WO2009154083A1 - 積層体及び回路配線基板 - Google Patents
積層体及び回路配線基板 Download PDFInfo
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- WO2009154083A1 WO2009154083A1 PCT/JP2009/060266 JP2009060266W WO2009154083A1 WO 2009154083 A1 WO2009154083 A1 WO 2009154083A1 JP 2009060266 W JP2009060266 W JP 2009060266W WO 2009154083 A1 WO2009154083 A1 WO 2009154083A1
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- Prior art keywords
- molecular adhesive
- substrate
- adhesive layer
- layer
- group
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- 0 C*C(C)SC(C)N(C)c1nc(*)nc(S)n1 Chemical compound C*C(C)SC(C)N(C)c1nc(*)nc(S)n1 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/06—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J121/00—Adhesives based on unspecified rubbers
- C09J121/02—Latex
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/389—Improvement of the adhesion between the insulating substrate and the metal by the use of a coupling agent, e.g. silane
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/0133—Elastomeric or compliant polymer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Definitions
- the present invention is a laminate in which an entropy elastic molecular adhesive layer is formed between two substrates, the elastic molecular adhesive layer comprising an entropy elastic layer and a molecular adhesive layer. It relates to a laminate.
- the present invention relates to an electronic mounting component, a precision mechanical component, a building structure, a circuit wiring board, a decorative plating product, and an adhesive composite product made of the laminate.
- Patent Document 1 conversion from a physical bonding method to a chemical bonding method has been proposed (for example, Patent Document 1). To 3).
- the adhesion is caused by chemical bonding by molecules, the smoothness of the substrate surface is high at the time of the bonding process, the distance between the substrates is close to a reactable distance,
- the fact that the substrate is a material that can alleviate stress concentration is an important factor for achieving adhesion, such as relaxation of stress concentration, improved reliability, high adhesion (especially conductor layer), heat resistance, and almighty properties. It was practically insufficient for improving the adhesion between substrates having a large surface roughness and substrates having a shape-retaining function, such as (adherable regardless of the type of adherend).
- the present situation is that the laminated body that has solved the problems of the prior art as described above is not yet known.
- the present invention improves adhesion to a substrate having a large surface roughness, which is a problem particularly in the production of a laminate, relaxes stress concentration, improves reliability, high adhesion (especially a conductor layer), heat resistance, almighty ( It is an object of the present invention to provide a laminate that can solve the problems of the conventional methods, such as adhering regardless of the type of adherend.
- the elastic molecular adhesion layer of the present invention can be said to be a truly revolutionary invention that has changed the concept of conventional adhesives.
- the present invention is as follows.
- Item 1.2 A laminate obtained by forming an entropy elastic molecular adhesion layer between two substrates,
- the entropy elastic molecular adhesive layer is composed of an entropy elastic layer and a molecular adhesive layer.
- the entropy elastic molecular adhesive layer forms the molecular adhesive layer 1 on the substrate, forms the entropy elastic body layer on the molecular adhesive layer 1, and further stacks the molecular adhesive layer 2 on the entropy elastic body layer
- the laminate according to Item 1 wherein the laminate is formed as described above.
- the entropy elastic molecular adhesive layer is formed by previously forming a molecular adhesive layer on the surfaces of two substrates and sandwiching the entropy elastic layer between the two substrates on which the molecular adhesive layer is formed.
- Item 4. Item 4. The laminate according to any one of Items 1 to 3, wherein the molecular adhesive layer is formed by reacting an OH group present on the substrate surface with the molecular adhesive.
- Item 3. The laminate according to Item 1 or 2, wherein the molecular adhesive layer is formed by reacting an OH group present on the surface of the entropy elastic layer and the molecular adhesive.
- the entropy elastic layer is formed by bringing an uncrosslinked or cross-linked entropy elastic composition into contact with the entire surface or a part of the molecular adhesive layer, and adhering it with heat and / or an optical medium under pressure. 6.
- Entropy elastic layer is 1,4-cis butadiene rubber (BR), acrylonitrile-butadiene copolymer rubber (NBR), ethylene-propylene-diene rubber (EPDM), fluoro rubber (FKM), epichlorohydrin rubber (CHR) 8.
- the molecular adhesive layer has the general formula (1): A-SiX 1 3-n Y n (1) (In the formula, A is a group capable of binding to the entropy elastic layer, and X 1 may be the same or different, and each may have a hydrogen atom or a substituent having 1 to 1 carbon atoms. 10 is a saturated or unsaturated aliphatic hydrocarbon group, Y is an alkyloxy group having 1 to 10 carbon atoms, and n is an integer of 1 to 3) 9.
- Item 10 The laminate according to Item 9, wherein the molecular adhesive is a molecular adhesive represented by the following general formulas (2) to (6).
- R 1 and R 3 may be the same or different and each represents a single bond, a saturated or unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 20 carbon atoms).
- the aliphatic hydrocarbon group or aromatic hydrocarbon group may contain —NH—, —CO—, —O—, —S—, —COO—, wherein R 2 is a hydrogen atom, substituted A saturated or unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon residue having 1 to 10 carbon atoms which may have a group, X 1 may be the same or different from each other;
- R 4 and R 5 may be the same or different and each may have a substituent, a saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic group.
- X 2 to X 4 are each a linear or branched, saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic group, which may have a substituent.
- a divalent aliphatic hydrocarbon group or an aromatic hydrocarbon group may include--, -SH, -SCSN (CH 3 ) 2 , -SSCSN (CH 3 ) 2 , -SCSN (C 2 H 5 ) 2 , -SCSN (C 4 H 9 ) 2 , -SCSN (C 8 H 17 ) 2 , -SS-, -SSS-, -SSSS-,
- D is 0, 1 or 2, e is 1 or 2), H 2 N—R 7 —SiX 1 3-n Y n (6)
- R 7 is an optionally substituted saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group optionally having a substituent.
- X 1 and Y are the same as described above, and n is an integer from 1 to 3.
- Item 11. The laminate according to any one of Items 1 to 10, wherein the substrate is at least one substrate selected from the group consisting of metals, ceramics, resins, and composites thereof.
- Item 12 The laminate according to any one of Items 1 to 11, wherein at least one of the two substrates is a conductive substrate.
- Item 13. Item 13.
- the laminate according to Item 12 wherein the conductive substrate is formed on the entire surface or a part of the molecular adhesive layer.
- Item 14. The laminate according to Item 12 or 13, wherein the conductive substrate is formed by electroless plating after supporting the catalyst on the molecular adhesive layer.
- Item 15. The laminate according to Item 14, wherein the conductive substrate is copper plating.
- Item 16. A circuit wiring board comprising the laminate according to any one of items 1 to 15.
- a decorative plated product comprising the laminate according to any one of items 1 to 15.
- An adhesive composite product comprising the laminate according to any one of items 1 to 16.
- the present invention is a substrate having a large surface roughness, which becomes a problem when a laminate is manufactured by using an elastic molecular adhesive layer composed of an entropy elastic layer and a molecular adhesive layer when two substrates having a shape maintaining function are stacked.
- Problems of conventional technology such as adhesion to the surface, relaxation of stress concentration, improved reliability, high adhesion (especially conductor layer), heat resistance, almighty (adhesive regardless of the type of adherend) Can be solved at once.
- the present invention is a laminate in which an elastic molecular adhesive layer is formed between two substrates, the elastic molecular adhesive layer comprising an entropy elastic layer and a molecular adhesive layer. About the body.
- substrate 1 and substrate 2 may be the same or different, and are not particularly limited as long as they have a shape-retaining function.
- the “substrate having a shape-retaining function” means a fine shape (for example, fine irregularities) of several to several tens of nanometers on the surface of the substrate at the temperature (particularly room temperature) when the laminate of the present invention is used. ) Means a substrate that hardly changes at a pressure applied at the time of lamination (adhesion).
- substrates selected from the group consisting of metals, ceramics, resins, and composites thereof correspond to substrates having a shape maintaining function.
- entropy elastic bodies such as rubber often have a fine shape of several nanometers to several tens of nanometers on the surface, which changes with the pressure applied at the time of lamination (adhesion), and usually has a shape maintaining function. Not applicable to substrates.
- Examples of the metal serving as a substrate having a shape maintaining function include Al, Mg, Zn, Cu, Sn, Ag, Ni, Si, Au, Fe, Pt, Mo, W and their alloys and the like, foils, and laminates thereof. A plate, a curved body, etc. can be mentioned. Of these metal substrates, Cu, Ag, Ni, Au, Ni / Fe, Co, Fe, Pt, and brass can be formed by plating.
- Ceramics include plates such as Al, Mg, Zn, Cu, Sn, Ag, Ni, and Si oxides, foils, curved shapes, and laminates thereof.
- the resin examples include cellulose and derivatives thereof, hydroxyethyl cellulose, starch, cellulose diacetate, surface saponified vinyl acetate resin, low density polyethylene, high density polyethylene, i-polypropylene, petroleum resin, polystyrene, s-polystyrene, chroman indene resin.
- Terpene resin styrene-divinylbenzene copolymer, ABS resin, polymethyl acrylate, polyethyl acrylate, polyacrylonitrile, methyl methacrylate, ethyl methacrylate, polycyanoacrylate, polyvinyl acetate, polyvinyl alcohol, polyvinyl formal , Polyvinyl acetal, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, vinyl chloride / ethylene copolymer, polyvinylidene fluoride, vinylidene fluoride / ethylene copolymer, fluoride Nylidene / propylene copolymer, 1,4-transpolybutadiene, polyoxymethylene, polyethylene glycol, polypropylene glycol, phenol / formalin resin, cresol / formalin resin, resorcin resin, melamine resin, xylene resin, toluene resin, glyphal resin, Modified g
- metal powder metal fibers, ceramics, ceramic fibers, carbon black, calcium carbonate, talc, clay, kaolin, wet
- fillers such as dry silica, and fibers and fabrics such as rayon, nylon, polyester, vinylon, steel, Kevlar fiber (registered trademark of DuPont), carbon fiber, glass fiber, cross-linking agent such as peroxide, A polyfunctional monomer can be added and used in a three-dimensional form.
- a composite of metal, ceramics, and resin means a mixture of metal and ceramic powder and resin, such as a plate, foil, and curved body.
- the combination of the substrates 1 and 2 can be appropriately selected depending on the purpose of use of the laminate.
- an aluminum plate and a glass epoxy resin substrate, glass and copper, glass and glass, glass and SUS, glass epoxy and Copper, PET and copper, magnesium and aluminum, polyimide and copper, polypropylene and aluminum, nylon and iron and the like are preferable.
- the laminated body of this invention when using the laminated body of this invention as a circuit board etc., it is preferable that at least one of two board
- substrates is a conductive substrate, It is preferable that it is a conductive plating layer formed by plating, and copper plating It is particularly preferred that
- the thickness and size of the substrate can be appropriately selected according to the purpose of use, and are not particularly limited.
- the entropy elastic molecular adhesion layer used in the present invention comprises an entropy elastic layer and a molecular adhesive layer.
- the effective thickness of the entropy elastic molecular adhesive layer varies depending on the intended properties of the product, and therefore cannot be uniquely determined, and can be determined as appropriate depending on the form of the product. However, the strength at the interface is particularly required. In this case, the thickness is preferably 0.1 to 5,000 ⁇ m, more preferably 1 to 2,000 ⁇ m. If the thickness of the entropy elastic molecular adhesion layer is less than 0.1 ⁇ m, its film formability is difficult, and stress relaxation and reliability improvement may not be achieved sufficiently. In some cases, it is difficult to reduce the size and density of the laminated substrate, and the production cost increases and the productivity tends to decrease.
- the “molecular adhesive layer” refers to a layer composed of a molecular adhesive and is represented by the general formula (1): A-SiX 1 3-n Y n (1)
- A is a group capable of binding to the entropy elastic layer, and X 1 may be the same or different, and each may have a hydrogen atom or a substituent having 1 to 1 carbon atoms.
- 10 is a saturated or unsaturated aliphatic hydrocarbon group, Y is an alkyloxy group having 1 to 10 carbon atoms, and n is an integer of 1 to 3) It is preferable that it is a layer which contains one or more types of molecular adhesives shown by these.
- the molecular adhesive (alkoxysilyl group represented by SiX 1 3-n Y n in eg, the general formula (1),) OH groups capable of chemically bonding groups on the substrate surface or the like and an entropy elastic Including both a body layer and a group capable of chemically bonding (for example, a cross-linking reactive group represented by A in the general formula (1)), and the molecular adhesive is chemically applied to the surface of the substrate and the entropy elastic body.
- the molecular adhesive may further have another functional group, for example, a functional group that chemically bonds to a metal.
- the substrate is a metal plating, it is chemically bonded to the metal plating by a functional group that chemically bonds to the metal.
- molecular adhesive represented by the general formula (1) examples include molecular adhesives represented by the general formulas (2) to (6) having the following structures.
- R 1 and R 3 may be the same or different, and each is a single bond, a saturated or unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 20 carbon atoms.
- the aliphatic hydrocarbon group or aromatic hydrocarbon group may contain —NH—, —CO—, —O—, —S—, —COO—, wherein R 2 is a hydrogen atom, A saturated or unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon residue having 1 to 10 carbon atoms which may have a substituent, and X 1 may be the same or different from each other; , A hydrogen atom, an optionally substituted saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, Y is an alkyloxy group having 1 to 10 carbon atoms, and n and m are An integer of 1 to 3, and M 1 is H, Li, Na, K, Cs).
- R 1 and R 3 are a single bond, a saturated or unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 12, more preferably 2 to 8).
- a single bond —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 —, —CH 2 CH 2 SCH 2 CH 2 —, —CH 2 CH 2 CH 2 SCH 2 CH 2 CH 2 —, —CH 2 CH 2 NHCH 2 CH 2 CH 2 —, — (CH 2 CH 2 ) 2 NCH 2 CH 2 CH 2 —, —C 6 H 4 —, —C 6 H 4 C 6 H 4 —, —CH 2 C 6 H 4 CH 2 —, —CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 —, —CH 2 CH 2 OCONHCH 2 CH 2 CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 CH
- R 2 is a hydrogen atom, a saturated or unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 20 carbon atoms (preferably 2 to 8 carbon atoms) which may have a substituent, Specifically, for example, CH 3 —, C 2 H 5 —, nC 3 H 7 —, CH 2 ⁇ CHCH 2 —, nC 4 H 9 —, C 6 H 5 —, C 6 H 11 -And the like.
- X 1 may be the same or different and each is a hydrogen atom or a saturated or unsaturated aliphatic hydrocarbon having 1 to 10 carbon atoms (preferably 1 to 6) which may have a substituent.
- a group specifically, for example, H-, CH 3 -, C 2 H 5 -, n-C 3 H 7 -, i-C 3 H 7 -, n-C 4 H 9 -, i- C 4 H 9- , t-C 4 H 9- and the like can be mentioned.
- Y is an alkyloxy group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), for example, CH 3 O—, C 2 H 5 O—, nC 3 H 7 O—, iC 3 H 7 O—, nC 4 H 9 O—, iC 4 H 9 O—, tC 4 H 9 O— and the like can be mentioned.
- n and m are integers of 1 to 3
- M 1 is H, Li, Na, K, or Cs.
- Specific examples of the compounds represented by the general formulas (2) and (3) include 6- (3- (triethoxysilyl) propylamino) -1,3,5-triazine-2,4-dithiol monosodium ( TES), 6- (3- (triethoxysilyl) propylamino) -1,3,5-triazine-2,4-dithiol, 6- (3- (monomethyldiethoxysilyl) propylamino) -1,3 5-triazine-2,4-dithiol monosodium (DES), 6- (3- (dimethylmonoethoxysilyl) propylamino) -1,3,5-triazine-2,4-dithiol monosodium (MES) 6-di- (3-triethoxysilylpropylamino) -1,3,5-triazine-2,4-dithiol monosodium (BTES), 6-N-cyclohex Ru-N- (3- (trieth
- R 4 and R 5 may be the same or different from each other, and may have a substituent, a saturated or unsaturated aliphatic hydrocarbon having 1 to 10 (preferably 1 to 6) carbon atoms Group or aromatic hydrocarbon group, specifically, for example, CH 3 —, C 2 H 5 —, C 3 H 7 —, C 4 H 9 —, (CH 3 ) 2 CH—, (CH 3 ) 3 C—, C 6 H 5 —, CH 3 CH 2 CH 2 — and the like.
- a saturated or unsaturated aliphatic hydrocarbon having 1 to 10 (preferably 1 to 6) carbon atoms Group or aromatic hydrocarbon group specifically, for example, CH 3 —, C 2 H 5 —, C 3 H 7 —, C 4 H 9 —, (CH 3 ) 2 CH—, (CH 3 ) 3 C—, C 6 H 5 —, CH 3 CH 2 CH 2 — and the like.
- X 2 to X 4 are each a linear or fractional saturated or unsaturated aliphatic hydrocarbon group or aromatic group having 1 to 10 carbon atoms (preferably 1 to 6), which may have a substituent.
- X 2 to X 4 include, for example, CH 3 —, C 2 H 5 —, C 3 H 7 —, C 4 H 9 —, (CH 3 ) 2 CH—, (CH 3 ) 3 C— , C 6 H 5- , CF 3 CH 2 CH 2-, etc., CH 3 O-, C 2 H 5 O-, nC 3 H 7 O-, i-C 3 H 7 O-, n-C 4 H 9 O—, iC 4 H 9 O—, tC 4 H 9 O— and the like can be exemplified.
- a and c are each an integer from 0 to 3
- b is an integer from 0 to 2
- r is an integer from 0 to 100.
- Specific examples of the compound represented by the general formula (4) include vinyl methoxysiloxane homopolymer, vinyl terminal diethylsiloxane dimethylsiloxane copolymer, vinyl terminal trifluoropropylsiloxane dimethylsiloxane copolymer and the like.
- R 6 is a divalent aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 18 carbon atoms (preferably 1 to 12, more preferably 2 to 8 carbon atoms), and the aliphatic hydrocarbon group includes- NH—, —CO—, —O—, —S—, —COO—, —C 6 H 4 — may be contained.
- -CH 2 -, - CH 2 (CH 2) q-2 CH 2 - (q is 2-18 integer)
- Z includes -SH, -SCSN (CH 3 ) 2 , -SSCSN (CH 3 ) 2 , -SCSN (C 2 H 5 ) 2 , -SCSN (C 4 H 9 ) 2 , -SCSN (C 8 H 17 2 , -SS-, -SSS-, -SSSS-,
- —SH, —SS—, —SSS—, and —SSSS— are preferred from the viewpoint of crosslinkability with rubber.
- D is 0, 1 or 2, but is preferably 0 or 1 and more preferably 0 from the viewpoint of reactivity with the substrate.
- e is 1 or 2.
- molecular adhesive of the present invention represented by the general formula (5) include bis (triethoxysilylpropyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane and the like. be able to.
- R 7 is a saturated or unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms (preferably 2 to 12) which may have a substituent or an aromatic group which may have a substituent.
- X 1 , Y, and n are the same as described above.
- molecular adhesive used in the present invention represented by the general formula (6) include, for example, 3-aminopropyltriethoxysilane, 3- (3-aminopropoxy) -3,3-dimethyl-1-propenyltrimethoxy A silane etc. can be mentioned.
- the molecular adhesives represented by the general formulas (2) to (6) may be used alone or in combination of two or more.
- R 8 is —OR 9 , —NR 10 R 11, or —SM 2 .
- R 9 is an alkyl group having 1 to 4 carbon atoms, and any alkyl group having 1 to 4 carbon atoms described in the present specification can be used.
- R 10 and R 11 may be the same or different, and R 10 and R 11 may be bonded to each other, and each of H, an alkyl group having 1 to 4 carbon atoms, an alkylene group, an alkenyl group Group or a phenylene group.
- the alkylene group may contain —NH—, —CO—, —O—, —S—, and —COO—. Specifically, the thing similar to what was described in this specification can be mentioned.
- M 2 to M 4 may be the same or different and are an alkali metal or H.
- alkali metal examples include Li, Na, K, and Cs.
- triazine compound represented by the general formula (7) examples include 1,3,5-triazine-2,4,6-trithiol, 1,3,5-triazine-2-dibutylamino-4,6. -Dithiol, 1,3,5-triazine-2-diallylamino-4,6-dithithiol and the like.
- the thickness of the molecular adhesive layer is not particularly limited, but is preferably 1 ⁇ 10 ⁇ 4 to 1 ⁇ 10 2 ⁇ m, and more preferably 1 ⁇ 10 ⁇ 3 to 1 ⁇ 10 ⁇ 2 ⁇ m. When the thickness of the molecular adhesive layer exceeds 1 ⁇ 10 2 ⁇ m, the adhesiveness tends to decrease.
- the molecular adhesive used in the present invention is bonded to the surface of the substrate by an alkoxysilyl group. It can be chemically bonded to the OH group, and can have a cross-linking reaction with the entropy elastic body by having various functional groups. Accordingly, the entropy elastic body layer and the substrate, which will be described later, can be bonded to each other between different materials, and the laminate of the present invention having two or more such molecular adhesive layers has an entropy elastic body between them. Therefore, improvement of adhesion to substrates with large surface roughness, relaxation of stress concentration, improvement of reliability, high adhesion (especially conductive) Body layer), heat resistance, and almighty property (adhesion is possible regardless of the type of adherent).
- the “entropy elastic layer” used in the present invention is a layer made of an entropy elastic body, and the temperature (for example, 15 to 200 ° C.) at the time of forming the laminate is higher than the glass transition point. It is a layer formed from the entropy elastic body composition containing the polymeric material which is.
- the entropy elastic body include plastics that are in a rubber state at or above the glass transition point at the temperature at which the laminate is formed, as well as rubbers such as so-called natural rubber and synthetic rubber. Of these, rubbers, polyethylene, and the like that have a glass transition point lower than room temperature and are in a rubber state at room temperature are preferable.
- BR 1,4-cis butadiene rubber
- isoprene rubber polychloroprene
- styrene / butadiene copolymer rubber hydrogenated styrene / butadiene copolymer rubber
- acrylonitrile / butadiene copolymer rubber acrylonitrile / butadiene copolymer rubber.
- NBR hydrogenated acrylonitrile / butadiene copolymer rubber, polybutene, polyisobutylene, ethylene / propylene rubber, ethylene-propylene-diene rubber (EPDM), ethylene oxide-epichlorohydrin copolymer, polyethylene, polypropylene, polyamide, Chlorinated polyethylene, chlorosulfonated polyethylene, alkylated chlorosulfonated polyethylene, chloroprene rubber, chlorinated acrylic rubber, brominated acrylic rubber, fluororubber (FKM), epichlorohydrin rubber (CHR) Binary, terpolymers such as epichlorohydrin and its copolymer rubber, chlorinated ethylene propylene rubber, chlorinated butyl rubber, brominated butyl rubber tetrafluoroethylene, Teflon (registered trademark), hexafluoropropylene, vinylidene fluoride, Examples thereof include acrylic rubber, ethylene acrylic rubber, silicon resin,
- BR 1,4-cis butadiene rubber
- NBR acrylonitrile-butadiene copolymer rubber
- EPDM ethylene-propylene-diene rubber
- FKM fluorine rubber
- CHR epichlorohydrin rubber
- fluorine Silicone rubber peroxide type silicon rubber, addition type silicon rubber, condensation type silicon rubber, and polyethylene are preferable.
- the entropy elastic composition may further include one or more selected from a crosslinking agent, a crosslinking accelerator, a vulcanizing agent, a vulcanization accelerator, a filler, a metal activator, and a metal catalyst.
- a crosslinking agent e.g., a crosslinking accelerator
- a vulcanizing agent e.g., a vulcanizing agent
- a vulcanization accelerator e.g., a filler
- a metal activator e.g., a metal catalyst
- One or more selected from stabilizers, softeners, colorants, and ultraviolet absorbers can be included as necessary.
- crosslinking agent examples include sulfur, peroxide, triazine thiols, tetramethyl thiuram tetrasulfide, dithiomorpholine, and the like. More specifically, triazine trithiol, 2-dibutylamino-1,3,5-triazine-4,6-dithiol, ethylenethiourea, bisphenol A, sulfur, colloidal sulfur, dicumyl peroxide, di-t-butyl peroxide 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, di (t-butylperoxyisopropyl) benzene And peroxides such as benzoquinone dioxime, sarigen, dimethylol / phenol, and the like. These can be used alone or in combination of two or more.
- the blending amount of the crosslinking agent is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the polymer material.
- crosslinking accelerator examples include sulfenamides, mercaptobenzothiazoles, thiurams, guanamines and polyfunctional monomers. More specifically, dibenzothiazoyl disulfide, 4-morpholinodithiobenzothia Thiazoles such as Zole, N-cyclohexyl-2-benzothiazoylsulfenamide, Nt-butyl-2-benzothiazoylsulfenamide, N-oxydiethylene-2-benzothiazoylsulfenamide, Sulfenamides such as N-diisopropyl-2-benzothiazoyl sulfenamide, N-dicyclohexyl-2-benzothiazoyl sulfenamide, and tetramethylturum disulfide, tetraethylturum disulfide, tetrabutylturum disulfide Tulamic crosslinking accelerators such as tetraocty
- the blending amount of the crosslinking accelerator is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polymer material.
- the filler is added for the purpose of increasing the strength of the entropy elastic layer or increasing the amount.
- Fillers include various grades of carbon black such as HAF and FEF, calcium carbonate, talc, clay, kaolin, glass, wet and dry silica, rayon, nylon, polyester, vinylon, steel, Kevlar fiber ( (Registered trademark of DuPont), fibers and fabrics such as carbon fiber and glass fiber, and the like can be used alone or in combination of two or more.
- the blending amount of the filler is preferably 0 to 200 parts by weight and more preferably 10 to 100 parts by weight with respect to 100 parts by weight of the polymer material.
- the metal activator is added for the purpose of adjusting the crosslinking rate or accepting acid.
- Metal activators include zinc oxide, magnesium oxide, calcium oxide, barium oxide, aluminum oxide, bell oxide, iron oxide, calcium hydroxide, calcium carbonate, magnesium carbonate, fatty acid sodium, calcium octylate, potassium isooctylate, Toxides, cesium octylate, potassium isostearate and the like can be mentioned, and these can be used alone or in combination of two or more.
- the compounding amount of the metal activator is not particularly limited, but is preferably 0 to 20 parts by weight, more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the polymer material.
- the entropy elastic layer used in the present invention may be laminated after preparing the entropy elastic composition, molding the composition into a desired shape (for example, a sheet), or uncrosslinked entropy elasticity.
- the composition may be laminated without being particularly molded.
- the method for preparing the entropy elastic composition is not particularly limited, and can be performed by a method used for a normal rubber composition, for example, by mixing using an open roll, a Banbury mixer, a kneader, or the like. Can be prepared.
- crosslinking conditions are not particularly limited, and the conditions employed in ordinary rubber compositions can be used.
- the laminate is not particularly limited, between the two substrates, any method as long as the method of forming the elastic molecular bonding layer may also be employed .
- a molecular adhesive layer 1 (2) is formed on a substrate 1 (1) (FIG. 1 (a)) (FIG. 1 (b)), and the molecular adhesive layer 1 (2
- the entropy elastic body layer 1 (3) is laminated on (FIG. 1 (c)), and the molecular adhesive layer 2 (4) is further laminated on the entropy elastic body layer 1 (3) (FIG. 1 (d)
- a method of stacking the substrates 2 (5) to form a stacked body FIG. 1 (e)
- this method is called a stacking system.
- a molecular adhesive layer 1 (2) and a molecular adhesive layer 2 (4) are formed in advance on the surfaces of the substrate 1 (1) and the substrate 2 (5) (FIG. 2 ( a))
- a method of forming the entropy elastic layer 1 (3) between two substrates on which the molecular adhesive layers 1 and 2 are formed (FIGS. 2B and 2C) is also employed. be able to. In the present invention, this method is called a sandwich method.
- the molecular adhesive layer can be formed by reacting OH groups present on the surface of the substrate with the molecular adhesive.
- Examples of the pretreatment method include corona discharge treatment, atmospheric pressure plasma treatment, and UV irradiation treatment.
- corona treatment Journal of the Adhesion Society of Japan, Vol. 36, no. 3, 126 (2000)
- plasma treatment Journal of the Adhesion Society of Japan, Vol. 41, no. 1, 4 (2005)
- —OH groups, —COOH groups, —C ⁇ O groups and the like are generated on the solid surface or appear on the surface (LJ Gerenser: J. Adhesion Sci. Technol. 7, 1019). (1997)).
- the solid surface is contaminated by absorbing dirt components in the atmosphere.
- the corona discharge treatment is performed by using a corona surface reformer (for example, Corona Master manufactured by Shinko Electric Instrument Co., Ltd.), power source: AC 100 V, output voltage: 0 to 20 kV, oscillation frequency: 0.1 to 40 kHz. It can be carried out under the conditions of ⁇ 60 seconds and temperature of 0 ⁇ 60 ° C.
- a corona surface reformer for example, Corona Master manufactured by Shinko Electric Instrument Co., Ltd.
- power source AC 100 V
- output voltage 0 to 20 kV
- oscillation frequency 0.1 to 40 kHz. It can be carried out under the conditions of ⁇ 60 seconds and temperature of 0 ⁇ 60 ° C.
- the atmospheric pressure plasma treatment uses an atmospheric pressure plasma generator (for example, Aiplasma manufactured by Matsushita Electric Works Co., Ltd.), a plasma treatment speed of 10 to 100 mm / s, a power source: 200 or 220 V AC (30 A), and compressed air: 0. It can be performed under the conditions of 5 MPa (1 NL / min), 10 kHz / 300 W to 5 GHz, power: 100 W to 400 W, and irradiation time: 0.1 to 60 seconds.
- Aiplasma manufactured by Matsushita Electric Works Co., Ltd.
- a plasma treatment speed 10 to 100 mm / s
- a power source 200 or 220 V AC (30 A)
- compressed air 0. It can be performed under the conditions of 5 MPa (1 NL / min), 10 kHz / 300 W to 5 GHz, power: 100 W to 400 W, and irradiation time: 0.1 to 60 seconds.
- UV irradiation is performed using a UV-LED irradiation device (for example, UV-LED irradiation device ZUV-C30H manufactured by OMRON Corporation), wavelength: 200 to 400 nm, power source: 100 V AC, light source peak illuminance: 400 to 3000 mW / It can be performed under conditions of cm 2 and irradiation time: 1 to 60 seconds.
- a UV-LED irradiation device for example, UV-LED irradiation device ZUV-C30H manufactured by OMRON Corporation
- wavelength 200 to 400 nm
- power source 100 V AC
- light source peak illuminance 400 to 3000 mW / It can be performed under conditions of cm 2 and irradiation time: 1 to 60 seconds.
- the method for forming the molecular adhesive layer 1 on the substrate having an OH group is not particularly limited, and a known method can be used. For example, dipping, coating, spraying and the like can be mentioned, but a dipping method is preferred from the viewpoint that the solution can be uniformly contacted.
- the immersion method can be performed by immersing the substrate in a molecular adhesive solution, heating and drying.
- the concentration of the molecular adhesive solution is not particularly limited and may be appropriately selected.
- the concentration is preferably 5 ⁇ 10 ⁇ 3 to 5 wt%, and preferably 0.01 to 1 wt%. It is more preferable. By setting the concentration within the above range, the adhesive strength is increased, which is preferable.
- the solvent is not particularly limited.
- alcohols such as methanol, ethanol, isopropanol, ethylene glycol, and diethylene glycol
- ketones such as acetone and methyl ethyl ketone
- esters such as ethyl acetate
- methylene chloride methylene chloride
- the immersion treatment conditions are not particularly limited, but for example, it is preferable to immerse at a solution temperature of 0 to 100 ° C. for 1 second to 60 minutes. Immersion conditions are governed by the temperature, time, and concentration of the solution and cannot be uniquely determined. However, at a constant concentration, the time tends to be long when the temperature is low, and the time is short when the temperature is high. .
- the heating conditions are preferably 20 to 250 ° C. for 1 second to 120 minutes, more preferably 50 to 200 ° C. for 1 to 60 minutes, and further preferably 80 to 180 ° C. for 1 to 30 minutes. When the heating condition is within this range, productivity is high and economically preferable.
- the heating method is not particularly limited, and a known method can be used, and examples thereof include a method using an oven, a dryer, high-frequency heating, or the like.
- the above contact and heating can be repeated about 1 to 10 times. That is, it may be more effective to shorten the time of contact and heating and increase the number of reactions.
- a method for forming the molecular adhesive layer in part is not particularly limited, and examples thereof include protecting a part of the substrate by masking and decomposing the molecular adhesive by exposure using a mask.
- the entropy elastic layer is made by bringing an uncrosslinked or crosslinked entropy elastic composition into contact with the entire surface or a part of the molecular adhesive layer 1 formed on the substrate, and applying heat under pressure. And / or can be formed by bonding with an optical medium.
- part refers to a part of the molecular adhesive layer 1 that has been activated when the surface of a limited part of the molecular adhesive layer 1 is activated for the adhesion reaction, depending on the use of the laminate. It means to form an entropy elastic layer only in the above.
- the activation treatment includes, for example, reacting an alkali metal to increase the reactivity of the thiol group contained in the molecular adhesive, or further reacting the functional group by an exposure method using a mask.
- the entropy elastic body layer may be prepared by preparing the entropy elastic body composition, and pre-molding the composition into a desired shape (for example, a sheet shape). Also good.
- contact means that an uncrosslinked or crosslinked entropy elastic composition is bonded to the entire surface or a part of the molecular adhesive layer 1 formed on the substrate.
- the contact can be performed under a reduced pressure condition or a pressurized condition.
- the decompression and pressurization conditions are not particularly limited, and can be set as appropriate.
- the adhesion to the substrate is poor under conditions close to atmospheric pressure, and the physical properties of the entropy elastic body tend to decrease. Under extremely high pressure conditions, the substrate may be destroyed or the entropy elastic body may be thin. Tend to have insufficient functions.
- adhesion is obtained by heating at 0 to 300 ° C. (preferably 20 to 200 ° C.) for 0.1 to 1440 minutes (preferably 1 to 720 minutes). Is preferred. Examples of the heating method include an oven, a dryer, and high frequency heating.
- an adhesive by irradiating at 200 to 450 nm (preferably 254 to 365 nm) for 1 to 180 minutes (preferably 2 to 90 minutes).
- the optical medium include an ultraviolet irradiation device using a light source such as a mercury lamp (wavelength: 254, 303, 313, 365 nm), a metal halide lamp (200 to 450 nm), a hyper metal halide lamp (400 to 450 nm), and the like.
- Adhesion of the entropy elastic layer may be performed by either heat or an optical medium, and these methods may be used in combination.
- the molecular adhesive layer 1 and the entropy elastic body layer formed on the substrate 1 can provide a laminate having excellent adhesiveness by being chemically bonded by a crosslinking reaction.
- the method for forming the molecular adhesive layer 2 on the entropy elastic layer is not particularly limited, but the entropy elastic layer and the molecular adhesive are the same as described above. It can also be formed by reacting the OH group of the entropy elastic layer with a molecular adhesive.
- the molecular adhesive layer 2 is formed by reacting the OH group of the entropy elastic layer with the molecular adhesive, it is necessary to have —OH group on the surface of the entropy elastic layer, and there is no —OH group on the surface.
- the same method as the substrate pretreatment method can be exemplified.
- the method for forming the molecular adhesive layer 2 is the same as that for the molecular adhesive layer 1.
- the molecular adhesive layers 1 and 2 may use the same molecular adhesive or different molecular adhesives.
- the lamination of the present invention is performed by laminating the substrate 2 on the surface where the substrate 1, the molecular adhesive layer 1, the entropy elastic body layer, and the molecular adhesive layer 2 are laminated in this order. You can get a body.
- the substrate 2 is a metal plate or a resin plate
- pretreatment for imparting a functional group that reacts with the molecular adhesive constituting the molecular adhesive layer 2 on the substrate 2 may be performed. From this point, it is preferable.
- the substrate 2 can be formed by a plating method.
- the plating method is not particularly limited, and may be an electroless plating method or an electrolytic plating method.
- a plating catalyst serving as a nucleus is supported on the molecular adhesive layer 2 and electroless plating is performed using the plating catalyst as a nucleus to form an electroless plating layer on the molecular adhesive layer 2. Further, electrolytic plating may be further performed on the electroless plating layer.
- the catalyst is not particularly limited, and any catalyst that is usually used for electroless plating can be used. Specifically, palladium / Sn colloid, Ag complex, Pd complex, etc. can be mentioned.
- the plating layer is not particularly limited, but for example, copper is appropriately used when stress relaxation is desired, and nickel is appropriately used when metal surface hardness is desired.
- the substrate 2 may be formed on the entire surface of the molecular adhesive layer 2 or may be formed on a part of the molecular adhesive layer 2. Here, the part is the same as described above.
- the molecular adhesive constituting the molecular adhesive layer 2 is 6- (3- (triethoxysilyl) propylamino) -1,3,5-triazine- 2,4-dithiol monosodium (TES) is preferred.
- the molecular adhesive layer 1 and the molecular adhesive layer 2 are formed in advance on the surfaces of the substrate 1 and the substrate 2, respectively.
- As a forming method the same method as in the case of the stacking method can be adopted.
- Sandwich method A laminate can be formed by sandwiching an entropy elastic layer between two substrate surfaces on which the molecular adhesive layer is formed.
- the substrate 1 and the substrate 2 on which the molecular adhesive layer 1 and the molecular adhesive layer 2 are formed and the entropy elastic body layer are laminated, and a laminate is formed under reduced pressure or pressurized conditions. Is done.
- the decompression and pressurization conditions are not particularly limited, and can be set as appropriate.
- the shape of the laminate is a laminate in which an entropy elastic molecular adhesive layer is formed between two substrates 1 and 2, as shown in FIGS. Is a laminate comprising the entropy elastic body layer 1 and the molecular adhesive layers 1 and 2.
- the entropy elasticity is further provided on the laminate of FIGS.
- a molecular adhesive layer 3, an entropy elastic body layer 2, a molecular adhesive layer 4, and a substrate 3 are further formed on the laminate of FIGS.
- the method in the present specification can be adopted, and the substrate can be stacked in any number of layers as long as the elastic adhesive layer is interposed.
- the laminate of the present invention can be suitably used for electronic mounting parts, precision machine parts, building structures, circuit wiring boards, decorative plating products, and adhesive composite products.
- Example 1 Manufacture of OH-based substrate (I)
- Al Al
- a corona discharge device manufactured by Kasuga Electric Co., Ltd., an output of 13 kW
- Three reciprocal corona discharge treatments were performed at a speed of 2 m / min to produce an OH-based substrate (I).
- the catalyst After the catalyst is supported, it is immersed in an electroless copper plating bath at 30 ° C. for 10 minutes for electroless plating, and further energized for 60 minutes at 30 ° C. in an electrolytic copper plating bath.
- a laminate (V) having “may be indicated as“ copper plating ”.) was obtained.
- Example 2 A laminate (V) was obtained in the same manner as in Example 1 except that an alumina substrate (30 ⁇ 50 ⁇ 3 mm, hereinafter sometimes referred to as “alumina”) was used in place of the aluminum plate. It was.
- alumina alumina substrate
- Example 3 A glass epoxy resin substrate (0.2 ⁇ 30 ⁇ 50 mm, FR-4; manufactured by Matsushita Electric Works Co., Ltd., hereinafter sometimes referred to as “EP”) was used in place of the aluminum plate as the substrate. In the same manner as in Example 1, a laminate (V) was obtained.
- EP Matsushita Electric Works Co., Ltd.
- Example 4 Implemented except that instead of an aluminum plate, a polyimide resin substrate (0.05 ⁇ 30 ⁇ 50 mm, Kapton: manufactured by Toray DuPont Co., Ltd., hereinafter sometimes referred to as “PI”) was used as the substrate. In the same manner as in Example 1, a laminate (V) was obtained.
- PI polyimide resin substrate
- V laminate
- Comparative Examples 1 to 4 A laminate was obtained in the same manner as in Example 1 except that the substrate shown in Table 1 was used and the TES treatment was not performed.
- Example 5 Manufacture of OH-based substrate (I)) Using a copper plate (1 ⁇ 30 ⁇ 50 mm, manufactured by Nilaco Co., Ltd.) and copper foil (0.1 ⁇ 30 ⁇ 50 mm, manufactured by Nilaco Co., Ltd.) as a substrate, and using a corona discharge device manufactured by Kasuga Electric Co., Ltd. Three reciprocal corona discharge treatment was performed at an output of 13 kW and a speed of 2 m / min to produce an OH-based copper plate (I-1) and an OH-based copper foil (I-2).
- the obtained OH group-treated copper foil (I-2) was immersed in a 95% water / ethanol solution (0.2 wt%) of vinyl methoxysiloxane homopolymer (manufactured by Azomax Co., Ltd.) for 5 minutes and then 120 ° C. Was heated in an oven for 10 minutes, washed with ethanol and dried with a dryer to obtain a molecular adhesive (VMS) bonded copper foil (II-2).
- VMS molecular adhesive
- a sheet (approximately 2 mm) of the entropy elastic composition was prepared by molding the entropy elastic composition (2) shown in Table 8 below into a sheet shape.
- a sheet of entropy elastic composition (1) is sandwiched between the VMS bonding surfaces of the obtained substrates (II-1, II-2) between sandwiches, degassed and bonded together under vacuum, and heated at 50 ° C. for 12 hours.
- a laminate (V) of a substrate and a copper foil (conductor layer) with an entropy elastic adhesive layer interposed therebetween was obtained.
- Example 6 A laminated body in the same manner as in Example 5 except that a glass plate (2 ⁇ 30 ⁇ 50 mm, manufactured by Niraco Co., Ltd.) was used instead of the copper plate as the substrate (that is, the substrate was a glass plate and copper foil). (V) was obtained.
- Example 7 A laminate (in the same manner as in Example 5 except that a glass epoxy resin substrate (EP, 0.2 ⁇ 30 ⁇ 50 mm, FR-4; manufactured by Matsushita Electric Works Co., Ltd.) was used instead of the copper plate as the substrate. V) was obtained.
- a glass epoxy resin substrate EP, 0.2 ⁇ 30 ⁇ 50 mm, FR-4; manufactured by Matsushita Electric Works Co., Ltd.
- Example 8 A laminated body (V) in the same manner as in Example 5 except that a polyimide resin substrate (PI, 0.05 ⁇ 30 ⁇ 50 mm, Kapton: manufactured by Toray DuPont Co., Ltd.) was used instead of the copper plate as the substrate. )
- PI polyimide resin substrate
- Kapton Kapton: manufactured by Toray DuPont Co., Ltd.
- Comparative Examples 5-8 A laminate was obtained in the same manner as in Example 5 except that the substrate shown in Table 2 was used instead of the copper plate as the substrate, and the VMS treatment was not performed.
- the adhesive strength between the substrate and the copper foil is as follows. A 1 cm wide cut is put on the substrate and peeled at a rate of 50 mm / min by a tensile tester (Autograph P-100, manufactured by Shimadzu Corporation). Asked.
- Example 9 Manufacture of OH-based substrate (I)
- an aluminum plate Al, 1 ⁇ 30 ⁇ 50 mm, manufactured by Nilaco Co., Ltd.
- the substrate 2 SUS304 (1 ⁇ 30 ⁇ 50 mm, manufactured by Nilaco Co., Ltd., hereinafter “SUS” may be displayed.
- SUS Stufacture of OH-based substrate
- Example 10 A laminate (V) was obtained in the same manner as in Example 9 except that a glass epoxy resin substrate (EP, 0.2 ⁇ 30 ⁇ 50 mm, FR-4; manufactured by Matsushita Electric Works Co., Ltd.) was used as the substrate 2. It was.
- a glass epoxy resin substrate EP, 0.2 ⁇ 30 ⁇ 50 mm, FR-4; manufactured by Matsushita Electric Works Co., Ltd.
- Example 11 The substrate 1 was the same as in Example 10 except that a polyamide resin substrate (0.5 ⁇ 30 ⁇ 50 mm, 6 nylon sheet: manufactured by SK Co., Ltd., hereinafter sometimes referred to as “PA”) was used. Thus, a laminate (V) was obtained.
- a polyamide resin substrate 0.5 ⁇ 30 ⁇ 50 mm, 6 nylon sheet: manufactured by SK Co., Ltd., hereinafter sometimes referred to as “PA”
- PA polyamide resin substrate
- Example 12 Except that a glass plate (2 ⁇ 30 ⁇ 50 mm, manufactured by Matsunami Glass Co., Ltd.) was used as the substrate 1 and an aluminum plate (Al, 1 ⁇ 30 ⁇ 50 mm, manufactured by Niraco) was used as the substrate 2. In the same manner as in Example 9, a laminate (V) was obtained.
- Example 13 A laminate (V) was obtained in the same manner as in Example 12 except that a polyamide resin substrate (PA, 0.5 ⁇ 30 ⁇ 50 mm, 6 nylon sheet: manufactured by SK Corporation) was used as the substrate 2. .
- a polyamide resin substrate PA, 0.5 ⁇ 30 ⁇ 50 mm, 6 nylon sheet: manufactured by SK Corporation
- Example 14 A laminate (V) was obtained in the same manner as in Example 12 except that a glass plate (2 ⁇ 30 ⁇ 50 mm, manufactured by Matsunami Glass Co., Ltd.) was used as the substrate 2.
- Comparative Examples 9-14 A laminate (V) was obtained in the same manner as in Example 9 except that the substrate shown in Table 3 was used and the TES treatment was not performed.
- Example 15 Manufacture of OH-based substrate (I)
- the substrate 1 is an aluminum plate (Al, 1 ⁇ 30 ⁇ 50 mm, manufactured by Nilaco Corporation), and the substrate 2 is a glass epoxy resin substrate (EP, 0.2 ⁇ 30 ⁇ 50 mm, FR-4; manufactured by Matsushita Electric Works Co., Ltd.) ), And a corona discharge device manufactured by Kasuga Electric Co., Ltd., was subjected to a three-way reciprocal corona discharge treatment at an output of 13 kW and a speed of 2 m / min to obtain an OH-based substrate (I-1), (I-2) ) Was produced.
- Example 16 The laminate (V) was prepared in the same manner as in Example 15 except that 3-aminopropyltriethoxysilane (APS, manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903) was used as the molecular adhesive instead of TES. Obtained.
- 3-aminopropyltriethoxysilane APS, manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903
- Example 17 Bis (triethoxysilylpropyl) tetrasulfide (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-846) and 2-dibutylamino-1,3,5-triazine-4,6-dithiol as molecular adhesives instead of TES
- the entropy elastic composition shown in Table 8 below was used instead of the entropy elastic composition (3).
- a laminate (V) was obtained in the same manner as in Example 15 except that 4) was used.
- Example 18 Example 15 except that VMS was used instead of TES as the molecular adhesive and the sheet of the entropy elastic composition (1) used in Example 1 was used instead of the entropy elastic composition (3). In the same manner as above, a laminate (V) was obtained.
- Example 19 Example 15 except that 6-bis (3-triethoxysilylpropyl) amino-1,3,5-triazine-2,4-dithiol monosodium (BTES) was used as the molecular adhesive instead of TES. In the same manner as above, a laminate (V) was obtained.
- BTES 6-bis (3-triethoxysilylpropyl) amino-1,3,5-triazine-2,4-dithiol monosodium
- Comparative Examples 21-23 A laminate (V) was obtained in the same manner as in Example 15 except that the substrate and entropy elastic body shown in Table 4 were used and the molecular adhesive treatment was not performed.
- Adhesion between the substrates is obtained by placing a 1.25 cm ⁇ 0.6 cm entropy elastic body on the substrate end of 1.25 cm ⁇ 50 cm, producing a shear peel strength test sample, and tensile tester (Autograph manufactured by Shimadzu Corporation) P-100), and peeled at a speed of 50 mm / min to determine the shear peel strength.
- Table 4 shows the measurement results.
- the entropy elastic body described in the table after Table 4 is an entropy elastic body composition having the composition (part by weight ratio) shown in Table 8.
- the abbreviations shown in Table 8 are used. .
- Example 20 Manufacture of OH-based substrate (I)
- the substrate 1 is an aluminum plate (Al, 1 ⁇ 30 ⁇ 50 mm, manufactured by Nilaco Corporation), and the substrate 2 is a glass epoxy resin (EP, 0.2 ⁇ 30 ⁇ 50 mm, FR-4; manufactured by Matsushita Electric Works Co., Ltd.) ), And a corona discharge device manufactured by Kasuga Electric Co., Ltd., was subjected to a three-way reciprocal corona discharge treatment at an output of 13 kW and a speed of 2 m / min to obtain an OH-based substrate (I-1), (I-2) ) Was produced.
- Examples 21-28 A laminate (V) was obtained in the same manner as in Example 20 except that the substrate, molecular adhesive, and entropy elastic body shown in Table 5 were used.
- “PE” in Table 5 represents a commercially available sheet made of polyethylene (manufactured by Kokugo Co., Ltd., 30 ⁇ 60 ⁇ 1 mm product name: rigid polyethylene sheet).
- Comparative Examples 24-32 A laminate (V) was obtained in the same manner as in Example 20 except that the substrate and entropy elastic body shown in Table 5 were used and the molecular adhesive treatment was not performed.
- Examples 29-36 Manufacture of OH-based substrate (I) and molecular adhesive-bonded substrate (II)
- the obtained substrate (I) was treated with the molecular adhesive shown in the column of molecular adhesive 1 in Table 6 to obtain molecular adhesive-bonded substrate (II).
- the conditions for the treatment with the molecular adhesive are the same as in the above example using the same molecular adhesive.
- entropy elastic substrate (IV) Manufacture of entropy elastic substrate (IV)
- the surface of the elastic body of the obtained adhesive (III) is subjected to corona discharge in the same manner as described above, and then treated with the molecular adhesive shown in the column of molecular adhesive 2 in Table 6 to give an entropy elastic adhesive substrate (IV) was obtained.
- the conditions for the treatment with the molecular adhesive are the same as in the above example using the same molecular adhesive.
- Examples 37-53 Manufacture of OH-based substrate (I) and molecular adhesive-bonded substrate (II)
- the substrate shown in the column of the substrate 1 in Table 7 is used as the substrate 1
- the substrate shown in the column of the substrate 2 in Table 7 is used as the substrate 2
- the molecular adhesive shown in the column of the molecular adhesive in Table 7 is used as the molecular adhesive.
- a laminate (V) was obtained under the same conditions as in Example 9 except that the entropy elastic body shown in the column of elastic body in Table 7 was used as the entropy elastic body.
- the peel strength of this laminate (V) was measured in the same manner as in the above ⁇ Strength measuring method>. The results are shown in the column of peel strength in Table 7.
- S4 + DA shown in the column of molecular adhesive in Table 7 is bis (triethoxysilylpropyl) tetrasulfide (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-846) and 2-diallylamino-1,3,5 -Represents a 1: 1 (molar ratio) mixture of triazine-4,6-dithiol.
- Ethylene propylene terpolymer EPDM, EP92 manufactured by JSR
- CHR Acrylic nitrile butadiene copolymer rubber
- NBR Acrylic nitrile butadiene copolymer rubber
- FKM Fluoro rubber
- FKM Fluoro rubber
- BR 1,4-cisbutadiene rubber
- SiNBR 1,4-cisbutadiene rubber
- SiNBR Silicon rubber
- Q manufactured by Toray Dow Corning Silicone Co., Ltd., SH852U
- Carbon black SRF carbon Asahi # 40, manufactured by Asahi Carbon Co., Ltd.
- Silica manufactured by Nippon Silica Industry Co., Ltd., MFDF treated silica, trade name
- the present invention is useful in many fields such as the automobile industry, the electronic equipment industry, the medical equipment industry, the aerospace industry, and the construction industry.
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Abstract
Description
項1.2つの基板の間に、エントロピー弾性分子接着層を形成してなる積層体であって、
該エントロピー弾性分子接着層が、エントロピー弾性体層及び分子接着剤層からなることを特徴とする積層体。
項2.エントロピー弾性分子接着層が、基板上に分子接着剤層1を形成し、該分子接着剤層1上にエントロピー弾性体層を形成し、該エントロピー弾性体層上にさらに分子接着剤層2を積層して形成されることを特徴とする上記項1に記載の積層体。
項3.エントロピー弾性分子接着層が、2つの基板の表面に予め分子接着剤層を形成し、該分子接着剤層が形成された2つの基板で、エントロピー弾性体層を挟み込むことによって形成されることを特徴とする上記項1に記載の積層体。
項4.分子接着剤層が、基板表面に存在するOH基と分子接着剤とを反応させることにより形成されることを特徴とする上記項1~3のいずれかに記載の積層体。
項5.分子接着剤層が、エントロピー弾性体層表面に存在するOH基と分子接着剤とを反応させることにより形成されることを特徴とする上記項1又は2に記載の積層体。
項6.分子接着剤層が、基板の全面又は一部に形成されることを特徴とする上記項1~3に記載の積層体。
項7.エントロピー弾性体層が、分子接着剤層の全面又は一部に、未架橋又は架橋エントロピー弾性体組成物を接触させ、加圧下、熱及び/又は光媒体により接着して形成されることを特徴とする上記項1~5のいずれかに記載の積層体。
項8.エントロピー弾性体層が、1,4-シスブタジエンゴム(BR)、アクリルニトリル・ブタジエン共重合ゴム(NBR)、エチレン-プロピレン-ジエンゴム(EPDM)、フッ素ゴム(FKM)、エピクロロヒドリンゴム(CHR)、フッ素化シリコンゴム、パーオキサイド型シリコンゴム、付加型シリコンゴム及び縮合型シリコンゴムからなる群から選択される1種以上を含むことを特徴とする上記項1~7のいずれかに記載の積層体。
項9.分子接着剤層が、一般式(1):
A-SiX1 3-nYn (1)
(式中、Aはエントロピー弾性体層と結合可能な基であり、X1は、それぞれ同じであっても異なっていてもよく、水素原子、置換基を有していても良い炭素数1~10の飽和又は不飽和の脂肪族炭化水素基であり、Yは炭素数1~10のアルキルオキシ基であり、nは1~3の整数である)
で示される分子接着剤の1種類以上を含んでなることを特徴とする上記項1~8のいずれかに記載の積層体。
項10.分子接着剤が、下記一般式(2)~(6)で示される分子接着剤である上記項9に記載の積層体。
[X5 d(X6O)3-dSiR6]eZ (5)
(式中、X5、X6は、同じであっても異なっていてもよく、炭素数1~4の飽和又は不飽和の脂肪族炭化水素基であり、R6は炭素数1~18の2価の脂肪族炭化水素基又は芳香族炭化水素基であって、該脂肪族炭化水素基には-NH-、-CO-、-O-、-S-、-COO-、-C6H4-を含んでいてもよい。Zは、-SH、-SCSN(CH3)2、-SSCSN(CH3)2、-SCSN(C2H5)2、-SCSN(C4H9)2、-SCSN(C8H17)2、-SS-、-SSS-、-SSSS-、
H2N-R7-SiX1 3-nYn (6)
(式中、R7は、置換基を有していても良い炭素数1~10の飽和又は不飽和の脂肪族炭化水素基もしくは置換機基を有しても良い芳香族炭化水素基であり、X1、Yは前記同様であり、nは1から3までの整数である)。
項11.基板が、金属、セラミックス、樹脂及びこれらの複合体からなる群から選択される1種以上の基板である上記項1~10のいずれかに記載の積層体。
項12.2つの基板の少なくとも一方が、導電性基板であることを特徴とする上記項1~11のいずれかに記載の積層体。
項13.導電性基板が、分子接着剤層の全面又は一部に形成されることを特徴とする上記項12に記載の積層体。
項14.導電性基板が、分子接着剤層上に触媒担持後、無電解めっきにより形成されることを特徴とする上記項12又は13に記載の積層体。
項15.導電性基板が、銅めっきであることを特徴とする上記項14に記載の積層体。
項16.上記項1~15のいずれかに記載の積層体からなることを特徴とする回路配線基板。
項17.上記項1~15のいずれかに記載の積層体からなることを特徴とする装飾めっき製品。
項18.上記項1~16のいずれかに記載の積層体からなることを特徴とする接着複合体製品。
2 分子接着剤層1
3 エントロピー弾性体層1
4 分子接着剤層2
5 基板2
6 分子接着剤層3
7 エントロピー弾性体層2
8 分子接着剤層4
9 基板3
本発明で用いる2つの基板(以下、基板1、基板2とする)は、同じであっても異なっていてもよく、形状保持機能を有する基板であれば特に限定されるものではない。
本発明で用いるエントロピー弾性分子接着層は、エントロピー弾性体層及び分子接着剤層からなる。エントロピー弾性分子接着層の有効な厚さは、製品の目的とする特性によって異なるため一義的に決められず、製品の形態により適宜決めることが可能であるが、界面での強度を特に必要とする場合は、0.1~5,000μmであることが好ましく、1~2,000μmであることがより好ましい。エントロピー弾性分子接着層の厚さが0.1μm未満であるとその成膜性が困難であり、応力の緩和、信頼性の向上が十分達せられない場合があり、5,000μmを超えると、製品によっては、積層基板の小型化、高密度化が難しく、また、生産コストが増加し、生産性が低下する傾向がある。
本発明において「分子接着剤層」とは、分子接着剤からなる層を示すものであり、一般式(1):
A-SiX1 3-nYn (1)
(式中、Aはエントロピー弾性体層と結合可能な基であり、X1は、それぞれ同じであっても異なっていてもよく、水素原子、置換基を有していても良い炭素数1~10の飽和又は不飽和の脂肪族炭化水素基であり、Yは炭素数1~10のアルキルオキシ基であり、nは1~3の整数である)
で示される分子接着剤を1種類以上含んでなる層であることが好ましい。
[X5 d(X6O)3-dSiR6]eZ (5)
X5、X6は、同じであっても異なっていてもよく、炭素数1~4(好ましくは1~2)の飽和又は不飽和の脂肪族炭化水素基であり、CH3-、C2H5-、n-C3H7-、i-C3H7-、CH2=CHCH2-、n-C4H9-、i-C4H9-、t-C4H9-を挙げることができる。
H2N-R7-SiX1 3-nYn (6)
上記一般式(2)~(6)で示される分子接着剤は、単独で用いても2種以上を組み合わせて用いてもよい。
本発明に用いられる「エントロピー弾性体層」とは、エントロピー弾性体からなる層であって、積層体形成時の温度(例えば、15~200℃)がガラス移転点以上である高分子材料を含むエントロピー弾性体組成物から形成される層である。エントロピー弾性体としては、所謂天然ゴム、合成ゴム等のゴム類とともに、積層体形成時の温度で、ガラス移転点以上のゴム状態であるプラスチックも含まれる。中でも、ガラス移転点が室温より低く、室温においてゴム状態であるゴム類やポリエチレン等が好ましい。具体的には、例えば、天然ゴム、1,4-シスブタジエンゴム(BR)、イソプレンゴム、ポリクロロプレン、スチレン・ブタジエン共重合ゴム、水素添加スチレン・ブタジエン共重合ゴム、アクリルニトリル・ブタジエン共重合ゴム(NBR)、水素添加アクリルニトリル・ブタジエン共重合ゴム、ポリブテン、ポリイソブチレン、エチレン・プロピレンゴム、エチレン-プロピレン-ジエンゴム(EPDM)、エチレンオキサイド-エピクロロヒドリン共重合体、ポリエチレン、ポリプロピレン、ポリアミド、塩素化ポリエチレン、クロルスルフォン化ポリエチレン、アルキル化クロルスルフォン化ポリエチレン、クロロプレンゴム、塩素化アクリルゴム、臭素化アクリルゴム、フッ素ゴム(FKM)、エピクロロヒドリンゴム(CHR)、エピクロルヒドリンとその共重合ゴム、塩素化エチレンプロピレンゴム、塩素化ブチルゴム、臭素化ブチルゴムテトラフロロエチレン、テフロン(登録商標)、ヘキサフロロプピレン、フッ化ビニリデンなどの二元、三元共重合体、アクリルゴム、エチレンアクリルゴム、シリコン樹脂、フッ素化シリコンゴム、パーオキサイド型シリコンゴム、付加型シリコンゴム、縮合型シリコンゴム、エポキシゴム、ウレタンゴム及び両末端不飽和基エラストマー等を挙げることができる。これらの中でも、1,4-シスブタジエンゴム(BR)、アクリルニトリル・ブタジエン共重合ゴム(NBR)、エチレン-プロピレン-ジエンゴム(EPDM)、フッ素ゴム(FKM)、エピクロロヒドリンゴム(CHR)、フッ素化シリコンゴム、パーオキサイド型シリコンゴム、付加型シリコンゴム、縮合型シリコンゴム、ポリエチレンが好ましい。
本発明の積層体の製造方法としては、特に限定されるものではなく、2つの基板の間に、弾性分子接着層を形成する方法であればいかなる方法も採用することができる。
(1)基板の前処理方法
本発明においては、分子接着剤層は、基板の表面に存在するOH基と分子接着剤とを反応させることにより形成させることができる。
OH基を有する基板上に、分子接着剤層1を形成する方法としては、特に限定されるものはなく、公知の方法を用いることができる。例えば、浸漬、塗布、噴霧等を挙げることができるが、均一に前記溶液と接触することができる点から、浸漬による方法が好ましい。
エントロピー弾性体層は、基板上に形成した分子接着剤層1の全面又は一部に、未架橋又は架橋エントロピー弾性体組成物を接触させ、加圧下、熱及び/又は光媒体により接着して形成することができる。
エントロピー弾性体層上に分子接着剤層2を形成する方法としては、特に限定されるものではないが、前述と同様にエントロピー弾性体層と分子接着剤の架橋反応により化学的に結合することもでき、また、エントロピー弾性体層のOH基と分子接着剤とを反応させることにより形成させることもできる。
例えば、基板1、分子接着剤層1、エントロピー弾性体層、分子接着剤層2がこの順番で積層された表面に、基板2を積層させることで本発明の積層体を得ることができる。なお、基板2が金属板、樹脂板の場合は、この際基板2上に分子接着剤層2を構成する分子接着剤と反応する官能基を付与する前処理を行っておくことが、接着性の点から好ましい。
(1)分子接着剤層の形成方法
基板1及び基板2のそれぞれの表面に予め分子接着剤層1、分子接着剤層2を形成しておく。形成方法としては、積み上げ方式の場合と同様の方法を採用することができる。
該分子接着剤層が形成された2つの基板表面で、エントロピー弾性体層を挟み込むことによって積層体を形成することができる。
本発明は、図1、2に示すように、基板1、基板2の2つの基板の間に、エントロピー弾性分子接着層を形成してなる積層体であり、該弾性分子接着層が、エントロピー弾性体層1及び分子接着剤層1、2からなることを特徴とする積層体であるが、例えば、図3に示すように、図1、2の積層体上にさらに、エントロピー弾性分子接着層を介して別の基板を接着することも可能である。具体的には、図3に示すように、図1、2の積層体上にさらに、分子接着剤層3、エントロピー弾性体層2、分子接着剤層4、基板3を形成する等である。
(OH基化処理基板(I)の製造)
基板として、アルミニウム板(1×30×50mm、(株)ニラコ製、以後「Al」と表示することがある。)を用い、春日電機(株)製コロナ放電装置を用いて、13kWの出力、2m/minの速度で3往復コロナ放電処理を行い、OH基化処理基板(I)を作製した。
得られた基板(I)を6-(3-(トリエトキシシリル)プロピルアミノ)-1,3,5-トリアジン-2,4-ジチオール・モノナトリウム(TES)の95%水/エタノール溶液(0.2wt%)に5分間浸漬後150℃、10分間オーブン中加熱をし、エタノール洗浄・ドライヤー乾燥をすると分子接着剤(TES)結合基板(II)を得た。
得られた基板(II)の分子接着剤層形成面と下記表8に示すエントロピー弾性体組成物(1)のシート(厚さ約1.5mm)を貼り合わせて、5MPaの圧力下で160℃、10分間加熱したところ、基板とEPDM弾性体の接着物(III)(弾性体の厚みは約1.2mm)が得られた。
得られた接着物(III)のEPDM表面に同様にコロナ放電し、TESの95%水/エタノール溶液(0.2wt%)に5分間浸漬後150℃、10分間オーブン中加熱をし、エタノール洗浄・ドライヤー乾燥すると分子接着剤(TES)結合したEPDM弾性体接着基板(IV)を得た。
得られた基板(IV)をPd/Snコロイド触媒(ロームアンドハース電子材料(株)製、キャタポジット44)溶液中に5分間浸漬して水洗後、さらにアクセレーター(ロームアンドハース電子材料(株)製、アクセレーター19E)溶液に7分間浸漬、水洗後、乾燥して触媒担持を行った。
基板として、アルミニウム板に代えて、アルミナ基板(30×50×3mm、以後「アルミナ」と表示することがある。)を用いた以外は、実施例1と同様にして積層体(V)を得た。
基板として、アルミニウム板に代えて、ガラスエポキシ樹脂基板(0.2×30×50mm、FR-4;松下電工(株)製、以後「EP」と表示することがある。)を用いた以外は、実施例1と同様にして積層体(V)を得た。
基板として、アルミニウム板に代えて、ポリイミド樹脂基板(0.05×30×50mm、カプトン:東レ・デュポン(株)製、以後「PI」と表示することがある。)を用いた以外は、実施例1と同様にして積層体(V)を得た。
表1に示す基板を用いTES処理を行わない以外は、実施例1と同様に行って積層体を得た。
基板とTESの結合確認及びEPDM弾性体とTESの結合確認は、基板上にTES層形成後とEPDM弾性体層上TES層形成後、X線光電子分光XPS(アルバックファイ社製、パーキンエルマPHI5600ESCAシステム)により全ての元素を測定することにより行った。
1)EPDM弾性体層の接着性
基板とEPDM弾性体の接着物(III)のEPDM弾性体層に1cm幅の切をいれ、引張試験機((株)島津製作所製オートグラフP-100)により、50mm/minの速度で剥離して剥離強度を測定した。
2)導電体層の接着性
積層体(V)の導電体層(銅めっき層)も前記同様の方法で剥離強度で評価した。
(OH基化処理基板(I)の製造)
基板として、銅板(1×30×50mm、(株)ニラコ製)及び銅箔(0.1×30×50mm、(株)ニラコ製)を用い、春日電機(株)製コロナ放電装置を用いて、13kWの出力、2m/minの速度で3往復コロナ放電処理を行い、OH基化処理銅板(I-1)、及びOH基化処理銅箔(I-2)を作製した。
得られたOH基化処理銅板(I-1)を下記式で示されるビニルメトキシシロキサンホモポリマー(VMS、Gelest inc.製)の95%水/エタノール溶液(0.2wt%)に5分間浸漬後150℃で10分間オーブン中加熱し、エタノール洗浄・ドライヤー乾燥して分子接着剤(VMS)結合基板(II-1)を得た。
エントロピー弾性体組成物のシート(およそ2mm)は、下記表8に示すエントロピー弾性体組成物(2)をシート状に成形して調製した。
得られた基板(II-1、II-2)のVMS結合面でエントロピー弾性体組成物(1)のシートをサンドイッチに挟んで、真空下脱気して貼り合わせ、50℃で12時間加熱し、エントロピー弾性体接着層を介在した基板と銅箔(導電体層)の積層体(V)を得た。
基板としての銅板に代えて、ガラス板(2×30×50mm、(株)ニラコ製)を用いた(すなわち、基板は、ガラス板及び銅箔)以外は、実施例5と同様にして積層体(V)を得た。
基板としての銅板に代えて、ガラスエポキシ樹脂基板(EP、0.2×30×50mm、FR-4;松下電工(株)製)を用いた以外は、実施例5と同様にして積層体(V)を得た。
基板としての銅板に代えて、ポリイミド樹脂基板(PI、0.05×30×50mm、カプトン:東レ・デュポン(株)社製)を用いた以外は、実施例5と同様にして積層体(V)を得た。
基板としての銅板に代えて表2に示す基板を用い、かつVMS処理を行わない以外は、実施例5と同様に行って積層体を得た。
基板とVMSの結合確認及び銅箔とVMSの結合確認は、いずれも処理後、X線光電子分光XPS(アルバックファイ社製、パーキンエルマPHI5600ESCAシステム)により全ての元素を測定することにより行った。
基板と銅箔の接着性は、1cm幅の切を基板の上までいれて、引張試験機((株)島津製作所製オートグラフP-100)により、50mm/minの速度で剥離して剥離強度を求めた。
(OH基化処理基板(I)の製造)
基板1として、アルミニウム板(Al、1×30×50mm、(株)ニラコ製)、基板2として、SUS304(1×30×50mm、(株)ニラコ製、以後「SUS」と表示することがある。)を用い、春日電機(株)製コロナ放電装置を用いて、13kWの出力、2m/minの速度で3往復コロナ放電処理を行い、OH基化処理基板(I-1)、(I-2)を作製した。
得られた基板(I-1)、(I-2)を6-(3-(トリエトキシシリル)プロピルアミノ)-1,3,5-トリアジン-2,4-ジチオール・モノナトリウム(TES)の95%水/エタノール溶液(0.2wt%)に5分間浸漬後150℃、10分間オーブン中加熱をし、エタノール洗浄・ドライヤー乾燥をすると分子接着剤(TES)結合基板(II-1)、(II-2)を得た。
エピクロロヒドリンゴム(CHR)100重量部に対して、SRFブラック(旭#40、旭カーボン(株)製)、ステアリン酸1重量部添加してバンバリーミキサーで80℃、20分間混合し、その後ロールで10分間ブレンドして、マスターバッチとした。次に、
ZISNET-F(架橋剤、三協化成(株)製)1重量部、酸化マグネシウム(MgO)3重量部をロール上でブレンドして、下記表8に示すエントロピー弾性体組成物(3)を得た。
基板(II-1)、(II-2)で、エントロピー弾性体組成物(3)のシートをサンドイッチに挟んで、加圧下、160℃で30分加熱して、エントロピー弾性体接着層を介在した基板同士の積層体(V)を得た。
基板2として、ガラスエポキシ樹脂基板(EP、0.2×30×50mm、FR-4;松下電工(株)製)を用いた以外は、実施例9と同様にして積層体(V)を得た。
基板1として、ポリアミド樹脂基板(0.5×30×50mm、6ナイロンシート:(株)エスケー社製、以後「PA」と表示することがある。)を用いた以外は、実施例10と同様にして積層体(V)を得た。
基板1として、ガラス板(2×30×50mm、(株)松浪ガラス社製)、基板2として、アルミニウム板(Al、1×30×50mm、(株)ニラコ製)を用いた以外は、実施例9と同様にして積層体(V)を得た。
基板2として、ポリアミド樹脂基板(PA、0.5×30×50mm、6ナイロンシート:(株)エスケー社製)を用いた以外は、実施例12と同様にして積層体(V)を得た。
基板2として、ガラス板(2×30×50mm、(株)松浪ガラス社製)を用いた以外は、実施例12と同様にして積層体(V)を得た。
表3に示す基板を用いTES処理を行わない以外は、実施例9と同様に行って積層体(V)を得た。
表3に示す基板を用い弾性体を使用しない以外は、実施例9と同様に行って積層体(V)を得た。
基板とTESの結合確認は処理後、X線光電子分光XPS(アルバックファイ社製、パーキンエルマPHI5600ESCAシステム)により全ての元素を測定し行った。
基板同士の接着性は、1.25cm×5cmの基板端に1.25cm×0.6cmのエントロピー弾性体をのせ、せん断剥離強度試験サンプルを作製し、引張試験機((株)島津製作所製オートグラフP-100)により、50mm/minの速度で剥離してせん断剥離強度を求めた。
(OH基化処理基板(I)の製造)
基板1として、アルミニウム板(Al、1×30×50mm、(株)ニラコ製)、基板2としてガラスエポキシ樹脂基板(EP、0.2×30×50mm、FR-4;松下電工(株)製)を用い、春日電機(株)製コロナ放電装置を用いて、13kWの出力、2m/minの速度で3往復コロナ放電処理を行い、OH基化処理基板(I-1)、(I-2)を作製した。
得られた基板(I-1)、(I-2)を分子接着剤TESの95%水/エタノール溶液(0.2wt%)に5分間浸漬後150℃、10分間オーブン中加熱をし、エタノール洗浄・ドライヤー乾燥をすると分子接着剤結合基板(II-1)、(II-2)を得た。
基板(II-1)、(II-2)で、実施例9で用いたエントロピー弾性体組成物(3)のシートをサンドイッチに挟んで、加圧下、160℃で30分加熱して、エントロピー弾性体接着層を介在した基板同士の積層体(V)を得た。
分子接着剤として、TESの代わりに3-アミノプロピルトリエトキシシラン(APS、信越化学工業(株)製、KBE-903)を用いた以外は、実施例15と同様にして積層体(V)を得た。
分子接着剤として、TESの代わりにビス(トリエトキシシリルプロピル)テトラスルフィド(信越化学工業(株)製、KBE-846)及び2-ジブチルアミノ-1,3,5-トリアジン-4,6-ジチオールの1:1(モル比)の混合物(以後、「S4+DB」と表示することがある。)を用い、エントロピー弾性体組成物(3)の代わりに、下記表8に示すエントロピー弾性体組成物(4)を用いた以外は、実施例15と同様にして、積層体(V)を得た。
分子接着剤として、TESの代わりにVMSを用い、エントロピー弾性体組成物(3)の代わりに、実施例1で用いたエントロピー弾性体組成物(1)のシートを用いた以外は、実施例15と同様にして、積層体(V)を得た。
分子接着剤として、TESの代わりに6-ビス(3-トリエトキシシリルプロピル)アミノ-1,3,5-トリアジン-2,4-ジチオール・モノナトリウム(BTES)を用いた以外は、実施例15と同様にして、積層体(V)を得た。
表4に示す基板、エントロピー弾性体を用い、分子接着剤処理を行わない以外は、実施例15と同様にして積層体(V)を得た。
基板と各種分子接着剤の結合確認は処理後、X線光電子分光XPS(アルバックファイ社製、パーキンエルマPHI5600ESCAシステム)により全ての元素を測定し行った。
基板同士の接着性は1.25cm×50cmの基板端に1.25cm×0.6cmのエントロピー弾性体をのせ、せん断剥離強度試験サンプルを作製し、引張試験機((株)島津製作所製オートグラフP-100)により、50mm/minの速度で剥離して、せん断剥離強度を求めた。
(OH基化処理基板(I)の製造)
基板1として、アルミニウム板(Al、1×30×50mm、(株)ニラコ製)、基板2として、ガラスエポキシ樹脂(EP、0.2×30×50mm、FR-4;松下電工(株)製)を用い、春日電機(株)製コロナ放電装置を用いて、13kWの出力、2m/minの速度で3往復コロナ放電処理を行い、OH基化処理基板(I-1)、(I-2)を作製した。
得られた基板(I-1)、(I-2)を分子接着剤TESの95%水/エタノール溶液(0.2wt%)に5分間浸漬後150℃、10分間オーブン中加熱をし、エタノール洗浄・ドライヤー乾燥をすると分子接着剤結合基板(II-1)、(II-2)を得た。
得られた基板(II-1)、(II-2)に、実施例9で用いたエントロピー弾性体組成物(3)のシートをサンドイッチに挟んで、加圧下、160℃で30分加熱して、エントロピー弾性体接着層を介在した基板同士の積層体(V)を得た。
表5に示す基板、分子接着剤、エントロピー弾性体にした以外は、実施例20と同様にして積層体(V)を得た。なお、表5中の「PE」は、市販品であるポリエチレンからなるシート(コクゴ社製、30×60×1mm 商品名:硬質ポリエチレンシート)を示す。
表5に示す基板、エントロピー弾性体を用い、分子接着剤処理を行わない以外は、実施例20と同様にして積層体(V)を得た。
基板にコロナ放電後、各種分子接着剤処理をすると、XPS測定の結果から、TES、S4由来の硫黄原子に基づくS2pピークが、APS由来のケイ素原子に基づくSi2pピークの存在がそれぞれ観察され、基板と各種分子接着剤が結合していることが明らかになった(図4参照)。しかしながら、分子接着剤処理しない比較例では、硫黄、ケイ素の原子は検出されなかった。
(OH基化処理基板(I)、分子接着剤結合基板(II)の製造)
表6の基板1の欄に示す基板を用い、実施例1と同様な条件にてコロナ放電処理を行い、OH基化処理基板(I)を作製した。得られた基板(I)を、表6の分子接着剤1の欄に示す分子接着剤で処理して、分子接着剤結合基板(II)を得た。なお、分子接着剤での処理の条件は、同じ分子接着剤を用いた前記の例と同じである。
得られた基板(II)の分子接着剤層形成面と、表6の弾性体の欄に示すエントロピー弾性体組成物のシート(およそ1.5mm)を貼り合わせて、5MPaの圧力下で160℃、10分間加熱したところ、基板とエントロピー弾性体の接着物(III)(弾性体の厚みは約1.2mm)が得られた。この接着物(III)について、前記<強度測定方法>と同様にして剥離強度を測定した。その結果を表6の剥離強度1の欄に示す。
得られた接着物(III)の弾性体の表面に前記と同様にしてコロナ放電を行い、その後、表6の分子接着剤2の欄に示す分子接着剤で処理して、エントロピー弾性体接着基板(IV)を得た。なお、分子接着剤での処理の条件は、同じ分子接着剤を用いた前記の例と同じである。
得られたエントロピー弾性体接着基板(IV)に、実施例1と同様な条件にて無電解めっき、さらに電気銅めっきを施し、およそ40μmのめっき厚のめっき層を有する積層体(V)が得られた。この積層体(V)について、前記<強度測定方法>と同様にして剥離強度を測定した。その結果を表6の剥離強度2の欄に示す。
(OH基化処理基板(I)、分子接着剤結合基板(II)の製造)
基板1として表7の基板1の欄に示す基板を用い、基板2として表7の基板2の欄に示す基板を用い、分子接着剤として表7の分子接着剤の欄に示す分子接着剤を用い、エントロピー弾性体として表7の弾性体の欄に示すエントロピー弾性体を用いた以外は、実施例9と同様な条件にて積層体(V)を得た。この積層体(V)ついて、前記<強度測定方法>と同様にして剥離強度を測定した。その結果を表7の剥離強度の欄に示す。なお、表7の分子接着剤の欄に示す「S4+DA」とはビス(トリエトキシシリルプロピル)テトラスルフィド(信越化学工業(株)製、KBE-846)及び2-ジアリルアミノ-1,3,5-トリアジン-4,6-ジチオールの1:1(モル比)の混合物を示す。
2)エピクロロヒドリンゴム(CHR、日本ゼオン(株)製、商品名 ゼクロン2000)
3)アクリルニトリル・ブタジエン共重合ゴム(NBR、日本ゼオン(株)製、商品名nipole1042)
4)フッ素ゴム(FKM、ダイキン工業(株)製、商品名 ダイエルG80-1)
5)1,4-シスブタジエンゴム(BR、日本ゼオン(株)製、商品名 nipoleBR)
6)シリコンゴム(Q、東レダウコーニングシリコーン(株)製、SH852U)
7)カーボンブラック(SRFカーボン旭#40、旭カーボン(株)製)
8)シリカ(日本シリカ工業(株)製、MHDF処理シリカ、商品名ニップシール)
9)ZISNET-F(架橋剤、三協化成(株)製)
10)ジクミルパーオキサイド(日本油脂製、DCP)
11)2,5-ジメチル-2,5-ジ(t-ブチルパーオキシ)ヘキサン:(日本油脂(株)製、パーヘキサ25B)
13)MBTS(大内新興化学工業(株)製、DM)
14)TMTD(大内新興化学工業(株)製、TT)
15)天然ゴム(NR)
Claims (18)
- 2つの基板の間に、エントロピー弾性分子接着層を形成してなる積層体であって、
該エントロピー弾性分子接着層が、エントロピー弾性体層及び分子接着剤層からなることを特徴とする積層体。 - エントロピー弾性分子接着層が、基板上に分子接着剤層1を形成し、該分子接着剤層1上にエントロピー弾性体層を形成し、該エントロピー弾性体層上にさらに分子接着剤層2を積層して形成されることを特徴とする請求項1に記載の積層体。
- エントロピー弾性分子接着層が、2つの基板の表面に予め分子接着剤層を形成し、該分子接着剤層が形成された2つの基板で、エントロピー弾性体層を挟み込むことによって形成されることを特徴とする請求項1に記載の積層体。
- 分子接着剤層が、基板表面に存在するOH基と分子接着剤とを反応させることにより形成されることを特徴とする請求項1~3のいずれかに記載の積層体。
- 分子接着剤層が、エントロピー弾性体層表面に存在するOH基と分子接着剤とを反応させることにより形成されることを特徴とする請求項1又は2に記載の積層体。
- 分子接着剤層が、基板の全面又は一部に形成されることを特徴とする請求項1~3に記載の積層体。
- エントロピー弾性体層が、分子接着剤層の全面又は一部に、未架橋又は架橋エントロピー弾性体組成物を接触させ、加圧下、熱及び/又は光媒体により接着して形成されることを特徴とする請求項1~5のいずれかに記載の積層体。
- エントロピー弾性体層が、1,4-シスブタジエンゴム(BR)、アクリルニトリル・ブタジエン共重合ゴム(NBR)、エチレン-プロピレン-ジエンゴム(EPDM)、フッ素ゴム(FKM)、エピクロロヒドリンゴム(CHR)、フッ素化シリコンゴム、パーオキサイド型シリコンゴム、付加型シリコンゴム及び縮合型シリコンゴムから選択される1種以上を含むことを特徴とする請求項1~7のいずれかに記載の積層体。
- 分子接着剤層が、一般式(1):
A-SiX1 3-nYn (1)
(式中、Aはエントロピー弾性体層と結合可能な基であり、X1は、それぞれ同じであっても異なっていてもよく、水素原子、置換基を有していても良い炭素数1~10の飽和又は不飽和の脂肪族炭化水素基であり、Yは炭素数1~10のアルキルオキシ基であり、nは1~3の整数である)
で示される分子接着剤の1種類以上を含んでなることを特徴とする請求項1~8のいずれかに記載の積層体。 - 分子接着剤が、下記一般式(2)~(6)で示される分子接着剤である請求項9に記載の積層体。
[X5 d(X6O)3-dSiR6]eZ (5)
(式中、X5、X6は、同じであっても異なっていてもよく、炭素数1~4の飽和又は不飽和の脂肪族炭化水素基であり、R6は炭素数1~18の2価の脂肪族炭化水素基又は芳香族炭化水素基であって、該脂肪族炭化水素基には-NH-、-CO-、-O-、-S-、-COO-、-C6H4-を含んでいてもよい。Zは、-SH、-SCSN(CH3)2、-SSCSN(CH3)2、-SCSN(C2H5)2、-SCSN(C4H9)2、-SCSN(C8H17)2、-SS-、-SSS-、-SSSS-、
H2N-R7-SiX1 3-nYn (6)
(式中、R7は、置換基を有していても良い炭素数1~10の飽和又は不飽和の脂肪族炭化水素基もしくは置換機基を有しても良い芳香族炭化水素基であり、X1、Yは前記同様であり、nは1から3までの整数である)。 - 基板が、金属、セラミックス、樹脂及びこれらの複合体からなる群から選択される1種以上の基板である請求項1~10のいずれかに記載の積層体。
- 2つの基板の少なくとも一方が、導電性基板であることを特徴とする請求項1~11のいずれかに記載の積層体。
- 導電性基板が、分子接着剤層の全面又は一部に形成されることを特徴とする請求項12に記載の積層体。
- 導電性基板が、分子接着剤層上に触媒担持後、無電解めっきにより形成されることを特徴とする請求項12又は13に記載の積層体。
- 導電性基板が、銅めっきであることを特徴とする請求項14に記載の積層体。
- 請求項1~15のいずれかに記載の積層体からなることを特徴とする回路配線基板。
- 請求項1~15のいずれかに記載の積層体からなることを特徴とする装飾めっき製品。
- 請求項1~16のいずれかに記載の積層体からなることを特徴とする接着複合体製品。
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JP6699119B2 (ja) * | 2015-01-22 | 2020-05-27 | 株式会社リコー | 素子及び発電装置 |
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JPWO2009154083A1 (ja) | 2011-11-24 |
US20110104505A1 (en) | 2011-05-05 |
JP5302309B2 (ja) | 2013-10-02 |
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