WO2013186941A1 - 表面処理方法、表面処理剤、及び新規化合物 - Google Patents
表面処理方法、表面処理剤、及び新規化合物 Download PDFInfo
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- WO2013186941A1 WO2013186941A1 PCT/JP2012/072174 JP2012072174W WO2013186941A1 WO 2013186941 A1 WO2013186941 A1 WO 2013186941A1 JP 2012072174 W JP2012072174 W JP 2012072174W WO 2013186941 A1 WO2013186941 A1 WO 2013186941A1
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- Prior art keywords
- amino
- triazine
- aminoethyl
- group
- bis
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- GTFHSIFICBLTAL-UHFFFAOYSA-N CC(C)=N/C(/N)=N\C(C)=N Chemical compound CC(C)=N/C(/N)=N\C(C)=N GTFHSIFICBLTAL-UHFFFAOYSA-N 0.000 description 1
- 0 CCCC(N=C(C)C)=NC(N[*-])=N Chemical compound CCCC(N=C(C)C)=NC(N[*-])=N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- 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
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
- A61K31/53—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with three nitrogens as the only ring hetero atoms, e.g. chlorazanil, melamine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/70—Other substituted melamines
-
- 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
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
-
- 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
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
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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]
- Y10T428/31678—Of metal
Definitions
- the present invention relates to a surface treatment technique.
- Mankind has created various products using various substances (materials). These materials are classified into metal materials, ceramic materials, polymer materials, and composite materials in which the materials are combined. Each material has its own characteristics. This characteristic demonstrates the characteristics of the product. Metals and ceramics can be products alone. However, alloys and multi-element ceramics are made by melting and mixing two or more elements. The polymer material is constructed (synthesized) by appropriately using elements such as C, H, O, N, X (halogen), P, and S. It can be said that the kind is infinite.
- Material properties are the sum of bulk properties and surface properties. Bulk properties are almost determined once the type and composition of materials are determined. The properties of the surface are not always constant even if the types and compositions of the elements constituting the bulk are the same.
- Identical material surfaces can be made as follows. For example, if a film (thin film) having the same chemical composition and surface characteristics can be applied to any material at any time, it can be realized by a surface treatment method capable of providing such a film (thin film).
- the inventors refer to such agents in particular as identical surface functionalizing agents.
- the same surface functionalizing agent that makes the surface of the material the same is brought into close contact with the material (eg, metal material, ceramic material, polymer material, organic solid, or other composite material), or chemically applied to the surface. Bind (react).
- the surface features are the same regardless of the type of material. That is, there is no difference in surface characteristics depending on the material.
- the agent having such an action is the same surface functionalizing agent.
- the same surface functionalizing agent has a function of forming a film (thin film) by strongly adhering (or bonding) to the surface of the material.
- the same surface functionalizing agent that is strongly adhered (or bonded) to the surface of the material has a function of reacting with other functional groups.
- the same surface functionalizing agent has a function that works effectively for many materials. That is, it is rich in diversity. Agents having such characteristics are specially referred to as the same surface functionalizing agent.
- Some past surface treatment agents for example, have a function to adhere to the material surface. However, the reactivity may be poor. Or it lacks diversity. For example, it can be applied to material A but not material B. That is, the range of use is narrow (it lacks diversity).
- Non-Patent Document 3 discloses a disclosure similar to that after treatment with the surface treatment agent of the present invention. However, Non-Patent Document 3 does not disclose the present invention.
- the problem to be solved by the present invention is to provide a surface treatment technology rich in adhesion function, reaction function, and diversity.
- the problem is A surface treatment method in which the compound ⁇ is provided on a substrate by applying a solution containing the compound ⁇ ,
- the compound ⁇ is An M-OH group and / or an M-OH generating group (M: metal element);
- M-OH groups and / or M-OH generating groups M: metal element
- M metal element
- There are one or more triazine rings At least one amino group of the amino group is indirectly bonded to C of the triazine ring;
- the indirectly bonded amino group is present at least at a terminal position;
- This is solved by a surface treatment method characterized by having one or more amino groups at the terminal positions.
- the problem is A surface treatment method in which the compound ⁇ is provided on a substrate by evaporation of the compound ⁇ ,
- the compound ⁇ is An M-OH group and / or an M-OH generating group (M: metal element);
- M-OH groups and / or M-OH generating groups M: metal element
- M metal element
- There are one or more triazine rings At least one amino group of the amino group is indirectly bonded to C of the triazine ring;
- the indirectly bonded amino group is present at least at a terminal position;
- This is solved by a surface treatment method characterized by having one or more amino groups at the terminal positions.
- the subject is the surface treatment method, preferably, before the compound ⁇ is provided on the substrate, cleaning treatment, corona discharge treatment, plasma discharge treatment, ultraviolet irradiation, acid treatment, alkali treatment, water vapor treatment and It is solved by a surface treatment method characterized in that one or more treatments selected from the group of chemical conversion treatments are performed on the substrate.
- the surface treatment method which is characterized in that, for example, after the compound ⁇ is provided on the substrate, a heat treatment is performed.
- the problem is A surface treatment agent used in the surface treatment method,
- the surface treatment agent contains compound ⁇ or compound ⁇ ,
- the compound ⁇ is An M-OH group and / or an M-OH generating group (M: metal element);
- M-OH groups and / or M-OH generating groups M: metal element
- M metal element
- There are one or more triazine rings At least one amino group of the amino group is indirectly bonded to C of the triazine ring;
- the indirectly bonded amino group is present at least at a terminal position;
- This is solved by a surface treatment agent characterized by having one or more amino groups at the terminal positions.
- the amino group bonded to the terminal is preferably a primary amino group.
- the M-OH group and / or M-OH generating group (M: metal element) is preferably an alkoxysilyl group.
- the compound ⁇ is preferably a compound represented by the following general formula [I]. Furthermore, a compound represented by the following general formula [II] or [III] is preferable.
- R 1 , R 2 , R 3 and R 4 are H or a functional group.
- R 1 , R 2 , R 3 and R 4 may be all the same or different.
- X, Z, Q, and V are linking groups, and there may be cases where the linking groups X, Z, and Q are absent (except when all of X, Z, and Q are absent), and Y is a skeleton.
- X and Q are linking groups, which may or may not be present (except when all of X and Q are absent)
- Y is a skeleton, which is a triazine ring (C 3 having N 3). the said triazine ring directly, -NH 2, -N 3 is not bound .
- a is an integer of 1 or more
- b is 1 or 2
- e is 1 or 2
- b + e 3
- m is an integer of 1 or more
- n is 0, 1 or 2.
- the compound ⁇ is preferably N, N′-bis (2-aminoethyl) -6- (3-triethoxysilylpropyl) amino-1,3,5-triazine-2,4-diamine, 6- ( 3-triethoxysilylpropyl) amino-2,4-dihydrazinyl-1,3,5-triazine, 2- (N, N′-di-3-triethoxysilylpropyl) amino-4,6-di (2- Aminoethyl) amino-1,3,5-triazine, 2- (2-aminoethyl) amino-4,6-di (3-triethoxysilylpropyl) amino-1,3,5-triazine, 6- (2 -Aminoethyl) amino-2,4-bis (methylethylketoximinosilyl) propylamino-1,3,5-triazine, 6- (2-aminoethyl) amino-2,4-di (triiso
- a material having a film with excellent adhesion, reactivity, and diversity on the surface can be obtained.
- the first invention is a novel compound. Particularly preferred are novel compounds that serve as the same surface functionalizing agent.
- the novel compound is represented by the general formula [I].
- R 1 , R 2 , R 3 and R 4 are H or a functional group.
- This functional group has at least one element selected from the group of elements C, O, N, and S, for example.
- the functional group is preferably a hydrocarbon group.
- the hydrocarbon group is preferably an aliphatic hydrocarbon group.
- the aliphatic hydrocarbon group is preferably an alkyl group.
- the hydrocarbon group may be linear or branched.
- the hydrocarbon group preferably has 1 to 10 carbon atoms.
- the linking group X, Z, Q, V has at least one element selected from the group of elements C, O, N, S, for example.
- the linking groups X and V are preferably hydrocarbon groups. Among these, hydrocarbon groups having 1 to 18 carbon atoms.
- the hydrocarbon group is preferably an aliphatic hydrocarbon group.
- the aliphatic hydrocarbon group is preferably an alkyl group.
- the hydrocarbon group may be linear or branched.
- the hydrocarbon group may include —S—, —O—, —NHCO—, —N ⁇ , —NH—.
- the linking groups Q and Z are preferably —NH—, —N ⁇ , —O—, —S—, —NHCO—.
- the functional group W is preferably —NR 5 R 6 , —NHOH, —NH (CH 2 ) p OH, —N ((CH 2 ) p OH) 2 , —N (CH 2 ) p NH—Y (Z (VM (R 3 ) n (OR 4 ) 3-n ) (Q (X—NR 1 R 2 )), where R 1 , R 2 , R 3 , and R 4 are H or a functional group.
- R 1 , R 2 , R 3, and R 4 may be all the same or different, and this functional group may be, for example, at least one element selected from the group of elements C, O, N, and S.
- the functional group is preferably a hydrocarbon group, particularly a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group is preferably an aliphatic hydrocarbon group. .R 5, R 6 is an alkyl group is a hydrocarbon group. Among them, a hydrocarbon group having 1 to 10 carbon atoms. before The hydrocarbon group is preferably an aliphatic hydrocarbon group, the aliphatic hydrocarbon group is preferably an alkyl group, and X, Z, Q, and V are linking groups. In some cases, Q may be absent (except when all of X, Z, and Q are absent.)
- the linking groups X, Z, Q, and V are selected from the group of elements C, O, N, and S, for example.
- the linking groups X and V are preferably a hydrocarbon group, and particularly a hydrocarbon group having 1 to 18 carbon atoms, and the hydrocarbon group is preferably an aliphatic group.
- the aliphatic hydrocarbon group is preferably an alkyl group, and the hydrocarbon group may be linear or branched, and the hydrocarbon group may be —S—, —O—, —NHCO. -, -N ⁇ , -NH- may be included
- the linking groups Q, Z are preferably -NH-, -N ⁇ .
- Y is a skeleton, and this skeleton has a triazine ring (C 3 N 3 ), preferably, the triazine ring is directly bonded to —NH 2 , -N 3 (azi group) is not bonded, M is at least one selected from the group consisting of Si, Al, and Ti, p is an integer of 1 or more, particularly an integer of 1 to 12 N is 0, 1 or 2. a is preferably an integer of 8 or less.
- the novel compound is particularly represented by the general formula [II] or the general formula [III].
- R 1 , R 2 , R 3 , and R 4 are H or a functional group.
- the functional group is preferably a hydrocarbon group.
- the hydrocarbon group is preferably an aliphatic hydrocarbon group.
- the aliphatic hydrocarbon group is preferably an alkyl group.
- the hydrocarbon group may be linear or branched.
- the hydrocarbon group preferably has 1 to 10 carbon atoms.
- the linking group X, Q has at least one element selected from the group of elements C, O, N, S, for example.
- the linking group X is preferably a hydrocarbon group.
- the hydrocarbon group is preferably an aliphatic hydrocarbon group.
- the aliphatic hydrocarbon group is preferably an alkyl group.
- the hydrocarbon group may be linear or branched.
- the hydrocarbon group preferably has 1 to 18 carbon atoms.
- the hydrocarbon group may include —S—, —O—, —NHCO—, —N ⁇ , —NH—.
- the linking group Q is preferably —NH—, —N ⁇ , —O—, —S—, —NHCO—.
- the triazine ring may be a heterocyclic ring having C 3 N 3 .
- the triazine ring is used in a sense including a melamine structure (C 3 N 3 N 3 H 3 ).
- the triazine ring is preferably a 1,3,5-triazine ring.
- a is preferably an integer of 8 or less.
- m is preferably an integer of 1 to 18.
- —NH 2 , —N 3 (azi group) is not directly bonded to the triazine ring.
- the functional group ⁇ (NR 1 R 2 ) a XQ ⁇ , W, ⁇ Z (VM (R 3 ) n (OR 4 ) 3-n ) ⁇ , ⁇ NH (CH 2 ) m Si (R 3) n (OR 4) 3-n ⁇ , n ⁇ (CH 2) m Si (R 3) n (OR 4) 3-n ⁇ 2 is preferably Is bonded to C of the skeleton (Y) of the triazine ring.
- the skeleton Y is bonded to the skeleton Y via a bond to C (CN bond).
- ⁇ (NR 1 R 2 ) a XQ ⁇ , ⁇ Z (VM (R 3 ) n (OR 4 ) 3-n ) ⁇ are the elements of the terminal functional groups of X, Q, Z, and V
- the skeleton (Y) is bonded to the skeleton Y via a bond with C (CN bond, CC bond, CO bond).
- the amino group bonded to the terminal is preferably a primary amino group.
- the novel compound include N, N′-bis (2-aminoethyl) -6- (3-triethoxysilylpropyl) amino-1,3,5-triazine-2,4-diamine, 6- (3- Triethoxysilylpropyl) amino-2,4-dihydrazinyl-1,3,5-triazine, 2- (N, N′-di-3-triethoxysilylpropyl) amino-4,6-di (2-aminoethyl) ) Amino-1,3,5-triazine, 2- (2-aminoethyl) amino-4,6-di (3-triethoxysilylpropyl) amino-1,3,5-triazine, 6- (2-amino) Ethyl) amino-2,4-bis (methylethylketoximinosilyl) propylamino-1,3,5-triazin
- A -N (R a ) R b -Si (R c ) n (OR d ) 3-n , or -N ⁇ R b -Si (R c ) n (OR d) 3-n ⁇ 2
- B —N (R e ) R f (NH 2 ) m , or —N ⁇ R f (NH 2 ) m ⁇ 2
- C A, B, or -N (R g )
- R h D R i [However, R a , R e and R g are H or a hydrocarbon group.
- R b , R c , R d , R f , R h , R i are hydrocarbon groups.
- n 0, 1 or 2.
- m is 1 or 2.
- the hydrocarbon group may or may not contain —S—, —O—, —NHCO—, —N ⁇ , —NH—.
- the hydrocarbon group may have a substituent or may not have a substituent.
- the hydrocarbon group is preferably an aliphatic hydrocarbon group.
- the aliphatic hydrocarbon group is preferably an alkyl group.
- R a preferably has 1 to 12 carbon atoms.
- R b preferably has 1 to 12 carbon atoms.
- R c preferably has 1 to 6 carbon atoms.
- R d preferably has 1 to 6 carbon atoms.
- R e preferably has 1 to 12 carbon atoms.
- R f preferably has 1 to 12 carbon atoms.
- R g preferably has 1 to 12 carbon atoms.
- R h preferably has 1 to 12 carbon atoms.
- R i preferably has 1 to 12 carbon atoms.
- ⁇ A -NH- (CH 2) l-Si (O (CH 2) n (CH 3)) 3, -N ((CH 2) l- Si (O (CH 2) n (CH 3) 3, -NH- (CH 2) l-Si (CH 3) (O (CH 2) n (CH 3)) 2, or -NH-C 6 H 4 -O- ( CH 2) l-Si (O (CH 2) n (CH 3)) 3
- the second invention is a surface treatment agent.
- a surface treating agent that can be said to be the same surface functionalizing agent.
- the surface treatment agent is an agent made for the purpose of adhesion with the compound ⁇ , for example.
- the surface treating agent is an agent made for the purpose of chemical reaction or physical adsorption by the compound ⁇ , for example.
- the surface treatment agent is compound ⁇ .
- the compound ⁇ is included.
- the compound ⁇ has at least an M—OH group and / or an M—OH generating group (M: metal element), an amino group, and a triazine ring.
- M-OH group and / or M-OH-forming group is preferably bonded directly or indirectly (via a linking group) to a carbon atom of the triazine ring.
- the amino group is preferably bonded directly or indirectly (via a linking group) to the carbon atom (C) of the triazine ring. At least one amino group of the amino group is indirectly bonded to the carbon atom (C) of the triazine ring.
- the indirectly bonded amino group is present at least at the terminal position. There are one or more amino groups at the terminal positions. For example, one or two. There are one or more M-OH groups and / or M-OH generating groups (M: metal element). M is preferably Si, Al, or Ti.
- the triazine ring is one or more. For example, one or two.
- the amino group bonded to the terminal is preferably a primary amino group.
- the M—OH group and / or M—OH generating group is particularly preferably an alkoxysilyl group.
- M metal element
- the compound ⁇ having a primary amino group and an alkoxysilyl group in one molecule is in contact with a material selected from a metal material, a ceramic material, a polymer material, etc., these materials and compounds It is strongly bonded to the surface of the material by the generation of chemical bonds (or strong adsorption) by reaction with ⁇ .
- strong adhesion adsorption
- silane coupling agent In the case of chemical bonding (reaction), of course, the volatilization of the compound ⁇ does not occur. Such a state can be analyzed by XPS.
- a compound having both a primary amino group and an alkoxysilyl group in one molecule is commercially available as a silane coupling agent.
- conventional silane coupling agents do not adsorb (react) to any of metal materials, ceramic materials, polymer materials, and the like.
- the type of material changes, the type of silane coupling agent and the processing conditions also differ.
- a material having almost no —OH on the surface for example, a polymer material
- strong adhesion and chemical bonding hardly occur.
- the compound ⁇ of the present invention is greatly different from the conventional silane coupling agent.
- the compound ⁇ is preferably a compound represented by the general formula [I]. Especially, it is a compound represented by the said general formula [II] or [III]. For example, it is a compound represented by the general formulas [IV] and [V].
- —NH 2 , —N 3 (azi group) is not directly bonded to the triazine ring.
- the amino group bonded to the terminal is preferably a primary amino group.
- the third invention is a surface treatment method. This is a treatment method using the compound ⁇ .
- the surface treatment is performed for the purpose of adhesion with the compound ⁇ , for example.
- the surface treatment is performed for the purpose of chemical reaction or physical adsorption with the compound ⁇ , for example.
- a third invention is a method of applying a solution containing the compound ⁇ on a substrate, for example. Examples of the application method include a dipping method, a spraying method, and a brush coating method. Of course, it is not limited to this. An evaporation method may be used instead of the coating method.
- the third invention is a method of evaporating the compound ⁇ , for example, and depositing (depositing) the evaporated compound ⁇ on the substrate.
- the coating method is simpler than the evaporation method.
- the cost is low.
- one or more treatments preferably selected from the following group are performed on the substrate. For example, cleaning treatment, corona discharge treatment, plasma discharge treatment, ultraviolet irradiation, acid treatment, alkali treatment, steam treatment and chemical conversion treatment.
- heat treatment is performed as necessary.
- the chemical conversion treatment include group I element hydroxides, group I element salts, group II element hydroxides, group II element salts, ammonia, ammonium salts, hydrazine, hydrazine derivatives, amines, and phosphoric acid. Phosphate, carbonate, carboxylic acid, carboxylate, silicic acid, silicate and fluoride are used.
- a film or the like is formed on the metal surface by the chemical conversion treatment.
- a substrate made of various materials is treated with the compound ⁇ (for example, provided on the substrate surface by applying the compound ⁇ ), a material having the same surface function can be obtained.
- the physical properties of the substrate are basically the same, although the physical properties of the bulk are different. Surface properties of these materials include metal catalyst adsorption, chemical and biological compound reactivity, metallizing properties, heat resistance, corrosion resistance, antioxidant properties, UV stability, hydrophobicity, hydrophilicity, and solder adhesion. Bondability, electrical conductivity, colorability, dyeability, printability and transferability are expected.
- a functional group and a function-imparting agent such as various functional compounds and functional group-containing compounds (silane coupling agents), catalytic properties, chemical and biological reactivity, metallizing properties, heat resistance , Corrosion resistance, antioxidant, UV stability, hydrophobicity, water repellency, lipophilicity and hydrophilicity, solder adhesion, bondability, adhesiveness, electrical insulation, electrical conductivity, antifouling, antibacterial Heterogeneous functionality that enables the provision of smoothness and roughness, abrasion resistance, colorability, dyeability, printability, transferability, decorating properties, biocompatibility, luminescence, light selective absorption, etc. It is considered that a functional group surface-containing material surface is obtained.
- a functional group surface-containing material surface is obtained.
- the same surface functionalized film obtained with the same surface functionalizing agent has a certain adhesion strength (indicating cohesive failure) regardless of the type of material. It is important not to cause interfacial delamination for many materials by a delamination test. That is, it is important to show sufficient adhesion strength and cohesive failure even if the material changes. Furthermore, the reactive function is utilized when the same surface functionalizing agent is changed to various different functional surfaces. Therefore, it is necessary to cause a chemical reaction to the whole (or part) of the film and to change the part to a different function. It is also important that the material provided with such a function has a diversity function in which the material surface plays various roles. Moreover, it is important to say that it is given by a simple method. If it cannot be realized without a special method, it is difficult to put it into practical use.
- the physical properties of all materials are the sum of the bulk properties and the surface properties. For manufacturing, these properties must be well known.
- the surface characteristics of a material have many factors such as wettability, tackiness, water repellency, hydrophilicity, adhesiveness, adsorptivity, smoothness, water retention, chargeability, reactivity, and hardness. Just understanding this requires a lot of time and effort.
- it is important that the surface of the material is in the same state. That is, if the same surface is achieved, it is more convenient to understand the multiple factors as described above. And it is practical.
- there is no known method for homogenizing the surface state of many materials (metals, ceramics, and organic materials) to a degree of about 90% or more with a single compound.
- the compound ⁇ When the compound ⁇ is brought into contact with the substrate surface, the compound ⁇ reacts (or strongly adsorbs) with the substrate material so that the surface has, for example, a hydroxysilyl group (or alkoxysilyl group) or an amino group. Thus, the characteristics of the substrate are greatly modified. Whether the surface functionalizing agent (the compound ⁇ ) reacts with the substrate and is bonded by a chemical bond or is in close contact with a strong adsorbing force is determined by the characteristic of the surface functionalizing agent (the compound ⁇ ) in XPS analysis. It is clear from the detection of elements N and Si.
- the surface functionalizing agent (the compound ⁇ ) When the surface functionalizing agent (the compound ⁇ ) is brought into contact with another compound that reacts (or adsorbs) with a hydroxysilyl group and / or an amino group, the surface changes to a surface having another function. In this way, it can be modified to the intended functional or useful surface.
- the resulting surface functionalized material is an amphiphile material that can be reversibly converted to hydrophilization and hydrophobization, entire and partial metallization of the functionalized organic material, functionalized organic material and metal material, ceramic material, organic material, etc. Many applications such as fluid adhesion and non-fluid adhesion with the above materials, electroless plating and electroplating of the functionalized metal material, anticorrosion of the functionalized metal material and prevention of surface oxidation are possible.
- the substrate provided with the compound ⁇ may be the final product itself. However, it is often said that the intermediate material proceeds to the next step.
- the compound ⁇ When the compound ⁇ is treated with a functional group and / or a function-imparting agent, the former and the latter react. And a different functional group and a different functional surface containing material are obtained.
- These materials may be useful as composite products by becoming products with their own functions, or by joining, laminating and assembling these same and different materials. In some cases, plating is performed.
- the surface treatment agent of the present invention has “adhesion function”, “reactivity function”, and “diversity function”. More specifically, it is the compound ⁇ . Or it is a mixture containing the said compound (alpha).
- the compound ⁇ is more preferably represented by the general formula [I]. More preferably, it is represented by, for example, the general formula [II] or the general formula [III]. For example, it is represented by the general formula [IV] or [V].
- the compound is synthesized through, for example, [Reaction Formula 1] [Reaction Formula 2].
- the solvent used in the above reaction does not react with the functional group contained in the amino group, alkoxysilyl group, and alkoxysilyl group.
- the solvent satisfying such conditions varies depending on the combination of the amino group and the alkoxysilyl group-containing functional group. Therefore, it is difficult to determine uniquely.
- water eg, water, alcohol (eg, methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, cellosolve, carbitol, etc.), ketone (eg, acetone, methyl ethyl ketone, cyclohexanone, etc.), aromatic hydrocarbon (eg, benzene, toluene) , Xylene, etc.), aliphatic hydrocarbons (eg, hexane, octane, decane, dodecane, octadecane, etc.), esters (eg, ethyl acetate, methyl propionate, methyl phthalate), ethers (eg, tetrahydrofuran, ethyl butyl ether, anisole) Etc.), and mixtures thereof.
- alcohol eg, methanol, ethanol, isopropanol, ethylene glycol, propylene glycol,
- the reaction temperature is unambiguous because it is governed by the activity of the triazine compound as a skeleton and the functional group of an amino group (for example, primary diamine or primary triamine) or an alkoxysilyl group-containing compound. Is not decided. However, it is generally -20 ° C to 200 ° C. Preferably, it is ⁇ 10 ° C. to 100 ° C. When the temperature is lower than ⁇ 20 ° C., the reaction rate is slow and the productivity is inferior. At 200 ° C. or higher, there are more cases where equipment such as an autoclave is required. And reaction rate becomes high too much and it becomes easy to produce
- the ratio of the amino compound (primary diamine or primary triamine) (molar ratio) to one carbon element of the triazine compound as a skeleton is 1 or more in the latter / the former.
- the ratio is 2-10.
- the ratio is less than 1, the target product is hardly obtained or the raw material remains.
- the ratio exceeds 10 and the amount of impurities produced decreases, it takes time to remove unreacted amines. And production efficiency is poor.
- the ratio (molar ratio) of the alkoxysilyl group-containing compound it is important that the latter / the former is 1 or more. In general, the ratio is 1.05 to 1.50. When the ratio is less than 1, unreacted raw materials remain and the yield decreases. When the ratio exceeds 1.50, the amount of impurities generated increases. And production efficiency is bad.
- the treatment is effective even when the compound ⁇ is a mixture of two or more kinds. Therefore, the reaction product can be used as it is without being isolated to a single compound.
- the compounds obtained here are mainly monomers represented by compound ⁇ , but dimers, oligomers, alkoxysilyl groups in which triazines having terminal amino groups and by-products having unreacted carbon atoms are reacted in the synthesis process. Condensates and / or mixtures thereof.
- the obtained compound ⁇ (compound represented by the general formula [I]) is provided on the substrate by a coating means.
- a coating means For example, if the compound ⁇ (the compound represented by the general formula [I]) is not liquid, it is added to a solvent. The substrate is immersed in this solution, so that the compound ⁇ is provided on the substrate. Even when the solution is sprayed, the compound ⁇ is provided on the substrate.
- a spin coating method can also be used.
- a brush coating method can also be used.
- various application methods can be employed. Other than the coating method, a method of evaporating the compound ⁇ and depositing it on the substrate can also be used. In any case, however, the application method can be carried out very simply.
- the compound ⁇ is strongly adhered to the substrate.
- a chemical reaction takes place and binds. That is, only the compound ⁇ is in contact with the substrate, and both are in close contact with each other. Therefore, the same surface function is exhibited.
- the average film thickness of the compound ⁇ is about 1 nm to 20 nm.
- the compound ⁇ is thinner.
- the bond is not a chemical reaction but the adhesion is strong, the film thickness of the compound ⁇ is relatively thick. Even if it is thick, it is only thicker than in the case of bonding by chemical reaction.
- the average film thickness is about 1 to 5 nm.
- the compound ⁇ is bonded to the substrate by strong adsorption, it is thicker than the thickness (1 to 5 nm).
- the strong adhesion is when the compound ⁇ does not volatilize even if left for a long time in an ultrahigh vacuum of 10 ⁇ 6 Pa. If it is in such a state, the analysis by XPS is possible.
- the adhesion strength is a level at which the silicone rubber phase is destroyed when the silicone rubber is adhered. And it can be said that this force corresponds to the case of chemical bonding.
- Such an adhesive force is a strength that cannot be considered by intermolecular force.
- the solvent used for the coating can be the same as the solvent used for the reaction. That is, water, alcohol, ketone, aromatic hydrocarbon, aliphatic hydrocarbon, ester, ether, and a mixture thereof can be mentioned.
- the concentration of compound ⁇ is about 0.001 wt% to 10 wt%. If it is too thin, less than 0.001 wt%, the effect is poor. If it is too thick exceeding 10 wt%, it takes time for post-processing.
- the temperature during the coating process is about ⁇ 20 ° C. to 200 ° C.
- the processing time is about 0.1 second to 12 hours.
- the concentration of the compound ⁇ , the treatment temperature, and the treatment time are related to each other, and the optimum solution can be obtained by repeating the experiment.
- the treated substrate is heated to ⁇ 20 ° C. (preferably 15 ° C. or more) to 200 ° C. under a vacuum atmosphere, normal pressure, or pressure. Retained.
- the holding time is 0.1 second to 12 hours. This can be considered as a fixing treatment of the compound ⁇ on the substrate.
- the film of the compound ⁇ when the film is accompanied by a chemical reaction, has an acid amide group (—CONH—), an amino group (NH 2 —, —NH—), an alkoxysilyl group (—SiOR), and / or hydro It has an oxysilyl group (—SiOH).
- the film When the film is formed by strong adhesion, it has an amino group (NH 2 —, —NH—), an alkoxysilyl group (—SiOR), and / or a hydroxysilyl group (—SiOH).
- the alkoxysilyl group is hydrolyzed and changed to a hydroxysilyl group.
- the alkoxysilyl group is hydrolyzed and changed to a hydroxysilyl group while exposed to moisture.
- Amino group (NH 2 -, - NH-) in between the electron localization nitrogen and Hydroxyfluoran silyl group and a triazine ring, a hydrogen bond (H ... N ... H), and / or salt linkages (> NH 2 - ... + OSi ⁇ ) is formed. This seems to make the substrate surfaces substantially the same. That is, the film of the compound ⁇ is considered to have the same surface functionalization.
- the film of the compound ⁇ is strongly bonded to many materials (for example, resin materials such as olefin resin, nylon resin, and polyvinyl alcohol: ceramic materials such as glass and alumina: metal materials such as Cu and Al). Yes.
- resin materials such as olefin resin, nylon resin, and polyvinyl alcohol: ceramic materials such as glass and alumina: metal materials such as Cu and Al.
- This binding force cannot be explained in the scope of primary and secondary bonds.
- resin materials such as olefin resin, nylon resin, and polyvinyl alcohol: ceramic materials such as glass and alumina: metal materials such as Cu and Al.
- the film of the compound ⁇ bonded to the substrate by reaction or adsorption has an amino group, an alkoxysilyl group, and / or a hydroxysilyl group on the surface. Accordingly, the surface of the film of the compound ⁇ has a reactive functional group. This reactive functional group is used to give more reactivity and functionality.
- the homofunctional reagent contains two or more identical functional groups.
- di (hydroxyphenyl) methane, di (2,4-hydroxymethyl) phenol, di (2,4-hydroxymethyl) -3,5-xylenol, di (2,4-hydroxymethyl) -m-cresol Melamine, trimethylolmelamine, hexamethylolmelamine, trimethoxymethylmelamine, hexamethoxymethylmelamine, guanamine, tetramethylurea, cyanuric acid, phthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, trimellitic acid, pyromellitic Acid, rosin succinic acid, phthalic anhydride, trimellitic anhydride, rosin maleic anhydride, pyromellitic anhydride, dihydroxydimethyl silicon, trihydroxymethyl silicon, octanedithiol, pentaerythritol tetrathioglycol
- heterofunctional reagent examples include the following compounds.
- 6-alkoxysilylpropylamino-1,3,5-triazine-2,4-dithiol monosodium 6-bis (3-alkoxysilylpropyl) amino-1,3,5-triazine-2,4-dithiol Monosodium, 6-N-cyclohexyl-N- (3- (triethoxysilyl) propylamino) -1,3,5-triazine-2,4-dithiol monosodium, vinylmethoxysiloxane homopolymer, bis (triethoxy Silylpropyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2,4-bis (2-aminoethylamino) -6- (3-triethoxysilylpropylamino) -1,3 , 5-triazine, 2,
- Nanoparticle-dispersed reagents are biologically-relevant nanoparticle-dispersed reagents such as proteins and enzymes having a particle size of 1 nm to 100 nm, polymer nanoparticle (monodispersed or polydisperse polymer nanoparticle) dispersed reagents, metal nanoparticle dispersed reagents, metal Examples thereof include oxide nanoparticle dispersion reagents, metal inorganic salt nanoparticle dispersion reagents, and metal nanoparticle dispersion reagents.
- vapor phase methods chemical reaction method, thermal CVD method, plasma CVD method, molecular beam epitaxy method, evaporation concentration method, sputtering method, EB heating method, gas evaporation method, laser ablation method, resistance heating method
- Liquid phase method chemical liquid phase method, chemical reaction precipitation method, microwave heating method, reverse micelle method, normal micelle method, hydrothermal synthesis method, sol-gel method, physical liquid phase method, spray drying method
- solid phase Manufactured by a method firing method, heating furnace method
- the metal nanoparticles include nanoparticles such as Fe, Co, Ni, Au, Ag, Cu, Sn, Pb, Ge, In, Pt, and Zn.
- metal oxide nanoparticles Fe 3 O 4 , CeO 2 , BaTiO 3 , PbSrTiO 3 , CaPt 0.05 Ti 0.95 O 3 , Al 2 O 3 , MgO, Mn 3 O 4 , NiO, SiO 2 , Examples thereof include nanoparticles such as TiO 2 , ZrO 2 , YO 3 —ZnO 2 , and clay.
- metal inorganic salt nanoparticles examples include AgCl, AgBr, tin compounds (for example, stannous formate, stannous acetate, stannous propionate, stannous butyrate, stannous valerate, stannous caproate, Stannous caprylate, stannous caprate, stannous laurate, stannous benzoate, stannous maleate, stannous fumarate, stannous methoxy, stannous ethoxy, stannous propoxy , Butoxy stannous, pentaoxy stannous, hexaoxy stannous, phenoxy stannous, benzyloxy stannous, etc.).
- tin compounds for example, stannous formate, stannous acetate, stannous propionate, stannous butyrate, stannous valerate, stannous caproate, Stannous caprylate, stannous caprate, stannous laurate, stannous benzoate, stannous maleate,
- Examples of biologically relevant nanoparticles include nanoparticles of proteins, bacteria, viruses, DNA, antibodies, enzymes, hormones, and the like.
- Examples of polymer nanoparticles include polyethylene, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polyethyl acrylate, polyhexyl acrylate, polyacrylic amide, polydimethylacrylic acid amide, polyisopropylacrylic acid amide.
- nanoparticles such as polyvinyl acetate.
- Other examples include nanoparticles such as fullerene, carbon nanotube, carbon black, ZnS, and PbSe.
- the agent functional imparting agent and / or reactive imparting agent
- a material having various functions is obtained.
- an appropriate means selected from a coating method, a vapor deposition method, a sputtering method, and the like is employed.
- the solvent used for the coating the same solvents as mentioned for coating the compound ⁇ can be used.
- the technical idea mentioned in the application of the compound ⁇ can be applied to the concentration, treatment time, treatment temperature, and post-treatment.
- the film thickness of the agent (functional agent and / or reactive agent) is appropriately set.
- the compound ⁇ and the agent (functional agent and / or reactive agent) are bonded to each other by an adhesive force such as a chemical bond, an ionic bond, a hydrogen bond, a van der Waals force, or a London dispersion force.
- substrate in the present invention, various substrates can be used as the target substrate.
- a metal material It is a ceramic material.
- Organic polymer material It is an inorganic polymer material.
- it is a composite material in which the materials are combined.
- the form is not particularly limited.
- the present invention can be applied to various forms such as a plate, a rod, a column, a sphere, a hemisphere, a frame, a fiber, a thread, a powder, a nonwoven fabric, a cloth, a net, a foamed body, a film, a sheet, and a laminated body.
- Examples of the metal material include various metals, alloys, shape memory alloys, superelastic alloys, functional metals, amorphous metals, and fiber reinforced metal blocks.
- metal material constituent elements include Be, Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Rh, Ir, Examples thereof include Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ge, Sn, Pb, Sb, Bi, and Nd.
- alloys include iron alloys (steel, carbon steel, cast iron), copper alloys (phosphor bronze, brass, cupronickel, beryllium copper, titanium copper), aluminum alloys (alloy components other than Al are Cu, Mn, Zn, Ni, etc., as appropriate), magnesium alloys (alloy components other than Mg are appropriately selected from the group such as Zn, Ca, etc.), zinc alloys, bell alloys, nickel alloys, gold alloys, silver alloys, Platinum alloy, palladium alloy, lead alloy, titanium alloy ( ⁇ -type, ⁇ -type, ⁇ + ⁇ -type alloy), cadmium alloy, zirconium alloy, cobalt alloy, chromium alloy, molybdenum alloy, tungsten alloy, manganese alloy, ferritic stainless steel, martensite Stainless steel, austenitic stainless steel, precipitation strengthened stainless steel, nickel-titanium alloy, iron-manganese-titanium alloy, Elastic alloy (nickel - titanium alloy), and the like.
- the metal material Prior to the treatment with the compound ⁇ , the metal material is preferably subjected to surface cleaning.
- wet cleaning water-based: pure water, tap water, functional water, non-aqueous: hydrocarbon-based, non-flammable solvent-based
- dry cleaning ultraviolet ray, ozone, ultraviolet ray + ozone, plasma, corona discharge, argon aerosol, liquefied carbon dioxide gas
- the ceramic material examples include ceramics (kaolin, glazed clay, porcelain stone, feldspar, quartzite, quartz, alumina, etc.), glass, cement, plaster, and wandering. From the viewpoint of composition, oxide-based, zirconia-based, hydroxide-based, carbide-based, carbonate-based, nitride-based, halide-based, phosphate-based and the like can be mentioned.
- barium titanate, Bi 2 Sr 2 Ca 2 Cu 3 O 10 high-temperature superconducting ceramics, boron nitride, ferrite, lead zirconate titanate, silicon carbide, silicon nitride, steatite, zinc oxide, nitride
- the surface of the ceramic material is also preferably cleaned before it is treated with the compound ⁇ . For example, wet cleaning is performed. Alternatively, dry cleaning is performed.
- the organic polymer material typically has a C—C bond or a C—H bond.
- examples thereof include thermosetting resins, thermoplastic resins, fiber reinforced plastics, photocurable resins, vulcanized rubber, and uncrosslinked rubber.
- As the skeleton constituting the polymer there are a two-dimensional linear structure and a three-dimensional network structure.
- cellulose such as hydroxyethyl cellulose, cellulose ester (derivative) such as cellulose diacetate, starch, vinyl acetate resin, low density polyethylene, high density polyethylene, polypropylene, ethylene propylene copolymer, petroleum resin , Polystyrene, syndiotactic polystyrene, styrene copolymer, chroman indene resin, terpene resin, styrene / divinylbenzene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS) resin, polymethyl acrylate, polyacrylic acid Ethyl, polyacrylonitrile, polymethyl acrylate, polymethyl methacrylate, polyethyl methacrylate, polycyanoacrylate, polyvinyl acetate, ethylene / vinyl acetate copolymer (EVA) resin, polyvinyl Lucol,
- EVA ethylene / vinyl
- the polymer material is a crosslinking agent, a crosslinking accelerator, a crosslinking assistant, a radical initiator, a cationic initiator, a photopolymerization initiator, a scorch inhibitor, a stabilizer, an anti-aging agent, an ultraviolet ray inhibitor, a filling agent. Including some additives such as agents, reinforcing agents, plasticizers, softeners, colorants, viscosity modifiers.
- the three-dimensional network structure polymer is a composition obtained by adding a cross-linking agent (if necessary, a cross-linking accelerator or a cross-linking auxiliary agent) to the two-dimensional linear polymer in the presence of heat and / or light. (Polymer cross-linked polymer).
- the monomer in the monomer-crosslinked polymer is a polymerizable monomer such as a vinyl group, an acrylate group, a methacrylate group, an epoxy group, an isocyanate group, or an oxetane group.
- a crosslinking agent if necessary, a crosslinking accelerator or a crosslinking assistant
- the monomer in the monomer-crosslinked polymer is a polymerizable monomer such as a vinyl group, an acrylate group, a methacrylate group, an epoxy group, an isocyanate group, or an oxetane group.
- examples thereof include urethane acrylate monomers, epoxy acrylate monomers, ester acrylate monomers, acrylate monomers, epoxy monomers, vinyl ether monomers, and the like. Specific examples include acrylates.
- methacrylates For example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, hexyl methacrylate, octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate Stearyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-dimethylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate, 2-t-butylaminoethyl methacrylate, glycidyl methacrylate, allyl methacrylate, cyclohexyl methacrylate,
- a polymerization initiator a crosslinking agent, a crosslinking accelerator, and a crosslinking assistant.
- peroxides cationic polymerization initiators, photoinitiators, sulfur, sulfur crosslinking accelerators, polyol crosslinking agents, polyamine crosslinking agents, Examples thereof include a polythiol-based crosslinking agent, an acrylate-based crosslinking aid, a methacrylate-based crosslinking aid, and an allyl-based crosslinking aid.
- azobisbutyronitrile benzophenone, mihira arctone, benzoin isopropyl ether, chlorothioxanthone, isopropylthioxanthone, benzyldimethyl ketal, acetophenone diethyl ketal, ⁇ -hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-phenylpropane Is mentioned. Also included are acetophenone derivatives.
- a benzoin ether type compound is also mentioned. Examples thereof include benzoin ethyl ether and benzoin propyl ether. Examples also include ketal derivative compounds such as benzyldimethyl ketal.
- halogenated ketones include acyl phosphine oxides, acyl phosphonates, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide, phenyl dimethyl sulfone chloride, triaryl
- sulfone hexafluorophosphate include sulfone hexafluorophosphate, triazine dithiol-based crosslinking agent, resin crosslinking agent, polyol crosslinking agent, H-terminal siloxane crosslinking agent, and silanol condensation crosslinking agent.
- the three-dimensional network structure polymer contains, for example, a cross-linking agent, a cross-linking accelerator, and a cross-linking auxiliary with respect to 100 parts by weight of the two-dimensional linear polymer (or low molecular monomer), respectively.
- a two-dimensional linear structure polymer thermoplastic resin, uncrosslinked rubber
- the photo-curing resin is a UV device (for example, a high-pressure mercury UV lamp, a low-pressure mercury UV lamp, a fluorescent UV) in the air, in a nitrogen atmosphere, in an argon atmosphere, or under reduced pressure.
- a lamp short ARC xenon lamp, chemical lamp
- metal halide lamp it is obtained by irradiating ultraviolet rays in the range of 200 to 400 nm at a rate of 10 mJ / m 2 to 20 kJ / m 2 .
- the composition constituting the photocurable resin contains, for example, a photopolymerization catalyst.
- the amount is, for example, 0.01 to 5 parts by weight with respect to 100 parts by weight of the compound having an epoxy group.
- the vulcanized rubber has a composition containing a linear polymer having a glass transition temperature of ⁇ 20 ° C. or less, a crosslinking agent, and desired components such as a crosslinking accelerator, at 0 to 300 ° C. (preferably 60 to 180 ° C.). ) At a temperature of 0.1 to 120 minutes (preferably 5 to 60 minutes). If the temperature is low, the reaction time is too long and the productivity is deteriorated. Conversely, if the temperature is high, the energy cost is too high.
- the process is performed under the above conditions.
- An example of the polymer material is a coating film.
- the coating film is often a composite material.
- the coating film is generally obtained by mixing a two-dimensional linear polymer (thermoplastic resin) with a crosslinking agent, a crosslinking accelerator, a crosslinking assistant, and a solvent, and applying and drying the mixture. If necessary, a polymerization process is also performed.
- the organic polymer material has a filler and a functional additive as necessary.
- the functional additive is an additive that exhibits a desired function.
- the functional additive may be a reinforcing agent.
- Examples of the agent include carbon black, calcium carbonate, talc, flat talc, mistron talc, clay, kaolin, flat kaolin, cellulose, celite, flat clay, kaolin, glass, barium titanate, strontium titanate, mica, silica.
- Examples of the reinforcing agent include rayon, nylon, polyester, vinylon, steel, kevlar, carbon fiber, and glass fiber. These may be in the form of fibers or cloth.
- powders such as copper, nickel, silver, gold, tin, and carbon are listed.
- a conductive material is also mentioned.
- Examples of the heat transfer material include alumina, silicon nitride, alumina nitride, silicon carbide, and diamond.
- the amount added is an amount according to the purpose.
- Stabilizers anti-aging agents, UV inhibitors
- the stabilizer increases the reliability of the polymer material.
- amine-ketone condensates for example, poly (2,2,4-trimethyl-1,2-dihydroquinoline), 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline
- Aromatic secondary amine compounds for example, octyl diphenylamine, 4,4-bis ( ⁇ , ⁇ -dimethylbenzyl) diphenylamine, N, N-diphenyl-p-phenylenediamine, N-phenyl-N′-isopropyl-p- Phenylenediamine, N-phenyl-N′-isopropyl-1,3-dimethylbutyl-p-phenylenediamine, etc.), mono and bisphenol compounds (for example, styrenated phenol, 2,6-di-t-butyl-4- Phen
- the composite material is an appropriate combination of the metal material, the ceramics material, and the polymer material.
- a ceramic material is provided on the surface of a metal material.
- a polymer material is provided on the surface of a metal material.
- a metal material is provided on the surface of the ceramic material.
- a polymer material is provided on the surface of a ceramic material.
- the material A and the material B are joined. Of course, it is not limited to this.
- each material is subjected to a cleaning process in advance. Alternatively, for example, it is treated with a silane coupling agent or the like.
- One of the substrates treated with the surface treatment agent is used as an adherend, the other of the substrates treated (or not treated) with the surface treatment agent is used as an adhesive, and the two are joined together.
- a plated product is obtained by immersing (or spraying) these materials in an electroless plating solution, followed by electroplating.
- a circuit board can also be made by applying a resist to the metallized product after plating and etching the plating film. If a groove or a channel is made on the substrate surface and the same material is bonded after hydrophobization (or after hydrophilization), a hydrophobized (or hydrophilized) microchannel can be easily made.
- fluid bonding processing bonding or cross-linking
- metal materials ceramic materials, polymer materials, or composite polymer materials. Bonding) or non-fluid bonding (assembly bonding) is possible.
- the present invention is effective in many industrial fields such as electronic equipment, materials field, automobile field, robot field, architecture / construction field, environment / energy field.
- digital devices, portable / mobile devices, high-frequency module devices, and network devices are rapidly becoming multifunctional, high-performance, and miniaturized.
- SiP System in Package
- Example 1 6- (3-Triethoxysilylpropyl) amino-1,3,5-triazine-2,4-dichloride (TEDC) and N, N′-bis (2-aminoethyl) -6- (3-triethoxysilyl) Propyl) amino-1,3,5-triazine-2,4-diamine (TEDDA) was synthesized according to the following reaction formulas (1-1) and (1-2).
- a stirrer and cyanuric chloride (CC: 18.325 g; 99.37 mmol: manufactured by Kanto Chemical Industry Co., Ltd.) were placed in a 500 mL three-necked flask. A thermometer and dropping funnel were attached. The flask was placed under an argon atmosphere. To this was added THF (200 mL). Cooled to -20 ° C. Thereafter, a solution of 3-triethoxysilylpropylamine (28 mL; 120 mmol: manufactured by Chisso Corporation) / THF (20 mL: manufactured by Kanto Chemical Industry Co., Ltd.) was gradually added dropwise over 30 minutes.
- a stirrer and ethylenediamine (11 mL; 165 mmol: manufactured by Tokyo Chemical Industry Co., Ltd .: purified by molecular sieve) were placed in a 300 mL three-necked flask. The flask was placed under an argon atmosphere. A mixed solution of 6- (3-triethoxysilylpropyl) amino-1,3,5-triazine-2,4-dichloride (7.821 g; 21.18 mmol) and THF (60 mL) was added dropwise. After the addition, the reaction solution was gradually heated to 90 ° C. This was followed by a reaction over 17 hours. This was followed by cooling to room temperature. Suction filtration was performed through celite.
- a stirring bar and hydrazine monohydrate (4.0 mL; 82 mmol: manufactured by Tokyo Chemical Industry Co., Ltd.) were placed in a 200 mL three-necked flask. The flask was placed under an argon atmosphere. This was cooled to 0 ° C. In this state, a mixed solution of 6- (3-triethoxysilylpropyl) amino-1,3,5-triazine-2,4-dichloride (3.734 g; 10.11 mmol) and ethanol (50 mL) was added dropwise. It was. After the addition, the reaction solution was gradually heated to 50 ° C. This was followed by a reaction at 50 ° C. for 2 hours.
- DTEDC was synthesized from cyanuric chloride (CC) and di (N, N'-triethoxysilylpropyl) amine. Thereafter, a reaction between DTEDC and ethylenediamine was carried out in the presence of ethanol and triethylamine (TEA). The reaction solution was filtered. Thereafter, the solvent and unreacted ethylenediamine were distilled off under reduced pressure of 1 to 10 mmHg. This was dissolved in a methanol solution and decolorized by adding activated carbon. After concentration, purification by silica gel chromatography column was performed. By concentrating this, a pale yellow syrup was obtained. This was obtained from elemental analysis data, NMR spectrum, etc. according to 2- (N, N′-di-3-triethoxysilylpropyl) amino-4,6-di (2-aminoethyl) amino-1,3,5. -Found to be triazine (DTEDEA).
- DTEC was synthesized from cyanuric chloride (CC) and di (triethoxysilylpropyl) amine. Thereafter, the reaction between DTEC and ethylenediamine was carried out in the presence of ethanol and triethylamine (TEA). The reaction solution was filtered. Thereafter, the solvent and unreacted ethylenediamine were distilled off under a reduced pressure of 10 mmHg. This was dissolved in a methanol solution. Decolorization with activated carbon was performed. After concentration, purification by silica gel chromatography column was performed. By concentrating this, a pale yellow syrup was obtained. This is 2- (2-aminoethyl) amino-4,6-di (3-triethoxysilylpropyl) amino-1,3,5-triazi (DTEEA) from elemental analysis data, NMR spectrum, etc. I understood.
- Example 5 the surface treatment with the compound (TEDDA) of Example 1 was performed.
- a substrate of 10 mm ⁇ 20 mm ⁇ 0.1 mm was prepared.
- the substrate is a Ti plate, Mo plate, Ni plate, Cu plate, Al plate, Ag plate, Pt plate, Sn plate, SUS316 plate, or brass plate. That is, 10 types of substrates were prepared.
- Each substrate was subjected to ultrasonic degreasing in ethanol at 40 ° C. for 15 minutes. This was followed by rinsing with ethanol. Thereby, the surface was cleaned. After cleaning, drying was performed in a vacuum desiccator.
- the substrate after the above treatment was immersed in an aqueous solution containing TEDDA (0.1 wt%). After 10 minutes, the substrate was lifted. This was followed by thorough rinsing with distilled water. Thereafter, it was left in a dry desiccator at 20 ° C. under a vacuum (0.1 mmHg or less) for 24 hours.
- TEDDA 0.1 wt%
- the XPS analyzer is a linear photoelectron spectrometer (manufactured by ULVAC-PHI: PHI-Quntera SXM Scanning X-ray Microprobe, irradiation angle 45 degrees).
- aminopropyltriethoxysilane (APS: AIS0610.0 manufactured by Amax Co.) was used instead of the TEDDA, and the same procedure was performed.
- Table 1 shows the following. As compared to the APS-treated substrate, the TEDDA-treated substrate as a whole has a reduced surface metal concentration and oxygen concentration, and a significantly increased nitrogen concentration and silicon concentration. This indicates that TEDDA strongly adsorbs (bonds) to the substrate surface, whereas APS hardly adsorbs (bonds) to the substrate surface. In this analysis, since the X-ray irradiation angle is 45 degrees, elements from the outermost surface to a depth of 7 nm are measured. In the surface analysis of the TEDDA-treated substrate, metal atoms are sufficiently observed, so that the thickness of the TEDDA film is 7 nm or less. Since XPS analysis measures 10 ⁇ 6 Pa or less, it is understood that TEDDA is adsorbed (bonded) to the substrate with a higher binding force (bonding force comparable to chemical bonding) than the normal intermolecular force. Is done.
- Example 6 the surface treatment with the compound (TEDDA) of Example 1 was performed.
- a substrate of 10 mm ⁇ 10 mm ⁇ 0.1 mm was prepared.
- the substrate is an alumina plate, a silicon carbide plate, an aluminum nitride plate, a zinc oxide plate, a carbon plate, a glass plate, a zirconia plate, a ceramic plate, a cement plate, or a gypsum plate. That is, 10 types of substrates were prepared. And the process similar to the said Example 5 was performed.
- aminopropyltriethoxysilane APS was used instead of the TEDDA, and the same procedure was performed.
- Table 2 shows the following.
- the TEDDA-treated substrate as a whole has a reduced surface metal concentration and oxygen concentration, and a significantly increased nitrogen concentration and silicon concentration.
- the AlN plate is made of Al and N
- the SiC plate is made of Si and C
- the above-mentioned tendency is not remarkable, but the same can be said. That is, it can be seen that TEDDA is strongly adsorbed (bonded) to the surface of the ceramic material.
- the X-ray irradiation angle is 45 degrees, elements from the outermost surface to a depth of 7 nm are measured.
- TEDDA-treated substrate metal atoms are sufficiently observed, so that the thickness of the TEDDA film is 7 nm or less. Since XPS analysis measures 10 ⁇ 6 Pa or less, it is understood that TEDDA is adsorbed (bonded) to the substrate with a higher binding force (bonding force comparable to chemical bonding) than the normal intermolecular force. Is done.
- Example 7 the surface treatment with the compound (TEDDA) of Example 1 was performed.
- a substrate of 10 mm ⁇ 20 mm ⁇ 0.2 mm was prepared.
- the substrate includes a polyethylene plate (PE: LD-PE: 07-127-01: manufactured by Hagitec Co., Ltd.), a polypropylene plate (PP: manufactured by Kokugo: 07-175-04), a tetrafluoroethylene plate (PTFE: NO.903UL).
- PE polyethylene plate
- PP polypropylene plate
- PTFE NO.903UL
- POM Duracon M25-44: manufactured by Polyplastics
- nylon plate PA6: P07-142-04, manufactured by KOKUGO
- polyethylene-2,6-naphthalate plate PEN: manufactured by Teijin Jupon Co., Ltd .: Teonex (R)
- PET Toraycon, manufactured by Toray Industries, Inc.
- PEEK PEEK450G: manufactured by Yasojima Proceed Co., Ltd.
- PPS C-130SG: Idemitsu Kosan Co., Ltd.
- AEPS aminoethylaminopropyltriethoxysilane
- the TEDDA-treated substrate has a surface carbon concentration and an oxygen concentration that are reduced, and a nitrogen concentration and a silicon concentration are significantly increased, as compared with the AEPS-treated substrate (comparative example).
- the nitrogen concentration is significantly increased by TEDDA treatment except for PA6 containing nitrogen.
- all contain silicon because no resin containing silicon is used.
- PTFE has a small amount of adsorption, it is clearly bonded with a considerable adhesion. This indicates that TEDDA is strongly adsorbed on the surface of the resin material.
- the X-ray irradiation angle is 45 degrees, elements from the outermost surface to a depth of 7 nm are measured.
- the thickness of the TEDDA film is 7 nm or less. Since XPS analysis measures 10 ⁇ 6 Pa or less, it is understood that TEDDA is adsorbed (bonded) to the substrate with a higher binding force (bonding force comparable to chemical bonding) than the normal intermolecular force. Is done.
- Example 8 the surface treatment with the compound (TEDDA) of Example 1 was performed.
- Ethylene propylene diene rubber EPDM, JSR-EP
- silicone rubber plate Q: SH-851U: manufactured by Toray Dow Corning Co., Ltd.
- SBR styrene butadiene rubber
- NBR DN300: manufactured by Nippon Zeon Co., Ltd.
- FKM G-901: manufactured by Daikin Industries, Ltd.
- AEPS aminoethylaminopropyltriethoxysilane
- Table 4 shows the following.
- Q crosslinked silicone rubber
- NBR contains nitrogen as a constituent component of the material.
- other rubbers do not contain silicon or nitrogen. Therefore, in the surface analysis of the TEDDA-treated substrate and the untreated substrate, it can be seen that the presence / increase of N and Si is due to the presence of TEDDA on the surface due to the reaction (or strong adsorption) of the crosslinked rubber. It is surprising that TEDDA is bound (adsorbed) to rubber whose surface molecular chains are perturbed.
- Example 9 the surface treatment with the compound (TEDDA) of Example 1 was performed.
- the substrate is a composite material. That is, the fillers shown in Table-5 were blended with polymer materials such as Q, PE, SBR, PA6, and PPS.
- the filler blends for Q and SBR were two rolls and the filler blends for PE and PA6 were done using a kneader. Then, press molding with a mold was performed at a temperature of 120 ° C. to 180 ° C. for 5 minutes, and a 10 mm ⁇ 20 mm ⁇ 0.1 mm substrate was obtained. And the process similar to the said Example 5 was performed.
- AEPS aminoethylaminopropyltriethoxysilane
- Table-5 shows the following.
- Q cross-linked silicone rubber
- NBR contains N as a constituent component, but the others do not contain Si and N. Therefore, in the surface analysis of the TEDDA-treated composite material and the untreated composite material, it can be seen that the presence and increase of N and Si are present by the reaction (or strong adsorption) of TEDDA on the composite material surface.
- Example 10 Substrate of Example 5d (TEDDA-treated Cu plate), substrate of Example 5e (TEDDA-treated Al plate), substrate of Example 5i (TEDDA-treated SUS316 plate), substrate of Example 6f (TEDDA-treated SiO 2 plate), implementation A PI board (PI: Kapton, manufactured by Toray DuPont) processed in the same manner as in Example 7 and a UR board (UR: 07-007-01: manufactured by Kokugo) processed in the same manner as in Example 7 were prepared. A Cu plate used in Example 5d, a PP plate used in Example 7b, and a Q plate used in Example 8b were prepared. TEDDA processing is not performed. These substrates were subjected to ultrasonic degreasing (40 ° C.
- Example 5i A PI plate (PI: Kapton, manufactured by Toray DuPont Co., Ltd.) and a substrate of Example 5i (TEDDA-treated SUS316 plate) that had been treated in the same manner as in Example 7 were prepared.
- the TEDDA-treated SUS316 plate (the substrate of Example 5i) was further coated with an acrylic urethane-based paint (U: Urecoat, Composite Materials Co., Ltd.). And the hardening process (50 degreeC; 24 hours) was performed. Thereafter, similar to Example 5i, surface treatment with an aqueous TEDDA solution was performed on the acrylic urethane-based coating film.
- These TEDDA-treated substrates were immersed (temperature: 25 ° C.
- a catalyst treatment solution (NP-8 manufactured by Uemura Kogyo Co., Ltd .; 150 mL / L HCl; 150 mL / L).
- NP-8 manufactured by Uemura Kogyo Co., Ltd .
- 150 mL / L HCl 150 mL / L
- a Pd—Sn catalyst was supported on the surface.
- the substrate on which the Pd—Sn catalyst is supported is an electroless copper plating bath (Sulcup PSY-1A manufactured by Uemura Kogyo Co., Ltd .; 100 ml / L Sulcup PSY-1B; 55 ml / L 18.5% formalin aqueous solution; 20 mL / L ) Was immersed (temperature: 33 ° C. time: 20 minutes). This was followed by electroplating.
- the electrolytic bath used for this electroplating is a sulcup ETN bath (CuSO4 ⁇ 5H2O; 80 g / L H2SO4; 200 g / L Cl ⁇ ; 50 ppm) manufactured by Uemura Kogyo Co., Ltd., a sulcup ETN-1A bath (1 ml / L), Sulcup ETN-1B bath (10 ml / L).
- the current was 2.5 A / dm2.
- the time was 60 minutes.
- the temperature was 25 ° C.
- the thickness of the Cu plating film thus obtained was 30 ⁇ m.
- AEPS manufactured by Amax
- TEDDA TEDDA
- the sample according to the present invention has very high adhesive strength (adhesion strength).
- Example 11 A stirrer and N, N-dimethylethylenediamine (20.0 g; 0.230 mmol) were placed in a 500 mL three-necked flask. The flask was placed under an argon atmosphere. To this was added THF (200 mL). A mixed solution of 6- (3-triethoxysilylpropyl) amino-1,3,5-triazine-2,4-dichloride (8.3 g; 22.5 mmol) and THF (100 mL) was added dropwise. After the addition, the reaction solution was gradually heated to 90 ° C. This was followed by a reaction for 8 hours. This was followed by cooling to room temperature. Suction filtration was performed through celite.
- Example 12 A stirrer and 1,6-hexanediamine (46.5 g; 0.40 mol) were placed in a 300 mL three-necked flask. The flask was placed under an argon atmosphere. To this was added THF (80 g). A mixed solution of 6- (3-triethoxysilylpropyl) amino-1,3,5-triazine-2,4-dichloride (14.8 g; 0.04 mol) and THF (20 g) was added dropwise. After the addition, the reaction solution was gradually heated. This was followed by a reaction for 5 hours under reflux. This was followed by cooling to room temperature. Suction filtration was performed through celite. The filtrate was concentrated on a rotary evaporator.
- Example 13 A stirrer and tris (2-aminoethyl) amine (29.3 g; 0.20 mmol) were placed in a 300 mL three-necked flask. The flask was placed under an argon atmosphere. To this was added THF (40 g). A mixed solution of 6- (3-triethoxysilylpropyl) amino-1,3,5-triazine-2,4-dichloride (7.8 g; 0.02 mol) and THF (10 g) was added dropwise. After the addition, the reaction solution was gradually heated to 90 ° C. This was followed by a reaction for 8 hours. This was followed by cooling to room temperature. Suction filtration was performed through celite.
- Example 14 A stirrer and 1,12-dodecanediamine (40.1 g; 0.20 mol) were placed in a 500 mL three-necked flask. The flask was placed under an argon atmosphere. To this was added THF (200 g). A mixed solution of 6- (3-triethoxysilylpropyl) amino-1,3,5-triazine-2,4-dichloride (7.8 g; 0.02 mol) and THF (10 g) was added dropwise. After the addition, the reaction solution was gradually heated. This was followed by a reaction for 10 hours under reflux. This was followed by cooling to room temperature. Suction filtration was performed through celite. The filtrate was concentrated on a rotary evaporator.
- Example 15 The Cu plate used in Example 5d was prepared. TEDDA (Example 1), DTEDH (Example 2), DTEDEA (Example 3), DTEEA (Example 4), TEDDMA (Example 11), TEDHDA (Example 12), TEBTTA (Example 13), TEDDDA (Example 14) was used. The same surface treatment as in Example 5 was performed. The PP plate used in Example 7b was prepared. Treatment with compound ⁇ is not performed. This substrate was subjected to ultrasonic degreasing (40 ° C. for 15 minutes in ethanol). Thereafter, rinsing with ethanol was performed.
- corona discharge treatment (Corona master output voltage manufactured by Shinko Electric Measurement Co., Ltd .; 9 kV (surface voltage), oscillation frequency: 20 kHz, temperature: 20 ° C.) was performed.
- the treated Cu substrate of each compound and the untreated PP substrate were arranged to face each other so that each compound film was sandwiched. Thereafter, a 1 MPa press was applied.
- the press temperature was 120 ° C.
- the press time was 10 minutes.
- a PI plate (PI: Kapton, manufactured by Toray DuPont) was prepared.
- TEDDA (Example 1)
- TEDHDA (Example 12)
- TEBTTA (Example 13)
- TEDDDA Example 14
- the same surface treatment as in Example 5 was performed.
- These treatment substrates were immersed (temperature: 25 ° C. time: 1 minute) in a catalyst treatment solution (NP-8 manufactured by Uemura Kogyo Co., Ltd .; 150 mL / L HCl; 150 mL / L).
- NP-8 manufactured by Uemura Kogyo Co., Ltd .
- 150 mL / L HCl 150 mL / L
- the substrate on which the Pd—Sn catalyst is supported is an electroless copper plating bath (Sulcup PSY-1A manufactured by Uemura Kogyo Co., Ltd .; 100 ml / L Sulcup PSY-1B; 55 ml / L 18.5% formalin aqueous solution; 20 mL / L ) was immersed (temperature: 33 ° C. time: 20 minutes). This was followed by electroplating.
- an electroless copper plating bath (Sulcup PSY-1A manufactured by Uemura Kogyo Co., Ltd .; 100 ml / L Sulcup PSY-1B; 55 ml / L 18.5% formalin aqueous solution; 20 mL / L ) was immersed (temperature: 33 ° C. time: 20 minutes). This was followed by electroplating.
- the electrolytic bath used for this electroplating is a sulcup ETN bath (CuSO4 ⁇ 5H2O; 80 g / L H2SO4; 200 g / L Cl ⁇ ; 50 ppm) manufactured by Uemura Kogyo Co., Ltd., a sulcup ETN-1A bath (1 ml / L), Sulcup ETN-1B bath (10 ml / L).
- the current was 2.5 A / dm2.
- the time was 60 minutes.
- the temperature was 25 ° C.
- the thickness of the Cu plating film thus obtained was 30 ⁇ m.
- the sample according to the present invention has very high adhesive strength (adhesion strength).
- Example 1 was performed in the same manner except that ethylenediamine (11 mL) was changed to ethylenediamine (7 mL). As a result, a mixture of a TEDDA monomer and a TEDDA dimer (see the general formula described in the above [0027]) was obtained. That is, a mixture of a monomer and a dimer (the mixing ratio changed depending on the amount of ethylenediamine) was obtained. Isolation of the dimer from this mixture was not straightforward.
- the surface treatment with the mixture was performed in the same manner as in Example 5. The result of this surface treatment was the same as the result of the surface treatment of Example 5.
- the surface treating agent of the present invention can be applied to many substrates, it can be seen that the surface treating agent has diversity. Since the compound ⁇ provided on the substrate surface is rich in reactivity, it can be applied to various fields by utilizing this reaction characteristic. For example, even when it is desired to provide a compound X capable of reaction (adsorption) with the compound ⁇ on the substrate, this is simple. It is understood that the present invention can be applied to various fields (for example, decorative products, circuit boards, and other composite products).
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Description
非特許文献3には本発明の表面処理剤による処理後のものに似たものの開示が認められるようである。しかしながら、非特許文献3には本発明の開示は無い。
化合物αを含有する溶液が塗布されることにより前記化合物αが基板上に設けられる表面処理方法であって、
前記化合物αは、
M-OH基および/またはM-OH生成基(M:金属元素)と、
アミノ基と、
トリアジン環
とを少なくとも有し、
前記M-OH基および/またはM-OH生成基(M:金属元素)は一つ以上有り、
前記トリアジン環は一つ以上有り、
前記アミノ基の少なくとも一つのアミノ基は、前記トリアジン環のCに、間接的に、結合してなり、
前記間接的に結合したアミノ基は、少なくとも、末端位置に存在してなり、
前記末端位置のアミノ基は一つ以上有る
ことを特徴とする表面処理方法
によって解決される。
化合物αの蒸発により前記化合物αが基板上に設けられる表面処理方法であって、
前記化合物αは、
M-OH基および/またはM-OH生成基(M:金属元素)と、
アミノ基と、
トリアジン環
とを少なくとも有し、
前記M-OH基および/またはM-OH生成基(M:金属元素)は一つ以上有り、
前記トリアジン環は一つ以上有り、
前記アミノ基の少なくとも一つのアミノ基は、前記トリアジン環のCに、間接的に、結合してなり、
前記間接的に結合したアミノ基は、少なくとも、末端位置に存在してなり、
前記末端位置のアミノ基は一つ以上有る
ことを特徴とする表面処理方法
によって解決される。
前記表面処理方法に用いられる表面処理剤であって、
前記表面処理剤は化合物α、又は化合物αを含むものであり、
前記化合物αは、
M-OH基および/またはM-OH生成基(M:金属元素)と、
アミノ基と、
トリアジン環
とを少なくとも有し、
前記M-OH基および/またはM-OH生成基(M:金属元素)は一つ以上有り、
前記トリアジン環は一つ以上有り、
前記アミノ基の少なくとも一つのアミノ基は、前記トリアジン環のCに、間接的に、結合してなり、
前記間接的に結合したアミノ基は、少なくとも、末端位置に存在してなり、
前記末端位置のアミノ基は一つ以上有る
ことを特徴とする表面処理剤
によって解決される。
{(NR1R2)aX-Q}bY(W)c{Z(V-M(R3)n(OR4)3-n)}d
(式[I]中、R1,R2,R3,R4はH又は官能基である。R1とR2とR3とR4とは、全てが同じでも、異なるものでも良い。X,Z,Q,Vは連結基である。連結基X,Z,Qが無い場合も有る(但し、X,Z,Qの全てが無い場合は除かれる)。Yは骨格である。この骨格はトリアジン環(C3N3)を有する。前記トリアジン環には、直接、-NH2,-N3が結合していない。Wは、{Z(V-M(R3)n(OR4)3-n)}以外の官能基である。MはSi,Al,Tiの群の中から選ばれる少なくとも一つである。aは1以上の整数、bは1又は2、cは0又は1、dは1又は2、b+c+d=3、nは0,1又は2である。)
{(NR1R2)aX-Q}bY{NH(CH2)mSi(R3)n(OR4)3-n}e
一般式[III]
{(NR1R2)aX-Q}bY[N{(CH2)mSi(R3)n(OR4)3-n}2]e
(式[II][III]中、R1,R2、R3,R4はH又は官能基である。R1、R2、R3,R4とは、同じでも、異なるものでも良い。X,Qは連結基である。連結基X,Qが無い場合も有る(但し、X,Qの全てが無い場合は除かれる)。Yは骨格である。この骨格はトリアジン環(C3N3)を有する。前記トリアジン環には、直接、-NH2,-N3が結合していない。aは1以上の整数、bは1又は2、eは1又は2、b+e=3、mは1以上の整数、nは0,1又は2である。)
前記新規化合物は、特に、前記一般式[II]または前記一般式[III]で表される。前記一般式[II][III]中、R1,R2,R3,R4はH又は官能基である。前記官能基は、好ましくは、炭化水素基である。前記炭化水素基は、好ましくは、脂肪族炭化水素基である。脂肪族炭化水素基は、好ましくは、アルキル基である。前記炭化水素基は直鎖型でも分岐型でも良い。前記炭化水素基は、好ましくは、炭素数が1~10である。連結基X,Qは、例えば元素C,O,N,Sの群の中から選ばれる少なくとも一つの元素を有する。連結基Xは、好ましくは、炭化水素基である。前記炭化水素基は、好ましくは、脂肪族炭化水素基である。脂肪族炭化水素基は、好ましくは、アルキル基である。前記炭化水素基は直鎖型でも分岐型でも良い。前記炭化水素基は、好ましくは、炭素数が1~18である。前記炭化水素基は-S-,-O-,-NHCO-,-N<,-NH-を含んでも良い。連結基Qは、好ましくは、-NH-,-N<,-O-,-S-,-NHCO-である。本発明において、トリアジン環は、C3N3を有する複素環であれば良い。本発明において、トリアジン環は、メラミン構造(C3N3N3H3)をも含む意味で用いられている。トリアジン環は1,3,5-トリアジン環が好ましい。aは、好ましくは、8以下の整数である。mは、好ましくは、1~18の整数である。好ましくは、前記トリアジン環には、直接、-NH2,-N3(アジ基)が結合していない。前記一般式[I][II][III]において、前記官能基{(NR1R2)aX-Q},W,{Z(V-M(R3)n(OR4)3-n)},{NH(CH2)mSi(R3)n(OR4)3-n},N{(CH2)mSi(R3)n(OR4)3-n}2は、好ましくは、トリアジン環の骨格(Y)のCに結合している。特に、{NH(CH2)mSi(R3)n(OR4)3-n},N{(CH2)mSi(R3)n(OR4)3-n}2は、Nと前記骨格YのCとの結合(C-N結合)を介して、骨格Yに結合している。{(NR1R2)aX-Q},{Z(V-M(R3)n(OR4)3-n)}は、X,Q,Z,Vの末端官能基の元素と前記骨格(Y)のCとの結合(C-N結合、C-C結合、C-O結合)を介して、骨格Yに結合している。
前記新規化合物は、好ましくは、末端に結合したアミノ基が第1級アミノ基である。
前記新規化合物は、例えばN,N’-ビス(2-アミノエチル)-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-ジアミン、6-(3-トリエトキシシリルプロピル)アミノ-2,4-ジヒドラジニル-1,3,5-トリアジン、2-(N,N’-ジ-3-トリエトキシシリルプロピル)アミノ-4,6-ジ(2-アミノエチル)アミノ-1,3,5-トリアジン、2-(2-アミノエチル)アミノ-4,6-ジ(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、6-(2-アミノエチル)アミノ-2,4-ビス(メチルエチルケトキシミノシリル)プロピルアミノ-1,3,5-トリアジン、6-(2-アミノエチル)アミノ-2,4-ジ(トリイソプロポキシシリル)プロピルアミノ-1,3,5-トリアジン、6-(2-アミノエチル)アミノ-2,4-ジ(トリアセトキシシリル)プロピルアミノ-1,3,5-トリアジン、6-(2-アミノエチル)アミノ-2,4-ジ(トリイソプロペノオキシシシリル)プロピルアミノ-1,3,5-トリアジン、6-(2-アミノエチル)アミノ-2,4-ジ(トリイソプロポキシシリル)プロピルアミノ-1,3,5-トリアジン、6-(2-アミノエチル)アミノ-2,4-ジ(トリベンゾキシシリル)プロピルアミノ-1,3,5-トリアジン、6-(2-アミノエチル)アミノ-2,4-ビス(トリエトキシシリルへキシル)アミノ-1,3,5-トリアジン、6-(2-アミノエチル)アミノ-2,4-ビス(トリエトキシシリルドデシル)アミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ビス(メチルエチルケトキシミノシリル)プロピルアミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ビス(メチルエチルケトキシミノシリル)プロピルアミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ジ(トリイソプロポキシシリル)プロピルアミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ジ(トリアセトキシシリル)プロピルアミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ジ(トリイソプロペノオキシシシリル)プロピルアミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ジ(トリイソプロポキシシリル)プロピルアミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ジ(トリベンゾキシシリル)プロピルアミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ビス(トリエトキシシリルヘキシルアミノ)-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ビス(トリエトキシシリルプロピル)アミノ-1,3,5-トリアジン、N,N’-ビス(2-ジメチルアミノエチル)-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-ジアミン、N,N’-ビス(2-アミノヘキシル)-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-ジアミン、N,N’-ビス{2-[ビス-(2-アミノエチル)アミノ]エチル}-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-ジアミン、又はN,N’-ビス(12-アミノドデシル)-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-ジアミンである。前記具体例は、ほんの、数例が例示されたに過ぎない。勿論、これ以外にも、幾つもの化合物が挙げられる。しかし、限が無いので省略される。
前記新規化合物は、例えば下記一般式[IV]又は[V]で表される。
一般式[IV]
一般式[V]
上記一般式[IV][V]中、A,B,C,Dは、例えば下記の基である。
A=-N(Ra)Rb-Si(Rc)n(ORd)3-n,or
-N{Rb-Si(Rc)n(ORd)3-n}2
B=-N(Re)Rf(NH2)m,or -N{Rf(NH2)m}2
C=A,B,or -N(Rg)Rh
D=Ri
[但し、Ra,Re,RgはH又は炭化水素基である。Rb,Rc,Rd,Rf,Rh,Riは炭化水素基である。nは0,1又は2である。mは1又は2である。前記炭化水素基は、-S-,-O-,-NHCO-,-N<,-NH-を含む場合と、含まない場合とが有る。前記炭化水素基は、置換基を有する場合と、置換基を有さない場合とが有る。]
前記炭化水素基は、好ましくは、脂肪族炭化水素基である。前記脂肪族炭化水素基は、好ましくは、アルキル基である。
前記Raは、好ましくは、炭素数が1~12である。前記Rbは、好ましくは、炭素数が1~12である。前記Rcは、好ましくは、炭素数が1~6である。前記Rdは、好ましくは、炭素数が1~6である。前記Reは、好ましくは、炭素数が1~12である。前記Rfは、好ましくは、炭素数が1~12である。前記Rgは、好ましくは、炭素数が1~12である。前記Rhは、好ましくは、炭素数が1~12である。前記Riは、好ましくは、炭素数が1~12である。
A,B,C,Dの具体例が幾つか下記に示される。但し、これに限られない。
{A=-NH-(CH2)l-Si(O(CH2)n(CH3))3,
-N((CH2)l-Si(O(CH2)n(CH3)3,
-NH-(CH2)l-Si(CH3)(O(CH2)n(CH3))2,or
-NH-C6H4-O-(CH2)l-Si(O(CH2)n(CH3))3
B=-NH-(CH2)l(NH2),or -N((CH2)l(NH2)2
C=A,B,-NH(CH2)lCH3,-N((CH2)lCH3)2,or
-N(CH2CH=CH2)((CH2)mCH3)
D=-(CH2)p-
l,m,n,,p:1以上の整数}
{A=-NH-(CH2)l-Si(O(CH2)n(CH3))3,
-NH-(CH2)l-Si(CH3)(O(CH2)n(CH3))2,or
-NH-C6H4-O-(CH2)l-Si(O(CH2)n(CH3))3,
B=-NH-(CH2)l(NH2),or -N((CH2)l(NH2)2
C=A,orB
D=-(CH2)p-
l,n,p:1以上の整数}
{A=-N((CH2)l-Si(O(CH2)n(CH3))3,
-N((CH2)l-Si(CH3)(O(CH2)n(CH3))2)2,or
-N-(C6H4-O-(CH2)l-Si(O(CH2)n(CH3)2)((CH2)pCH3)
B=-NH-(CH2)l(NH2),or -N((CH2)l(NH2)2
C=A,orB
D=-(CH2)p-
l,n,p:1以上の整数}
本発明の表面処理剤は、「密着性機能」「反応性機能」「多様性機能」を有する。
より具体的に説明すると、前記化合物αである。又は、前記化合物αを含む混合物である。
前記化合物αの膜の表面には、アミノ基、アルコキシシリル基、及び/又はハイドロキシシリル基が存在する。これ等の官能基は反応性を有する。従って、各種の物質(試薬)との反応が可能になる。例えば、同種官能性試薬、異種官能性試薬、ナノ粒子分散試薬との間で反応が起きる。このような物質(試薬)による表面処理により、多種多様な機能を有する材料に変換される。
本発明において、対象となる基板は、各種のものが挙げられる。例えば、金属材料である。セラミックス材料である。有機高分子材料である。無機高分子材料である。或いは、前記材料が複合された複合材料である。形態も特に限定されることは無い。例えば、板、棒、柱、球、半球、枠、繊維、糸、粉体、不織布、布、網、発砲体、フイルム、シート、積層体など各種の形態のものに適用できる。
ポリチオール系架橋剤、アクリレート系架橋助剤、メタクリレート系架橋助剤、アリル系架橋助剤等である。具体的には、アゾビスブチロニトリル、ベンゾフェノン、ミヒラアーケトン、ベンゾインイソプロピルエーテル、クロロチオキサントン、イソプロピルチオキサントン、ベンジルジメチルケタール、アセトフェノンジエチルケタール、α-ヒドロキシシクロヘキシルフェニルケトン、2-ヒドロキシ-2-メチル-フェニルプロパンが挙げられる。アセトフェノン誘導体も挙げられる。例えば、4-(2-ヒドロキシエトキシ)フェニル(2-ヒドロキシ-2-プロピル)ケトン、α-ヒドロキシ-α,α’-ジメチルアセトフェノン、メトキシアセトフェノン、2,2-ジメトキシ-2-フェニルアセトフェノン等である。ベンゾインエーテル系化合物も挙げられる。例えば、ベンゾインエチルエーテル、ベンゾインプロピルエーテル等である。ベンジルジメチルケタールなどのケタール誘導体化合物も挙げられる。その他にも、ハロゲン化ケトン、アシルフォスフィンオキシド、アシルフォスフォナート、ビス-(2,6-ジメトキシベンゾイル)-2,4,4-トリメチルペンチルフォスフィンオキシド、フェニルジメチルスルホニュウムクロリド、トリアリールスルホニュウムヘキサフルオロフォスフェート、トリアジンジチオール系架橋剤、樹脂架橋剤、ポリオール架橋剤、H末端シロキサン系架橋剤、シラノール縮合系架橋剤なども挙げられる。ジベンゾチアゾイルジスルフィド、4-モルホリノジチオベンゾチアゾール、N-シクロヘキシル-2-ベンゾチアゾイルスルフェンアミド、N-t-ブチル-2-ベンゾチアゾイルスルフェンアミド、N-オキシジエチレン-2-ベンゾチアゾイルスルフェンアミド、N-ジイソプロピル-2-ベンゾチアゾイルスルフェンアミドN-ジシクロヘキシル-2-ベンゾチアゾイルスルフェンアミド、テトラメチルチューラムジスルフィド、テトラエチルチューラムジスルフィド、テトラブチルチューラムジスルフィド、テトラオクチルチューラムジスルフィド、アミン類、ヘキサメチレンテトラミン、ザリゲン、第四級アンモニュウム塩、ホスホニュウム塩、ジアルキルスズ有機酸塩、チタネート、ポリエチレングリコール、塩化白金酸、酸化亜鉛、酸化マグネシウム、酸化カルシウム、酸化バリウム、酸化アルミニウム、水酸化カルシウム、酸化鈴、酸化鉄、水酸化カルシウム、炭酸カルシウム、炭酸マグネシウム、脂肪酸ナトリウム、オクチル酸カルシウム、イソオクチル酸カリウム、カリウムブトキサイド、オクチル酸セシウム、イソステアリン酸カリウム、ポリエチレングリコール、ポリプロピレングリコール、ヘキサンジオール、シクロヘキサンジオール、ドデカンジオール、ヘキサメチレンジアミン、ドデカンジアミン、末端ジアミノポリエチレングリコール、末端ジアミノポリプロピレングリコール、ベンゼンジチオール、ヘキサンジチオール、1,10-デカンジチオール、1,12-ドデカンジチオール、ポリエチレングリコールジアクリレート、ポリエチレングリコールジメタアクリレート、ポリプロピレングリコールジアクリレート、ポリプロピレングリコールジメタアクリレート、ジアリルエーテル、トリアリルイソシアヌレート、トリアリルシアヌレートも挙げられる。三次元網目構造ポリマー(熱硬化性樹脂、架橋ゴム)は、例えば二次元線状ポリマー(又は低分子モノマー)100重量部に対し、架橋剤、架橋促進剤や架橋助剤を、各々、0.1~20重量部(好ましくは、0.5~10重量部)を添加した組成物を、20~350℃の温度で、0.1秒~200分間に亘って、ロールシーティング加工、カレンダーロール加工、プレス加工、押出加工及び射出成形加工することで得られる。二次元線状構造ポリマー(熱可塑性樹脂、未架橋ゴム)も公知の方法で得られる。光硬化樹脂は、光硬化樹脂を構成する組成物に対し、大気中、窒素雰囲気中、アルゴン雰囲気中、或いは減圧中で、UV装置(例えば、高圧水銀UVランプ、低圧水銀UVランプ、蛍光式UVランプ(ショートARCキセノンランプ、ケミカルランプ)、メタルハライドランプ)を用い、10mJ/m2~20kJ/m2の割合で、200~400nmの範囲の紫外線を照射することにより得られる。光硬化樹脂を構成する組成物は、例えば光重合触媒を含む。その量は、例えばエポキシ基を有する化合物100重量部に対し、0.01~5重量部である。光重合触媒の配合割合が0.01重量部未満の少ない場合には、光を照射しても、エポキシ基の開環反応が十分に進行しない。5重量部を越えて多く配合しても、反応が改善されるものでは無い。加硫ゴムは、ガラス転移温度が-20℃以下の線状重合体と、架橋剤と、架橋促進剤などの所望の成分を含む組成物が、0~300℃(好ましくは、60~180℃)の温度下で、0.1~120分間(好ましくは、5~60分間)維持することにより得られる。温度が低いと、反応時間が掛かり過ぎ、生産性が悪くなる。逆に、温度が高いと、エネルギーコストが掛かり過ぎる。従って、上記のような条件で行われる。高分子材料としては塗膜も挙げられる。尚、塗膜単独の場合は少ない。すなわち、塗膜は複合材の場合が多い。塗膜は、一般的には、二次元線状ポリマー(熱可塑性樹脂)に架橋剤、架橋促進剤、架橋助剤、溶剤を混合し、これを塗布、乾燥することで得られる。必要に応じて、重合処理も行われる。前記有機高分子材料は、必要に応じて、充填剤、機能性添加剤を有する。機能性添加剤は所望の機能を発現する添加剤である。機能性添加剤は補強剤であったりする。前記剤としては、例えばカーボンブラック、炭酸カルシウム、タルク、扁平タルク、ミストロンタルク、クレー、カオリン、扁平カオリン、セルロース、セライト、扁平クレー、カオリン、ガラス、チタン酸バリウム、チタン酸ストロンチウム、マイカ、シリカが挙げられる。補強剤としては、例えばレーヨン、ナイロン、ポリエステル、ビニロン、スチール、ケブラ、炭素繊維、ガラス繊維などが挙げられる。これ等は繊維の形態であったり、布の形態であったりする。その他、銅、ニッケル、銀、金、スズ、カーボンなどの紛体が挙げられる。導電材も挙げられる。アルミナ、窒化珪素、窒化アルミナ、炭化珪素、ダイヤモンドなどの伝熱材も挙げられる。添加量は、目的に応じた量である。安定剤(老化防止剤、紫外線防止剤)も用いられる場合が有る。安定剤は、高分子材料の信頼性を高める。例えば、アミン・ケトン系縮合物(例えば、ポリ(2,2,4-トリメチル-1,2-ジヒドロキノリン)、6-エトキシ-1,2-ジヒドロ-2,2,4-トリメチルキノリン等)、芳香族第二級アミン化合物(例えば、オクチルジフェニルアミン、4,4-ビス(α,α-ジメチルベンジル)ジフェニルアミン、N,N-ジフェニル-p-フェニレンジアミン、N-フェニル-N’-イソプロピル-p-フェニレンジアミン、N-フェニル-N’-イソプロピル-1,3-ジメチルブチル-p-フェニレンジアミン等)、モノ及びビスフェノール系化合物(例えば、スチレン化フェノール、2,6-ジ-t-ブチル-4-フェノール、2-t-ブチル-6-(3-t-ブチル-2-ヒドロキシ-5-メチルベンジル)-4-メチルフェニルアクリレート、2,2-メチレンビス(4-メチル-6-t-ブチルフェノール)、4,4-チオビス(3-メチル-6-t-ブチルフェノール)2,5-ジ-t-ブチルヒドロキノン等)、2-メルカプトベンゾイミダゾール、2-Znメルカプトベンゾイミダゾール、ニッケルジメチルジチオカーバメイト、1,3-ビス(ジメチルアミノプロピル)チオウレア、ジラウリル-3,3-チオジプロピオネート、トリス(ノニル化フェニル)フォスファイト、2-(4-ヒドロキシ-3,5-t-ブチル)アニリノ-1,3,5-トリアジン-4,6-ジチオール、2-(4-フェニルアミノ)アニリノ-1,3,5-トリアジン-4,6-ジチオール、2-(N-アニリノフェニル)-N’-イソプロピルアミノ-1,3,5-トリアジン-4,6-ジチオール、4-ジ(N-アニリノフェニル-N’-イソプロピルアミノ)-1,3,5-トリアジン-6-チオール、2,4-ジ(N-アニリノフェニル-N’-イソプロピルアミノ)-1,3,5-トリアジン-6-チオール、1,3,5-トリアジン-2,4,6-トリチオール,ビス(2,4-ジチオール-1,3,5-トリアジニル-6-アミノ)ベンゼン、2-トリエトキシシリルプロピルアミノ-1,3,5-トリアジン-4,6-ジチオール等が挙げられる。特に、抗酸化性基を有するトリアジンチオール等の硫黄系または燐系化合物が用いられる。添加量は、目的に応じた量である。
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-ジクロリド(TEDC)及びN,N’-ビス(2-アミノエチル)-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-ジアミン(TEDDA)は、以下の反応式(1-1)及び反応式(1-2)に従って、合成された。
実施例1の化合物(TEDDA)による表面処理が行われた例である。
10mm×20mm×0.1mmの基板が用意された。前記基板は、Ti板、Mo板、Ni板、Cu板、Al板、Ag板、Pt板、Sn板、SUS316板、黄銅板である。すなわち、10種類の基板が用意された。各々の基板に対して、エタノール中で、40℃下で、15分間に亘る超音波脱脂が行われた。この後、エタノールでリンスが行われた。これにより、表面が清浄化された。清浄化後、真空デシケータ中で乾燥が行われた。
実施例1の化合物(TEDDA)による表面処理が行われた例である。
10mm×10mm×0.1mmの基板が用意された。前記基板は、アルミナ板、炭化ケイ素板、窒化アルミニウム板、酸化亜鉛板、カーボン板、ガラス板、ジルコニア板、陶磁器板、セメント板、石膏板である。すなわち、10種類の基板が用意された。そして、前記実施例5と同様な処理が行われた。
実施例1の化合物(TEDDA)による表面処理が行われた例である。
10mm×20mm×0.2mmの基板が用意された。前記基板は、ポリエチレン板(PE:LD-PE:07-127-01:株式会社ハギテック製)、ポリプロピレン板(PP:コクゴ製:07-175-04)、テトラフルオロエチレン板(PTFE:NO.903UL:日東電工株式会社製)、ポリオキシメチレン板(POM:ジュラコンM25-44:ポリプラスチック社製)、ナイロン板(PA6:P07-142-04、コクゴ製)、ポリエチレン-2,6-ナフタレート板(PEN:帝人ジュポン株式会社製:テオネックス(R))、ポリエチレンテレフタレート板(PET:東レコン、東レ株式会社製)、ポリエーテルエーテルケトン板(PEEK:PEEK450G:八十島プロシード株式会社製)、ポリフェニレンサルファイド板(PPS:C-130SG:出光興産株式会社製)、及びポリカーボネート板(PC:07-145-04:コクゴ製)、ポリイミド板(PI:カプトン、東レデュポン社製)、ウレタン板(UR:07-007-01:コクゴ製)である。そして、前記実施例5と同様な処理が行われた。
実施例1の化合物(TEDDA)による表面処理が行われた例である。
エチレンプロピレンダイエンラバー(EPDM,JSR-EP)、シリコーンゴム板(Q:SH-851U:東レ・ダウコーニング株式会社製)、スチレンブタジエンゴム(SBR:Nipol 1500:日本ゼオン株式会社製)、ニトリルブタジエンゴム(NBR:DN300:日本ゼオン株式会社製)、フッ素ゴム(FKM:G-901:ダイキン工業株式会社製)が用意された。これ等の材料に、FEFブラック(東京材料株式会社製)、DCP、及びZnOが混合され、二本ロールで混練された。そして、厚さ2mmの未架橋ゴムシートが得られた。これらの未架橋ゴムシートを重ねて金型に入れ、真空熱加圧装置(ミカドテクノス株式会社製:バキュウムボーイVM01-1010VM)により、160℃で、30分間、2MPaのプレス圧が掛けられた。これにより、架橋が行われた。このようにして各々のゴム製の基板が得られた。そして、前記実施例5と同様な処理が行われた。
実施例1の化合物(TEDDA)による表面処理が行われた例である。
基板は複合材料である。すなわち、表-5に記載の充填剤がQ,PE,SBR,PA6,及びPPS等の高分子材料にブレンドされた。Q及びSBRに対する充填剤のブレンドは二本ロールで、PEとPA6に対する充填剤のブレンドはニーダーを用いて行われた。そして、120℃~180℃の温度で5分間に亘って金型によるプレス成形が行われ、10mm×20mm×0.1mmの基板が得られた。そして、前記実施例5と同様な処理が行われた。
実施例5dの基板(TEDDA処理Cu板)、実施例5eの基板(TEDDA処理Al板)、実施例5iの基板(TEDDA処理SUS316板)、実施例6fの基板(TEDDA処理SiO2板)、実施例7と同様な処理を経たPI板(PI:カプトン、東レデュポン社製)、実施例7と同様な処理を経たUR板(UR:07-007-01:コクゴ製)が用意された。
実施例5dで用いられたCu板、実施例7bで用いられたPP板、実施例8bで用いられたQ板が用意された。TEDDA処理は行われていない。これ等の基板に対して超音波脱脂(エタノール中 40℃ 15分間)が行われた。この後、エタノールによるリンスが行われた。更に、コロナ放電処理(信光電気計測株式会社製のコロナマスター 出力電圧;9kV(表面電圧) 発振周波数:20kHz 温度:20℃)が行われた。
上記TEDDA処理基板と、上記TEDDA未処理基板とが、TEDDA膜が挟まれるように、対向配置された。この後、1MPaのプレスが掛けられた。プレス温度は120℃であった。プレス時間は10分間であった。
TEDDA処理SUS316板(実施例5iの基板)に対しては、更に、アクリルウレタン系塗料(U:ウレッコート、複合資材株式会社)が塗布された。そして、硬化処理(50℃;24時間)が行われた。この後、実施例5iと同様に、アクリルウレタン系塗膜の上にTEDDA水溶液による表面処理が行われた。
これ等TEDDA処理基板が、触媒処理液(上村工業株式会社製のNP-8;150mL/L HCl;150mL/L)中に、浸漬(温度:25℃ 時間:1分間)された。これにより、表面にPd-Sn触媒が担持された。このPd-Sn触媒が担持された基板が、無電解銅メッキ浴(上村工業株式会社製のスルカップPSY-1A;100ml/L スルカップPSY-1B;55ml/L 18.5%ホルマリン水溶液;20mL/L)中に、浸漬(温度:33℃ 時間:20分間)された。この後、電気メッキが行われた。この電気メッキに用いられた電解浴は、上村工業株式会社製のスルカップETN浴(CuSO4・5H2O;80g/L H2SO4;200g/L Cl-;50ppm)、スルカップETN-1A浴(1ml/L)、スルカップETN-1B浴(10ml/L)である。電流は2.5A/dm2であった。時間は60分間であった。温度は25℃であった。このようにして得られたCuメッキ膜の厚さは30μmであった。
表-6
500mLの三ッ口フラスコに、撹拌子とN,N-ジメチルエチレンジアミン(20.0g;0.230mmol)とが入れられた。フラスコ内がアルゴン雰囲気下に置かれた。これに、THF(200mL)が加えられた。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-ジクロリド(8.3g;22.5mmol)とTHF(100mL)との混合溶液が、滴下された。滴下後、反応溶液が徐々に90℃に加熱された。この後、8時間に亘る反応が行われた。この後、室温に冷却された。セライトを通して、吸引濾過が行われた。濾液がロータリーエバポレーターにて濃縮された。この後、減圧乾燥が行われた。これにより、淡黄色オイルのN,N’-ビス(2-ジメチルアミノエチル)-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-ジアミン(9.1g;収率86%)が得られた。得られた化合物の同定は元素分析、NMRスペクトル、MS測定により行われた。元素分析値N%はパーキンエルマモデル2400CHN分析装置により、NMRスペクトル測定は日本ブルカーAC400Pにより、MSはJEOL JMS-700により行われた。
300mLの三ッ口フラスコに、撹拌子と1,6-へキサンジアミン(46.5g;0.40mol)とが入れられた。フラスコ内がアルゴン雰囲気下に置かれた。これに、THF(80g)が加えられた。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-ジクロリド(14.8g;0.04mol)とTHF(20g)との混合溶液が、滴下された。滴下後、反応溶液が徐々に加熱された。この後、還流下で5時間に亘る反応が行われた。この後、室温に冷却された。セライトを通して、吸引濾過が行われた。濾液がロータリーエバポレーターにて濃縮された。この後、減圧乾燥が行われた。これにより、淡黄色オイルのN,N’-ビス(2-アミノヘキシル)-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-ジアミン(TEDHDA,19.9g;収率94%)が得られた。得られた化合物の同定は元素分析、NMRスペクトル、MS測定により行われた。元素分析値N%はパーキンエルマモデル2400CHN分析装置により、NMRスペクトル測定は日本ブルカーAC400Pにより、MSはJEOL JMS-700により行われた。
300mLの三ッ口フラスコに、撹拌子とトリス(2-アミノエチル)アミン(29.3g;0.20mmol)とが入れられた。フラスコ内がアルゴン雰囲気下に置かれた。これに、THF(40g)が加えられた。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-ジクロリド(7.8g;0.02mol)とTHF(10g)との混合溶液が、滴下された。滴下後、反応溶液が徐々に90℃に加熱された。この後、8時間に亘る反応が行われた。この後、室温に冷却された。セライトを通して、吸引濾過が行われた。濾液がロータリーエバポレーターにて濃縮された。この後、減圧乾燥が行われた。これにより、淡黄色オイルのN,N’-ビス{2-[ビス-(2-アミノエチル)アミノ]エチル}-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-ジアミン(TEBTTA,11.2g;収率95%)が得られた。得られた化合物の同定は元素分析、NMRスペクトル、MS測定により行われた。元素分析値N%はパーキンエルマモデル2400CHN分析装置により、NMRスペクトル測定は日本ブルカーAC400Pにより、MSはJEOL JMS-700により行われた。
500mLの三ッ口フラスコに、撹拌子と1,12-ドデカンジアミン(40.1g;0.20mol)とが入れられた。フラスコ内がアルゴン雰囲気下に置かれた。これに、THF(200g)が加えられた。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-ジクロリド(7.8g;0.02mol)とTHF(10g)との混合溶液が、滴下された。滴下後、反応溶液が徐々に加熱された。この後、還流下で10時間に亘る反応が行われた。この後、室温に冷却された。セライトを通して、吸引濾過が行われた。濾液がロータリーエバポレーターにて濃縮された。この後、減圧乾燥が行われた。これにより、無色オイルのN,N’-ビス(12-アミノドデシル)-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-ジアミン(TEDDDA,13.1g;収率94%)が得られた。得られた化合物の同定は元素分析、NMRスペクトル、MS測定により行われた。元素分析値N%はパーキンエルマモデル2400CHN分析装置により、NMRスペクトル測定は日本ブルカーAC400Pにより、MSはJEOL JMS-700により行われた。
実施例5dで用いられたCu板が用意された。TEDDA(実施例1)、DTEDH(実施例2)、DTEDEA(実施例3)、DTEEA(実施例4)、TEDDMA(実施例11)、TEDHDA(実施例12)、TEBTTA(実施例13)、TEDDDA(実施例14)が用いられた。実施例5と同様な表面処理が行われた。
実施例7bで用いられたPP板が用意された。化合物αによる処理は行われていない。この基板に対して超音波脱脂(エタノール中 40℃ 15分間)が行われた。この後、エタノールによるリンスが行われた。更に、コロナ放電処理(信光電気計測株式会社製のコロナマスター 出力電圧;9kV(表面電圧) 発振周波数:20kHz 温度:20℃)が行われた。
上記各化合物の処理Cu基板と、上記未処理PP基板とが、各化合物膜が挟まれるように、対向配置された。この後、1MPaのプレスが掛けられた。プレス温度は120℃であった。プレス時間は10分間であった。
これ等の処理基板が、触媒処理液(上村工業株式会社製のNP-8;150mL/L HCl;150mL/L)中に、浸漬(温度:25℃ 時間:1分間)された。これにより、表面にPd-Sn触媒が担持された。このPd-Sn触媒が担持された基板が、無電解銅メッキ浴(上村工業株式会社製のスルカップPSY-1A;100ml/L スルカップPSY-1B;55ml/L 18.5%ホルマリン水溶液;20mL/L)中に、浸漬(温度:33℃ 時間:20分間)された。この後、電気メッキが行われた。この電気メッキに用いられた電解浴は、上村工業株式会社製のスルカップETN浴(CuSO4・5H2O;80g/L H2SO4;200g/L Cl-;50ppm)、スルカップETN-1A浴(1ml/L)、スルカップETN-1B浴(10ml/L)である。電流は2.5A/dm2であった。時間は60分間であった。温度は25℃であった。このようにして得られたCuメッキ膜の厚さは30μmであった。
表-7
基板表面に設けられた化合物αは反応性に富むことから、この反応特性を利用して、各種の分野に応用できる。例えば、化合物αとの反応(吸着)が可能な化合物Xを基板上に設けたい場合でも、これは簡単である。
本発明は様々な分野(例えば、装飾品、回路基板、その他複合化製品)に適用できることが理解される。
Claims (29)
- 化合物αを含有する溶液が塗布されることにより前記化合物αが基板上に設けられる表面処理方法であって、
前記化合物αは、
M-OH基および/またはM-OH生成基(M:金属元素)と、
アミノ基と、
トリアジン環
とを少なくとも有し、
前記M-OH基および/またはM-OH生成基(M:金属元素)は一つ以上有り、
前記トリアジン環は一つ以上有り、
前記アミノ基の少なくとも一つのアミノ基は、前記トリアジン環のCに、間接的に、結合してなり、
前記間接的に結合したアミノ基は、少なくとも、末端位置に存在してなり、
前記末端位置のアミノ基は一つ以上有る
ことを特徴とする表面処理方法。 - 前記化合物αは下記の一般式[I]で表される化合物である
ことを特徴とする請求項1の表面処理方法。
一般式[I]
{(NR1R2)aX-Q}bY(W)c{Z(V-M(R3)n(OR4)3-n)}d
(式中、R1,R2,R3,R4はH又は官能基である。R1とR2とR3とR4とは、全てが同じでも、異なるものでも良い。X,Z,Q,Vは連結基である。連結基X,Z,Qが無い場合も有る(但し、X、Z、Qの全てが無い場合は除く)。Yは骨格である。この骨格はトリアジン環(C3N3)を有する。前記トリアジン環には、直接、-NH2,-N3が結合していない。Wは、{Z(V-M(R3)n(OR4)3-n)}以外の官能基である。MはSi,Al,Tiの群の中から選ばれる少なくとも一つである。aは1以上の整数、bは1又は2、cは0又は1、dは1又は2、b+c+d=3、nは0,1又は2である。) - 前記化合物αは下記の一般式[II]又は一般式[III]で表される化合物である
ことを特徴とする請求項2の表面処理方法。
一般式[II]
{(NR1R2)aX-Q}bY{NH(CH2)mSi(R3)n(OR4)3-n}e
一般式[III]
{(NR1R2)aX-Q}bY[N{(CH2)mSi(R3)n(OR4)3-n}2]e
(式中、R1,R2、R3,R4はH又は官能基である。R1、R2、R3,R4とは、同じでも、異なるものでも良い。X,Qは連結基である。連結基X,Qが無い場合も有る(但し、X、Qの全てが無い場合は除く)。Yは骨格である。この骨格はトリアジン環(C3N3)を有する。前記トリアジン環には、直接、-NH2,-N3が結合していない。aは1以上の整数、bは1又は2、eは1又は2、b+e=3、mは1以上の整数、nは0,1又は2である。) - 前記化合物αの末端に結合したアミノ基が第1級アミノ基である
ことを特徴とする請求項3の表面処理方法。 - 前記化合物αは、N,N’-ビス(2-アミノエチル)-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-ジアミン、6-(3-トリエトキシシリルプロピル)アミノ-2,4-ジヒドラジニル-1,3,5-トリアジン、2-(N,N’-ジ-3-トリエトキシシリルプロピル)アミノ-4,6-ジ(2-アミノエチル)アミノ-1,3,5-トリアジン、2-(2-アミノエチル)アミノ-4,6-ジ(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、6-(2-アミノエチル)アミノ-2,4-ビス(メチルエチルケトキシミノシリル)プロピルアミノ-1,3,5-トリアジン、6-(2-アミノエチル)アミノ-2,4-ジ(トリイソプロポキシシリル)プロピルアミノ-1,3,5-トリアジン、6-(2-アミノエチル)アミノ-2,4-ジ(トリアセトキシシリル)プロピルアミノ-1,3,5-トリアジン、6-(2-アミノエチル)アミノ-2,4-ジ(トリイソプロペノオキシシシリル)プロピルアミノ-1,3,5-トリアジン、6-(2-アミノエチル)アミノ-2,4-ジ(トリイソプロポキシシリル)プロピルアミノ-1,3,5-トリアジン、6-(2-アミノエチル)アミノ-2,4-ジ(トリベンゾキシシリル)プロピルアミノ-1,3,5-トリアジン、6-(2-アミノエチル)アミノ-2,4-ビス(トリエトキシシリルへキシル)アミノ-1,3,5-トリアジン、6-(2-アミノエチル)アミノ-2,4-ビス(トリエトキシシリルドデシル)アミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ビス(メチルエチルケトキシミノシリル)プロピルアミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ビス(メチルエチルケトキシミノシリル)プロピルアミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ジ(トリイソプロポキシシリル)プロピルアミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ジ(トリアセトキシシリル)プロピルアミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ジ(トリイソプロペノオキシシシリル)プロピルアミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ジ(トリイソプロポキシシリル)プロピルアミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ジ(トリベンゾキシシリル)プロピルアミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ビス(トリエトキシシリルヘキシルアミノ)-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ビス(トリエトキシシリルプロピル)アミノ-1,3,5-トリアジン、N,N’-ビス(2-ジメチルアミノエチル)-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-ジアミン、N,N’-ビス(2-アミノヘキシル)-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-ジアミン、N,N’-ビス{2-[ビス-(2-アミノエチル)アミノ]エチル}-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-ジアミン、N,N’-ビス(12-アミノドデシル)-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-ジアミンの群の中から選ばれる少なくとも一つである
ことを特徴とする請求項5の表面処理方法。 - 前記M-OH基および/またはM-OH生成基(M:金属元素)がアルコキシシリル基である
ことを特徴とする請求項1~請求項5いずれかの表面処理方法。 - 化合物αの蒸発により前記化合物αが基板上に設けられる表面処理方法であって、
前記化合物αは、
M-OH基および/またはM-OH生成基(M:金属元素)と、
アミノ基と、
トリアジン環
とを少なくとも有し、
前記M-OH基および/またはM-OH生成基(M:金属元素)は一つ以上有り、
前記トリアジン環は一つ以上有り、
前記アミノ基の少なくとも一つのアミノ基は、前記トリアジン環のCに、間接的に、結合してなり、
前記間接的に結合したアミノ基は、少なくとも、末端位置に存在してなり、
前記末端位置のアミノ基は一つ以上有る
ことを特徴とする表面処理方法。 - 前記化合物αは下記の一般式[I]で表される化合物である
ことを特徴とする請求項8の表面処理方法。
一般式[I]
{(NR1R2)aX-Q}bY(W)c{Z(V-M(R3)n(OR4)3-n)}d
(式中、R1,R2,R3,R4はH又は官能基である。R1とR2とR3とR4とは、全てが同じでも、異なるものでも良い。X,Z,Q,Vは連結基である。連結基X,Z,Qが無い場合も有る(但し、X、Z、Qの全てが無い場合は除く)。Yは骨格である。この骨格はトリアジン環(C3N3)を有する。前記トリアジン環には、直接、-NH2,-N3が結合していない。Wは、{Z(V-M(R3)n(OR4)3-n)}以外の官能基である。MはSi,Al,Tiの群の中から選ばれる少なくとも一つである。aは1以上の整数、bは1又は2、cは0又は1、dは1又は2、b+c+d=3、nは0,1又は2である。) - 前記化合物αは下記の一般式[II]又は一般式[III]で表される化合物である
ことを特徴とする請求項9の表面処理方法。
一般式[II]
{(NR1R2)aX-Q}bY{NH(CH2)mSi(R3)n(OR4)3-n}e
一般式[III]
{(NR1R2)aX-Q}bY[N{(CH2)mSi(R3)n(OR4)3-n}2]e
(式中、R1,R2、R3,R4はH又は官能基である。R1、R2、R3,R4とは、同じでも、異なるものでも良い。X,Qは連結基である。連結基X,Qが無い場合も有る(但し、X、Qの全てが無い場合は除く)。Yは骨格である。この骨格はトリアジン環(C3N3)を有する。前記トリアジン環には、直接、-NH2,-N3が結合していない。aは1以上の整数、bは1又は2、eは1又は2、b+e=3、mは1以上の整数、nは0,1又は2である。) - 前記化合物αの末端に結合したアミノ基が第1級アミノ基であることを特徴とする請求項10の表面処理方法。
- 前記化合物αは、N,N’-ビス(2-アミノエチル)-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-ジアミン、6-(3-トリエトキシシリルプロピル)アミノ-2,4-ジヒドラジニル-1,3,5-トリアジン、2-(N,N’-ジ-3-トリエトキシシリルプロピル)アミノ-4,6-ジ(2-アミノエチル)アミノ-1,3,5-トリアジン、2-(2-アミノエチル)アミノ-4,6-ジ(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、6-(2-アミノエチル)アミノ-2,4-ビス(メチルエチルケトキシミノシリル)プロピルアミノ-1,3,5-トリアジン、6-(2-アミノエチル)アミノ-2,4-ジ(トリイソプロポキシシリル)プロピルアミノ-1,3,5-トリアジン、6-(2-アミノエチル)アミノ-2,4-ジ(トリアセトキシシリル)プロピルアミノ-1,3,5-トリアジン、6-(2-アミノエチル)アミノ-2,4-ジ(トリイソプロペノオキシシシリル)プロピルアミノ-1,3,5-トリアジン、6-(2-アミノエチル)アミノ-2,4-ジ(トリイソプロポキシシリル)プロピルアミノ-1,3,5-トリアジン、6-(2-アミノエチル)アミノ-2,4-ジ(トリベンゾキシシリル)プロピルアミノ-1,3,5-トリアジン、6-(2-アミノエチル)アミノ-2,4-ビス(トリエトキシシリルへキシル)アミノ-1,3,5-トリアジン、6-(2-アミノエチル)アミノ-2,4-ビス(トリエトキシシリルドデシル)アミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ビス(メチルエチルケトキシミノシリル)プロピルアミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ビス(メチルエチルケトキシミノシリル)プロピルアミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ジ(トリイソプロポキシシリル)プロピルアミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ジ(トリアセトキシシリル)プロピルアミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ジ(トリイソプロペノオキシシシリル)プロピルアミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ジ(トリイソプロポキシシリル)プロピルアミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ジ(トリベンゾキシシリル)プロピルアミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ビス(トリエトキシシリルヘキシルアミノ)-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ビス(トリエトキシシリルプロピル)アミノ-1,3,5-トリアジン、N,N’-ビス(2-ジメチルアミノエチル)-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-ジアミン、N,N’-ビス(2-アミノヘキシル)-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-ジアミン、N,N’-ビス{2-[ビス-(2-アミノエチル)アミノ]エチル}-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-ジアミン、N,N’-ビス(12-アミノドデシル)-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-ジアミンの群の中から選ばれる少なくとも一つである
ことを特徴とする請求項12の表面処理方法。 - 前記化合物αが基板上に設けられる前に、洗浄処理、コロナ放電処理、プラズマ放電処理、紫外線照射、酸処理、アルカリ処理、水蒸気処理及び化成処理の群の中から選ばれる一つまたは二つ以上の処理が前記基板に行われる
ことを特徴とする請求項1~請求項13いずれかの表面処理方法。 - 前記化合物αが基板上に設けられた後、加熱処理が行われる
ことを特徴とする請求項1~請求項14いずれかの表面処理方法。 - 前記表面処理は前記化合物αによる接着を目的としてなされる
ことを特徴とする請求項1~請求項15いずれかの表面処理方法。 - 前記表面処理は前記化合物αによる化学的反応または物理的吸着を目的としてなされる
ことを特徴とする請求項1~請求項15いずれかの表面処理方法。 - 請求項1~請求項17いずれかの表面処理方法に用いられる表面処理剤であって、
前記表面処理剤は化合物α、又は化合物αを含むものであり、
前記化合物αは、
M-OH基および/またはM-OH生成基(M:金属元素)と、
アミノ基と、
トリアジン環
とを少なくとも有し、
前記M-OH基および/またはM-OH生成基(M:金属元素)は一つ以上有り、
前記トリアジン環は一つ以上有り、
前記アミノ基の少なくとも一つのアミノ基は、前記トリアジン環のCに、間接的に、結合してなり、
前記間接的に結合したアミノ基は、少なくとも、末端位置に存在してなり、
前記末端位置のアミノ基は一つ以上有る
ことを特徴とする表面処理剤。 - 前記化合物αは下記の一般式[I]で表される化合物である
ことを特徴とする請求項18の表面処理剤。
一般式[I]
{(NR1R2)aX-Q}bY(W)c{Z(V-M(R3)n(OR4)3-n)}d
(式中、R1,R2,R3,R4はH又は官能基である。R1とR2とR3とR4とは、全てが同じでも、異なるものでも良い。X,Z,Q,Vは連結基である。連結基X,Z,Qが無い場合も有る(但し、X、Z、Qの全てが無い場合は除く)。Yは骨格である。この骨格はトリアジン環(C3N3)を有する。前記トリアジン環には、直接、-NH2,-N3が結合していない。Wは、{Z(V-M(R3)n(OR4)3-n)}以外の官能基である。MはSi,Al,Tiの群の中から選ばれる少なくとも一つである。aは1以上の整数、bは1又は2、cは0又は1、dは1又は2、b+c+d=3、nは0,1又は2である。) - 前記化合物αは下記の一般式[II]又は一般式[III]で表される化合物である
ことを特徴とする請求項19の表面処理剤。
一般式[II]
{(NR1R2)aX-Q}bY{NH(CH2)mSi(R3)n(OR4)3-n}e
一般式[III]
{(NR1R2)aX-Q}bY[N{(CH2)mSi(R3)n(OR4)3-n}2]e
(式中、R1,R2、R3,R4はH又は官能基である。R1、R2、R3,R4とは、同じでも、異なるものでも良い。X,Qは連結基である。連結基X,Qが無い場合も有る(但し、X、Qの全てが無い場合は除く)。Yは骨格である。この骨格はトリアジン環(C3N3)を有する。前記トリアジン環には、直接、-NH2,-N3が結合していない。aは1以上の整数、bは1又は2、eは1又は2、b+e=3、mは1以上の整数、nは0,1又は2である。) - 前記化合物αの末端に結合したアミノ基が第1級アミノ基であることを特徴とする請求項20の表面処理剤。
- 前記化合物αは、N,N’-ビス(2-アミノエチル)-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-ジアミン、6-(3-トリエトキシシリルプロピル)アミノ-2,4-ジヒドラジニル-1,3,5-トリアジン、2-(N,N’-ジ-3-トリエトキシシリルプロピル)アミノ-4,6-ジ(2-アミノエチル)アミノ-1,3,5-トリアジン、2-(2-アミノエチル)アミノ-4,6-ジ(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、6-(2-アミノエチル)アミノ-2,4-ビス(メチルエチルケトキシミノシリル)プロピルアミノ-1,3,5-トリアジン、6-(2-アミノエチル)アミノ-2,4-ジ(トリイソプロポキシシリル)プロピルアミノ-1,3,5-トリアジン、6-(2-アミノエチル)アミノ-2,4-ジ(トリアセトキシシリル)プロピルアミノ-1,3,5-トリアジン、6-(2-アミノエチル)アミノ-2,4-ジ(トリイソプロペノオキシシシリル)プロピルアミノ-1,3,5-トリアジン、6-(2-アミノエチル)アミノ-2,4-ジ(トリイソプロポキシシリル)プロピルアミノ-1,3,5-トリアジン、6-(2-アミノエチル)アミノ-2,4-ジ(トリベンゾキシシリル)プロピルアミノ-1,3,5-トリアジン、6-(2-アミノエチル)アミノ-2,4-ビス(トリエトキシシリルへキシル)アミノ-1,3,5-トリアジン、6-(2-アミノエチル)アミノ-2,4-ビス(トリエトキシシリルドデシル)アミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ビス(メチルエチルケトキシミノシリル)プロピルアミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ビス(メチルエチルケトキシミノシリル)プロピルアミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ジ(トリイソプロポキシシリル)プロピルアミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ジ(トリアセトキシシリル)プロピルアミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ジ(トリイソプロペノオキシシシリル)プロピルアミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ジ(トリイソプロポキシシリル)プロピルアミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ジ(トリベンゾキシシリル)プロピルアミノ-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ビス(トリエトキシシリルヘキシルアミノ)-1,3,5-トリアジン、2,4-ジ(2-アミノエチル)アミノ-6-ビス(トリエトキシシリルプロピル)アミノ-1,3,5-トリアジン、N,N’-ビス(2-ジメチルアミノエチル)-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-ジアミン、N,N’-ビス(2-アミノヘキシル)-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-ジアミン、N,N’-ビス{2-[ビス-(2-アミノエチル)アミノ]エチル}-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-ジアミン、N,N’-ビス(12-アミノドデシル)-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-ジアミンの群の中から選ばれる少なくとも一つである
ことを特徴とする請求項22の表面処理剤。 - 下記の一般式[I]で表される化合物である
ことを特徴とする新規化合物。
一般式[I]
{(NR1R2)aX-Q}bY(W)c{Z(V-M(R3)n(OR4)3-n)}d
(式中、R1,R2,R3,R4はH又は官能基である。R1とR2とR3とR4とは、全てが同じでも、異なるものでも良い。X,Z,Q,Vは連結基である。連結基X,Z,Qが無い場合も有る(但し、X、Z、Qの全てが無い場合は除く)。Yは骨格である。この骨格はトリアジン環(C3N3)を有する。前記トリアジン環には、直接、-NH2,-N3が結合していない。Wは、{Z(V-M(R3)n(OR4)3-n)}以外の官能基である。MはSi,Al,Tiの群の中から選ばれる少なくとも一つである。aは1以上の整数、bは1又は2、cは0又は1、dは1又は2、b+c+d=3、nは0,1又は2である。) - 前記一般式[I]で表される化合物は下記の一般式[II]で表される化合物である
ことを特徴とする請求項24の新規化合物。
一般式[II]
{(NR1R2)aX-Q}bY{NH(CH2)mSi(R3)n(OR4)3-n}e
(式中、R1,R2、R3,R4はH又は官能基である。R1、R2、R3,R4とは、同じでも、異なるものでも良い。X,Qは連結基である。連結基X,Qが無い場合も有る(但し、X、Qの全てが無い場合は除く)。Yは骨格である。この骨格はトリアジン環(C3N3)を有する。前記トリアジン環には、直接、-NH2,-N3が結合していない。aは1以上の整数、bは1又は2、eは1又は2、b+e=3、mは1以上の整数、nは0,1又は2である。) - 前記一般式[I]で表される化合物は下記の一般式[III]で表される化合物である
ことを特徴とする請求項24の新規化合物。
一般式[III]
{(NR1R2)aX-Q}bY[N{(CH2)mSi(R3)n(OR4)3-n}2]e
(式中、R1,R2、R3,R4はH又は官能基である。R1、R2、R3,R4とは、同じでも、異なるものでも良い。X,Qは連結基である。連結基X,Qが無い場合も有る(但し、X、Qの全てが無い場合は除く)。Yは骨格である。この骨格はトリアジン環(C3N3)を有する。前記トリアジン環には、直接、-NH2,-N3が結合していない。aは1以上の整数、bは1又は2、eは1又は2、b+e=3、mは1以上の整数、nは0,1又は2である。) - 請求項1~請求項17いずれかの表面処理方法によって得られた基板と接着体とが一体的に接合されてなる
ことを特徴とする接合製品。 - 請求項1~請求項17いずれかの表面処理方法によって得られた基板表面に金属膜が設けられてなる
ことを特徴とする金属膜製品。
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| WO2017217467A1 (ja) * | 2016-06-15 | 2017-12-21 | 株式会社新技術研究所 | ポリエステル系樹脂を含む銅合金物品およびその製造方法 |
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| KR102743538B1 (ko) | 2023-01-31 | 2024-12-16 | 멕크 가부시키가이샤 | 화합물, 표면 처리제, 표면 처리 방법, 및 금속-수지 복합체의 제조 방법 |
| US12404287B2 (en) | 2023-01-31 | 2025-09-02 | Mec Company Ltd. | Chemical compound, surface treating agent, surface treating method, and production method for metal-resin composite |
| JP7330578B1 (ja) | 2023-01-31 | 2023-08-22 | メック株式会社 | 化合物、表面処理剤、表面処理方法、および金属‐樹脂複合体の製造方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2859962A1 (en) | 2015-04-15 |
| KR20150006457A (ko) | 2015-01-16 |
| CN104349848A (zh) | 2015-02-11 |
| US20170334933A1 (en) | 2017-11-23 |
| HK1202486A1 (zh) | 2015-10-02 |
| US20150152124A1 (en) | 2015-06-04 |
| JPWO2013186941A1 (ja) | 2016-02-01 |
| US10385076B2 (en) | 2019-08-20 |
| EP3505522A1 (en) | 2019-07-03 |
| EP2859962B1 (en) | 2019-01-23 |
| CN104349848B (zh) | 2016-01-20 |
| EP2859962A4 (en) | 2016-02-17 |
| TW201418271A (zh) | 2014-05-16 |
| EP3505522B1 (en) | 2020-10-14 |
| KR101569128B1 (ko) | 2015-11-13 |
| JP5729852B2 (ja) | 2015-06-03 |
| TWI510498B (zh) | 2015-12-01 |
| US9790242B2 (en) | 2017-10-17 |
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