnetron sputtering apparatus or the like can be used.

When the metal plating layer (D) having a thickness of 0.05 μm to 100 μm is directly formed on the support (a) composed of the inorganic compound or ceramic containing silicon, cracks and warpage of the support (a) composed of the inorganic compound or ceramic containing silicon are generated, but the use of the present invention can suppress cracks and warpage.

The thickness of the metal plating layer (D) is preferably in the range of 0.05 to 100 μm, more preferably 1 to 50 μm, even more preferably 5 to 18 μm, from the viewpoint of cracks and warpage caused by the support (a) composed of an inorganic compound containing silicon or ceramic. The thickness of the metal plating layer (D) can be adjusted by controlling the treatment time, current density, the amount of the plating additive used, and the like in the plating treatment step when the metal plating layer (D) is formed.

Examples of the patterning method of the metal plating layer (D) include a photolithography-etching method such as a subtractive method and a semi-additive method, and a method of plating on the printed pattern of the plating base layer (C).

The above subtraction method is as follows: an etching resist layer having a shape corresponding to a desired pattern shape is formed on a metal plating layer (D) constituting a laminate of the present invention, and the plating base layer (C), the metal plating layer (D), and the like, from which the resist is removed by a subsequent development treatment, are dissolved and removed with a chemical agent to form a desired pattern. As the chemical agent, a chemical agent containing copper chloride, iron chloride, or the like can be used.

The semi-addition method comprises the following steps: the stress relaxing layer (B) and the plating base layer (C) are formed on both sides or one side of the support (A) composed of an inorganic compound containing silicon or ceramic, a plating resist layer having a shape corresponding to a desired pattern is formed on the surface of the plating base layer (C), and then a metal plating layer (D) is formed by a plating method, a chemical plating method or a combination thereof, and then the plating resist layer and the plating base layer (C) in contact therewith are removed by dissolution with a chemical agent or the like, thereby forming a desired pattern.

The method of plating the printed pattern of the plating base layer (C) is as follows: the pattern of the plating base layer (C) is printed on the stress relaxation layer (B) formed on both sides or one side of the support (a) composed of an inorganic compound containing silicon or ceramic by an inkjet method, a reverse printing method, or the like, and the metal plating layer (D) is formed on the surface of the plating base layer (C) by an electroplating method, an electroless plating method, or a combination thereof, thereby forming a desired pattern.

In the laminate of the present invention obtained by the above method, the support (a) composed of an inorganic compound or ceramic containing silicon has excellent adhesion to the metal plating layer (D) and excellent crack resistance after formation of a conductive pattern, as compared with the conventional method for forming a copper layer by vapor deposition or sputtering. In addition, when the conductive pattern is formed using the laminate of the present invention, the residual stress of the conductive pattern is effectively reduced by the stress relaxation layer (B), and thus the thickness of the copper film can be increased. Accordingly, the laminate of the present invention can be suitably used as an electronic component such as a printed wiring board, a rigid printed wiring board, a flexible printed wiring board, a package substrate, a metal mesh for a touch panel, an organic solar cell, an organic EL element, a wiring substrate for an LED electrode, an organic transistor, an RFID such as a noncontact IC card, an electromagnetic wave shield, an LED lighting substrate, a digital signage, a photo fusion device, an interposer, or the like, for example.

Examples

The present invention will be described in further detail with reference to examples and comparative examples. In the following examples and comparative examples, "parts" and "%" are on a mass basis.

Modulation example 1: preparation of coating liquid (1) for Forming stress-relaxing layer (B)

60 Parts by mass of a phenoxy resin 4250 (bisphenol A/bisphenol F mixed type manufactured by Mitsubishi chemical corporation, molecular weight 60,000, solid content 100% by mass), 33 parts by mass of an aminotriazine novolac resin (DIC corporation, "PHENOLITE LA-7052", solid content 60% by mass), 17 parts by mass of an epoxy resin (DIC corporation, "EPICLON EXA-830CRP"; bisphenol F type epoxy resin, epoxy equivalent 162 g/equivalent), 3 parts by mass of trimellitic anhydride, and 0.5 parts by mass of "TBZ" manufactured by Kabushiki Kaisha as a curing catalyst were mixed, and diluted with cyclohexanone so that the nonvolatile content became 2% by mass, and uniformly mixed, to thereby obtain a coating liquid (1) for forming a stress relaxation layer (B).

Modulation example 2: preparation of coating liquid (2) for Forming stress-relaxing layer (B)

In a nitrogen-substituted container equipped with a thermometer, a nitrogen inlet pipe, and a stirrer, 100 parts by mass of a polyester polyol (a polyester polyol obtained by reacting 1, 4-cyclohexanedimethanol, neopentyl glycol, and adipic acid), 17.6 parts by mass of 2, 2-dimethylolpropionic acid, 21.7 parts by mass of 1, 4-cyclohexanedimethanol, and 106.2 parts by mass of dicyclohexylmethane-4, 4' -diisocyanate were reacted in a mixed solvent of 178 parts by mass of methyl ethyl ketone to obtain a urethane prepolymer solution having an isocyanate group at the end.

Next, 13.3 parts by mass of triethylamine was added to the urethane prepolymer solution to neutralize the carboxyl group of the urethane prepolymer, and 380 parts by mass of water was further added thereto and sufficiently stirred to obtain an aqueous dispersion of the urethane prepolymer.

To the aqueous dispersion of the urethane prepolymer obtained above, 8.8 parts by mass of a 25% by mass aqueous ethylenediamine solution was added and stirred, whereby the urethane prepolymer was chain-extended. Then, the polyurethane resin was aged and desolvated to obtain an aqueous dispersion (nonvolatile matter: 30 mass%) of a polyurethane resin. The weight average molecular weight of the polyurethane resin was 53,000.

Next, 140 parts by mass of deionized water and 100 parts by mass of the aqueous dispersion of the polyurethane resin obtained above were charged into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet tube, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for dropping a polymerization catalyst, and the temperature was raised to 80℃while blowing nitrogen gas. Then, while maintaining the temperature in the reaction vessel at 80℃with stirring, a monomer mixture composed of 60 parts by mass of methyl methacrylate, 30 parts by mass of N-butyl acrylate and 10 parts by mass of N-N-butoxymethacrylamide and 20 parts by mass of a 0.5% ammonium persulfate aqueous solution were added dropwise from the respective addition funnels over 120 minutes.

After the completion of the dropping, the reaction vessel was further stirred at this temperature for 60 minutes, the temperature was cooled to 40 ℃, diluted with deionized water so that the nonvolatile content became 2 mass%, and then filtered with a 200-mesh filter cloth, whereby the coating liquid (2) for forming the stress relaxation layer (B) which was a core-shell type composite resin having the polyurethane resin as a shell layer and a vinyl resin having methyl methacrylate or the like as a core layer was obtained.

Modulation example 3: preparation of coating liquid (3) for Forming stress-relaxing layer (B)

In a reaction vessel with a thermometer, a nitrogen inlet pipe, and a stirrer, 6.3 parts by mass of 2, 2-dimethylolpropionic acid and 71.1 parts by mass of an urethane body of 4,4' -diphenylmethane diisocyanate were reacted with methyl ethyl ketone to prepare an isocyanate compound, and then 17.8 parts by mass of phenol as a blocking agent was supplied to the reaction vessel to react with each other to prepare a solvent solution of a blocked polyisocyanate.

Next, 4.8 parts by mass of triethylamine was added to the solvent solution of the blocked polyisocyanate to neutralize part or all of the carboxyl groups contained in the blocked polyisocyanate, 400 parts by mass of water was further added thereto and sufficiently stirred, and then the methyl ethyl ketone was distilled off and diluted with deionized water so that the nonvolatile components became 2% by mass and uniformly mixed, whereby the coating liquid (3) for forming the stress relaxation layer (B) containing the blocked polyisocyanate and water was obtained.

Modulation example 4: preparation of coating liquid (1) for Forming plating base layer (C)

A chloroform (30 ml) solution containing 9.6 parts by mass of p-toluenesulfonyl chloride was added dropwise to a mixture containing 20 parts by mass of methoxypolyethylene glycol (number average molecular weight 2,000), 8.0 parts by mass of pyridine and 20ml of chloroform under nitrogen with ice-cold stirring for 30 minutes, and then stirred at a bath temperature of 40℃for 4 hours, followed by mixing with 50ml of chloroform.

Then, the obtained product was washed with 100ml of a 5 mass% aqueous hydrochloric acid solution, then with 100ml of a saturated aqueous sodium hydrogen carbonate solution, then dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, washed with hexane several times, filtered, and dried under reduced pressure at 80℃to obtain methoxypolyethylene glycol having a p-toluenesulfonyloxy group.

5.39 Parts by mass of methoxypolyethylene glycol having a p-toluenesulfonyloxy group, 20 parts by mass of polyethyleneimine (manufactured by Aldrich, molecular weight 25,000), 0.07 parts by mass of potassium carbonate, and 100ml of N, N-dimethylacetamide were mixed, and stirred at 100℃for 6 hours under a nitrogen atmosphere.

Then, 300ml of a mixed solution of ethyl acetate and hexane (volume ratio of ethyl acetate/hexane=1/2) was added, and after stirring vigorously at room temperature, the solid of the product was filtered. The solid was washed with 100ml of a mixed solution of ethyl acetate and hexane (volume ratio of ethyl acetate/hexane=1/2), and then dried under reduced pressure, whereby a compound in which polyethylene glycol and polyethyleneimine were combined was obtained.

138.8 Parts by mass of an aqueous solution containing a compound obtained by combining 0.592 parts by mass of the polyethylene glycol with polyethyleneimine and 10 parts by mass of silver oxide were mixed, and stirred at 25℃for 30 minutes. Then, 46 parts by mass of dimethylethanolamine was slowly added while stirring, and the mixture was stirred at 25℃for 30 minutes. Subsequently, 15.2 parts by mass of a 10% by mass aqueous ascorbic acid solution was slowly added while stirring, and stirring was continued for 20 hours, thereby obtaining a silver dispersion.

To the silver dispersion obtained, a mixed solvent of 200ml of isopropyl alcohol and 200ml of hexane was added, and after stirring for 2 minutes, centrifugal concentration was performed at 3,000rpm for 5 minutes. After removing the supernatant, a mixed solvent of 50ml of isopropyl alcohol and 50ml of hexane was added to the precipitate and stirred for 2 minutes, followed by centrifugal concentration at2,000 rpm for 10 minutes. After removing the supernatant, 20 parts by mass of water was further added to the precipitate and stirred for 2 minutes, and the organic solvent was removed under reduced pressure. After 10 parts by mass of water was further added thereto and stirred and dispersed, the dispersion was allowed to stand in a freezer at-40℃for 1 day and night for freezing, and the resultant was treated in a freeze-dryer (FDU-2200, tokyo physical and chemical Co., ltd.) for 24 hours, whereby silver particles containing a dispersant having basic nitrogen atom-containing groups, which were composed of a grayish green sheet-like block having metallic luster, were obtained.

The obtained powder of silver particles containing a dispersant having a basic nitrogen atom-containing group was dispersed in a mixed solvent of 45 parts by mass of ethanol and 55 parts by mass of ion-exchanged water to prepare a coating solution (1) for forming a plating base layer (C) at 5% by mass. The proportion of the dispersant was calculated from the ash content of the silver particles obtained after heating at 500 ℃ for 1 hour in an electric furnace, and as a result, it was confirmed that the proportion was 5% by mass relative to 100% by mass of the silver solid content.

Modulation example 5: modulation of transfer laminate (1)

The surface of the release film (TN-200, manufactured by Toyo Co., ltd.; release PET film; thickness 38 μm) on which the release layer was formed was coated with the coating solution (1) for forming the plating base layer (C) obtained in preparation example 4 by using a bench-type small coater (KPRINTING PROOFER, manufactured by RK Print Coat Instruments Co., ltd.), and dried at 150℃for 5 minutes, whereby the silver layer corresponding to the plating base layer (C) was coated so that the thickness after drying became 0.1. Mu.m. Then, the coating solution (1) for forming the stress relaxation layer (B) obtained in preparation example 1 was applied with a bench-type mini coater (RK Print Coat Instruments, inc. "K PRINTING profer"), and dried at 180 ℃ for 3 minutes, whereby a layer corresponding to the stress relaxation layer (B) was applied so that the thickness after drying became 0.3 μm, and a plating base layer (C) and the stress relaxation layer (B) were formed on the surface of the release film corresponding to the temporary support (E), thereby obtaining the transfer laminate (1).

Modulation example 6: modulation of transfer laminate (2)

A transfer laminate (2) was obtained in the same manner as in preparation example 5, using the coating liquid (2) for forming the stress relaxation layer (B) instead of the coating liquid (1) for forming the stress relaxation layer (B).

Modulation example 7: modulation of transfer laminate (3)

A transfer laminate (3) was obtained in the same manner as in preparation example 5, using the coating liquid (3) for forming the stress relaxation layer (B) instead of the coating liquid (1) for forming the stress relaxation layer (B).

Modulation example 8: modulation of transfer laminate (4)

The surface of the release film (TN-200, manufactured by Toyo Co., ltd.; release PET film; thickness 38 μm) on which the release layer was formed was coated with the coating solution (1) for forming the plating base layer (C) obtained in preparation example 4 by using a bench-type small coater (KPRINTING PROOFER, manufactured by RK Print Coat Instruments Co., ltd.), and dried at 150℃for 5 minutes, whereby the silver layer corresponding to the plating base layer (C) was coated so that the thickness after drying became 0.1. Mu.m. Then, the coating liquid (1) for forming the stress relaxation layer (B) obtained in preparation example 1 was applied with a bench-type small coater (product of RK Print Coat Instruments company, "K PRINTING profer"), and dried at 180 ℃ for 3 minutes, whereby a layer corresponding to the stress relaxation layer (B) was applied so that the thickness after drying became 0.3 μm. Next, the coating solution (2) for forming the stress relaxation layer (B) obtained in preparation example 2 was applied with a bench-type mini coater (RK Print Coat Instruments, inc. "K PRINTING profer"), and dried at 180 ℃ for 3 minutes, whereby a layer corresponding to the stress relaxation layer (B) was applied so that the thickness after drying became 0.3 μm, and a plating base layer (C) and the stress relaxation layer (B) were formed on the surface of the release film corresponding to the temporary support (E), thereby obtaining the transfer laminate (4).

Example 1

A500 μm thick alkali-free glass substrate (OA-10G manufactured by Nitro Corp., japan) was subjected to corona treatment on both sides (Corona surface modification evaluation device TEC-4AX, manufactured by CHUNYAKO Co., ltd.) with an electrode-substrate distance of 0.5mm, 100W). Then, the coating liquid (2) for forming the stress relaxation layer (B) obtained in preparation example 2 was coated by a bar coater and dried to form the coating liquid. Then, the coating solution (1) for forming the plating base layer (C) obtained in preparation example 4 was sequentially coated with a bar coater and dried to form the coating solution. Then, a metal plating layer (D) having a thickness of 18 μm was formed by copper plating, thereby obtaining a laminate (1) in which layers were stacked.

Example 2

A500 μm thick alkali-free glass substrate (OA-10G manufactured by Nitro Corp., japan) was subjected to corona treatment on both sides (Corona surface modification evaluation device TEC-4AX, manufactured by CHUNYAKO Co., ltd.) with a distance between the electrode and the substrate of 0.5mm, 100W. Then, the surface of the transfer laminate (1) obtained in preparation example 5 on which the stress relaxation layer (B) was formed was bonded to both surfaces of alkali-free glass, and a hand press (a "small test press" manufactured by eastern chemical Co., ltd.) was used, the upper surface hot plate of the press was SUS, the lower surface hot plate was SUS, the upper surface hot plate temperature was 150℃and the lower surface hot plate temperature was 150℃and the laminate was thermally bonded under a pressure of 5MPa for 10 minutes. Then, the release films of the transfer laminate (1) thermally bonded to only the two sides of the alkali-free glass are peeled off, thereby forming the stress relaxing layer (B) and the plating base layer (C) on the two sides of the alkali-free glass. Then, a metal plating layer (D) having a thickness of 18 μm was formed by copper plating, thereby obtaining a laminate (2) in which layers were stacked.

Example 3

A laminate (3) was obtained in the same manner as in example 2, using an alkali-free glass having a thickness of 35 μm instead of an alkali-free glass having a thickness of 500 μm.

Example 4

A laminate (4) was obtained in the same manner as in example 2, using a silicon wafer having a thickness of 500 μm instead of the alkali-free glass having a thickness of 500. Mu.m.

Example 5

A laminate (5) was obtained in the same manner as in example 2, using an alumina substrate having a thickness of 500 μm instead of alkali-free glass having a thickness of 500 μm.

Example 6

A laminate (6) was obtained in the same manner as in example 2, except that the transfer laminate (2) produced in preparation example 6 was used.

Example 7

A laminate (7) was obtained in the same manner as in example 2, except that the transfer laminate (3) produced in preparation example 7 was used.

Example 8

A laminate (8) was obtained in the same manner as in example 2, except that the transfer laminate (4) produced in preparation example 8 was used.

Example 9

For alkali-free glass having a thickness of 500. Mu.m, a base glass substrate was immersed in a 1wt% aminosilane solution, and then dried, whereby a silane coupling agent treatment was performed. A laminate (9) was obtained in the same manner as in example 8, except that the alkali-free glass substrate treated with the silane coupling agent was used.

Comparative example 1

A Ti layer having a thickness of 20nm and a Cu layer having a thickness of 200nm were continuously formed on the surface of an alkali-free glass having a thickness of 500 μm by a sputtering method, and then a metal plating layer (D) having a thickness of 18 μm was formed by electroplating copper, thereby obtaining a laminate (R1) in which the layers were laminated.

Comparative example 2

A laminate (R2) was obtained in the same manner as in comparative example 1, using a silicon wafer having a thickness of 500 μm instead of the alkali-free glass having a thickness of 500 μm.

Method for evaluating cracks generated in support (A) made of inorganic Compound or ceramic containing silicon

Regarding the laminate formed by copper plating, wiring processing was performed so that the wiring length was 50mm and the wiring width was LINE/space=50/50 μm, and the number of cracks generated in the support made of an inorganic compound containing silicon or ceramic of the wiring board after the hot oil test was measured using an optical microscope. The test conditions for the hot oil test were 100 times of the operation of immersing in a solution at 260 c for 10 seconds and then immersing in a solution at 20 c for 20 seconds under a liquid phase atmosphere. Regarding the number of cracks generated in the support composed of an inorganic compound containing silicon or ceramic, 10 processed wires were observed, and the average value of each was evaluated.

A: the number of cracks is 0 or more and less than 2.

B: the number of cracks is 2 or more and less than 4.

C: the number of cracks is 4 or more and less than 7.

D: the number of cracks is 7 or more and less than 10.

E: the number of cracks is 10 or more.

< Measurement of warp amount of support (A) composed of inorganic Compound or ceramic containing silicon >

Regarding the laminate formed by copper plating, the amount of warpage of four corners was measured using a feeler gauge. For a 300mm×300mm glass substrate as a substrate, a measured value at a copper film thickness of 18 μm was evaluated. Regarding the value of the warpage amount, the maximum value of the warpage amount at four corners was evaluated.

A: the warpage amount is 0mm or more and less than 0.1mm.

B: the warpage amount is 0.1mm or more and less than 0.3mm.

C: the warpage amount is 0.3mm or more and less than 0.5mm.

D: the warpage amount is 0.5mm or more and less than 1.0mm.

E: the warpage amount is 1.0mm or more.

< Normal intensity: evaluation based on peel test

The peel strength of the laminate obtained above was measured by the method according to IPC-TM-650, NUMBER2.4.9. The lead width used in the measurement was 1mm, and the peeling angle was 90 °. The peel strength tends to be high as the thickness of the plating layer is thicker, but the peel strength in the present invention is measured based on the measurement value obtained when the plating layer is 18 μm, which is commonly used at present.

Based on the measured peel strength value before heating, the adhesion was evaluated according to the following criteria.

A: the peel strength was 700N/m or more.

B: the peel strength is 500N/m or more and less than 700N/m.

C: the peel strength is 300N/m or more and less than 500N/m.

D: the peel strength is 100N/m or more and less than 300N/m.

E: the peel strength has a value of less than 100N/m.

The results of evaluating the number of cracks, warpage and adhesion of examples 1 to 9 and comparative examples 1 and 2 are shown in tables 1 to 2.

TABLE 1

TABLE 2

	Comparative example 1	Comparative example 2
			Number of cracks	E	D
Amount of warpage	E	E
			Adhesion of	E	E

Claims

3. The laminate according to claim 1 or 2, further comprising a silane coupling layer (F) between the support (a) composed of an inorganic compound containing silicon or ceramic and the stress relaxing layer (B).

4. The laminate according to claim 1 or 2, wherein the thickness of the support (a) composed of an inorganic compound or ceramic containing silicon is 1 to 10,000 μm.

5. The laminate according to claim 1 or 2, wherein the stress relaxation layer (B) has a thickness of 0.01 to 100 μm.

6. The laminate according to claim 1 or 2, wherein the stress relaxation layer (B) is at least selected from the group consisting of urethane resins, acrylic resins, core-shell type composite resins having a urethane resin as a shell and an acrylic resin as a core, epoxy resins, phenoxy resins, imide resins, amide resins, melamine resins, phenolic resins, urea-formaldehyde resins, blocked isocyanates obtained by reacting a blocking agent such as phenol with a polyisocyanate, polyvinyl alcohol, and polyvinylpyrrolidone.

7. The laminate according to claim 1 or 2, wherein the stress relaxation layer (B) is one or more layers.

8. Laminate according to claim 1 or 2, characterized in that the thickness of the plating base layer (C) is 1-10,000 mg/m ².

9. The laminate according to claim 1, wherein the thickness of the metal plating layer (D) is 0.05 to 100 μm.

10. A laminate according to claim 3, wherein the silane coupling layer (F) has a thickness of 0.1 to 100nm.

11. The method for producing a laminate according to claim 1, comprising the steps of:

And step 3 of forming a metal plating layer (D) on the surface of the plating base layer (C).

12. The method for producing a laminate according to claim 2, comprising the steps of:

a step 2 of bonding a surface of the transfer laminate, on which the stress relaxing layer (B) is formed, to at least one surface of a support (a) made of an inorganic compound containing silicon or ceramic;

Step 3 of peeling off the temporary support (E) of the transfer laminate bonded to the support (a) made of an inorganic compound or ceramic containing silicon, and forming the stress relaxing layer (B) and the plating base layer (C) on at least one surface of the support (a) made of an inorganic compound or ceramic containing silicon;

13. The manufacturing method according to claim 11 or 12, characterized by comprising the steps of: the silane coupling layer (F) is formed on at least one surface of a support (A) composed of an inorganic compound containing silicon or a ceramic.

14. A printed wiring board, a package substrate, an interposer, a wiring substrate for LED electrodes, and a photo fusion device, comprising the laminate according to claim 1 or 2.