WO2012042665A1 - 接着剤組成物、塗料組成物およびこれを用いたプライマー、インクジェットインク、接着方法および積層体 - Google Patents
接着剤組成物、塗料組成物およびこれを用いたプライマー、インクジェットインク、接着方法および積層体 Download PDFInfo
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- WO2012042665A1 WO2012042665A1 PCT/JP2010/067250 JP2010067250W WO2012042665A1 WO 2012042665 A1 WO2012042665 A1 WO 2012042665A1 JP 2010067250 W JP2010067250 W JP 2010067250W WO 2012042665 A1 WO2012042665 A1 WO 2012042665A1
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- 0 *C1CC2OC2CC1 Chemical compound *C1CC2OC2CC1 0.000 description 1
- LLKNPRCWDLJCHQ-UHFFFAOYSA-N [O-][NH+](C1CC2=[O]C2CC1)O Chemical compound [O-][NH+](C1CC2=[O]C2CC1)O LLKNPRCWDLJCHQ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/061—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of metal
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- 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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- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
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- B41M5/52—Macromolecular coatings
- B41M5/5209—Coatings prepared by radiation-curing, e.g. using photopolymerisable compositions
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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- C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
- C08G59/4261—Macromolecular compounds obtained by reactions involving only unsaturated carbon-to-carbon bindings
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C09J7/35—Heat-activated
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1525—Four-membered rings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2463/00—Presence of epoxy resin
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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
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Definitions
- the present invention relates to an adhesive composition, a coating composition, a primer using the same, an inkjet ink, an adhesion method, and a laminate.
- the present invention relates to a soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; a polyolefin resin modified with a polar group-containing compound or a copolymer of an olefin and a polar group-containing compound;
- the present invention relates to an adhesive composition, a coating composition, and an inkjet ink excellent in adhesion to a butadiene-styrene copolymer; a polyester resin; or an acrylic resin layer.
- the ink-jet ink of the present invention has excellent long-term storage stability and excellent color development of images.
- the present invention also relates to a method for bonding the adhesive composition to the layers. Furthermore, this invention relates to the laminated body of the said adhesive composition or coating composition, and each said layer. In addition, the present invention also relates to a primer layer provided on an inkjet recording medium containing the coating material, and a printed matter printed using the inkjet ink.
- Plastic materials are used for various applications as substitute materials such as metal materials taking advantage of their toughness and workability.
- the surface of plastic materials is often soft and easily damaged.
- many methods for improving the hardness and scratch resistance of the plastic material surface have been proposed.
- an active energy ray-curable composition that is cured by active energy rays such as ultraviolet rays or electron beams.
- active energy rays such as ultraviolet rays or electron beams.
- Active energy ray-initiated cationic polymerization technology has been put to practical use as active energy ray-curing technology other than active energy ray-initiated radical polymerization.
- active energy ray-initiated cationic polymerization is not inhibited by oxygen, there is no limitation that it must be performed in an inert atmosphere, and there is an advantage that rapid and complete polymerization can be performed in air.
- active energy ray initiated cationic polymerization techniques have focused on the polymerization of two types of monomers: epoxy resins and vinyl ethers.
- the photocurable epoxy resin has excellent adhesiveness
- the coating film has good heat resistance and chemical resistance.
- the conventional photo-curable epoxy resin has a defect that the photopolymerization rate is relatively slow, and therefore cannot be used in applications where quick photo-curing is required, such as glass, various plastics, and metal materials.
- the adhesion of was not sufficient.
- the photo-curable vinyl ether alone has many volatility and strong odor, and the shrinkage at the time of curing is recognized compared with the photo-curing epoxy, and adhesion to glass, various plastics, and metal materials is improved. There were many things that were not enough.
- an active energy ray-curable composition for plastic coating made of a compound having a specific oxetane ring has excellent curability, and the coating film has adhesion, scratch resistance and surface smoothness.
- an image recording method for forming an image on a recording medium such as paper based on an image data signal
- an electrophotographic method there are an electrophotographic method, a sublimation type and melt type thermal transfer method, an ink jet method and the like.
- the electrophotographic system requires a process of forming an electrostatic latent image on a photosensitive drum by charging and exposure, and there is a problem that the system becomes complicated, resulting in high manufacturing costs.
- the thermal transfer system is inexpensive, there are problems such as high running costs and waste materials due to the use of ink ribbons.
- the ink jet method is an inexpensive device and ejects ink only to a required image portion to form an image directly on a recording medium. Therefore, the ink can be used efficiently and the running cost is low. Furthermore, there is little noise and it is excellent as an image recording method.
- Patent Document 2 discloses an ink composition containing vinylcaprolactam as an ink composition rich in flexibility of a cured film and adhesion to a substrate.
- the ink composition described in Patent Document 2 is a high-viscosity ink composition containing a polymer and an oligomer as main components of the ink, and is difficult to be ejected by inkjet.
- Patent Document 3 discloses (a) an oligo / resin component; (B) (i) 0.1 to 50 weight percent comprising one or more heterocyclic radiation curable monomers and / or alkoxylated monomers containing pendant alkoxylated functionality and not containing backbone alkoxylation functionality An adhesion promoting radiation curable component of (Ii) a radiation curable reactive diluent comprising about 10 weight percent or less of an optional alkoxylated radiation curable monomer comprising a main chain alkoxylated functionality; An ink jettable radiation curable ink jet ink composition is disclosed.
- Patent Document 4 discloses a film having an inkjet ink receiving layer on at least one surface of a synthetic resin base film, the receiving layer containing a hydrophobic polyurethane resin and a hydrophilic polyurethane resin, and An ink jet printing film in which the mass ratio of the content of the hydrophobic polyurethane resin and the hydrophilic polyurethane resin is 20 to 400 parts by mass of the hydrophilic polyurethane resin with respect to 100 parts by mass of the hydrophobic polyurethane resin. It is disclosed.
- JP-A-8-208832 Japanese Patent No. 2880845 JP-T-2004-514014 JP 2007-050620 A
- An object of the present invention is an adhesive composition, a coating composition, which has excellent adhesion to polar resins, ceramics, metals, etc., and has an excellent balance of transparency, surface smoothness, flexibility, and impact resistance. It is in providing the adhesion method and laminated body using this.
- An object of the present invention is to provide a coating material excellent in impact and flexibility, an inkjet ink, a primer layer provided on an inkjet recording medium containing the coating material, and a printed matter printed using the inkjet ink.
- the present invention is as follows. 1. (A) Epoxy resin 10-30% by mass (B) Oxetane compound 25-55 mass% (C) Vinyl ether compound 25 to 55% by mass (D) Denaturant 1 to 15% by mass (However, the total of the components (a) to (d) is 100% by mass) And (e) Photocationic polymerization initiator An adhesive composition containing 3 to 15 parts by mass with respect to a total of 100 parts by mass of the components (a) to (d). 2.
- the component (d) is a polyol (d-1) having a hydroxyl value of 40 to 330 mgKOH / g; and a polyol (d-2) having a hydroxyl value of 40 to 330 mgKOH / g and an acid value of 2 to 20 mgKOH / g
- the component (d-1) is a castor oil-based polyol (d-1-1) having a hydroxyl value of 40 to 330 mgKOH / g; a polybutadiene-based polyol (d-1-2) having a hydroxyl value of 40 to 330 mgKOH / g; 3.
- the adhesive composition as described in 2 above which is at least one selected from the group consisting of a polyisoprene-based polyol having a value of 40 to 330 mg KOH / g or a hydrogenated product thereof (d-1-3). 4). 4.
- the component (d-2) is a castor oil-based polyol (d-2-1) having a hydroxyl value of 40 to 330 mgKOH / g and an acid value of 2 to 20 mgKOH / g.
- the ionic liquid (f) contains an anion selected from the group consisting of halogen, carboxylate, sulfate, sulfonate, thiocyanate, aluminate, borate, phosphate, phosphinate, amide, antimonate, imide and methide. 11.
- an antistatic improver (g), wherein the antistatic enhancer (g) is at least one selected from the group consisting of an acidic phosphate ester (g-1) and a carbodiimide compound (g-2), Any of the above 9 to 11, wherein the blending amount of the antistatic improver (g) is in the range of 0.02 to 30 when the mass of the ionic liquid (f) is 1.
- the adherend of the adhesive composition is a soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; a polyolefin resin modified with a polar group-containing compound or a copolymer of an olefin and a polar group-containing compound
- the adhesive composition as described in any one of 1 to 12 above, which is magnesium; acrylonitrile-butadiene-styrene copolymer; polyester resin; or acrylic resin.
- Step I (A) Epoxy resin 10-30% by mass (B) Oxetane compound 25-55 mass% (C) Vinyl ether compound 25 to 55% by mass (D) Denaturant 1 to 15% by mass (However, the total of the components (a) to (d) is 100% by mass) And (e) a photocationic polymerization initiator, a step of preparing an adhesive composition by mixing 3 to 15 parts by mass in an arbitrary order with respect to a total of 100 parts by mass of the components (a) to (d), Step II: Soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; polyolefin resin modified with polar group-containing compound or copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer A step of laminating the adhesive composition obtained in Step I above on the surface of the layer (B1) of polyester resin; or acrylic resin; and forming the layer (A)
- Soft and hard vinyl chloride resin polystyrene; polycarbonate; glass; aluminum; steel plate; polyolefin resin modified with polar group-containing compound or copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer A polyester resin; or an acrylic resin layer (B1); (A) Epoxy resin 10-30% by mass (B) Oxetane compound 25-55 mass% (C) Vinyl ether compound 25 to 55% by mass (D) Denaturant 1 to 15% by mass (However, the total of the components (a) to (d) is 100% by mass) And (e) a cationic photopolymerization initiator layer (A) of an adhesive composition containing 3 to 15 parts by mass with respect to 100 parts by mass in total of the components (a) to (d); Soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; polyolefin resin modified with polar group-containing compound
- the component (d) is a polyol (d-1) having a hydroxyl value of 40 to 330 mgKOH / g; and a polyol (d-2) having a hydroxyl value of 40 to 330 mgKOH / g and an acid value of 2 to 20 mgKOH / g
- the coating composition as described in 17 above which is at least one selected from the group consisting of a modified rubber (d-3); a compound (d-4) having an epoxy equivalent of 150 to 700 g / mol . 19.
- the component (d-1) is a castor oil-based polyol (d-1-1) having a hydroxyl value of 40 to 330 mgKOH / g; a polybutadiene-based polyol (d-1-2) having a hydroxyl value of 40 to 330 mgKOH / g; 19.
- the coating composition as described in 18 above which is at least one selected from the group consisting of a polyisoprene-based polyol having a value of 40 to 330 mg KOH / g or a hydrogenated product (d-1-3) thereof. 20. 20.
- the component (d-2) is a castor oil-based polyol (d-2-1) having a hydroxyl value of 40 to 330 mgKOH / g and an acid value of 2 to 20 mgKOH / g.
- the ionic liquid as an antistatic material is contained in an amount of 0.5 to 10 parts by mass with respect to a total of 100 parts by mass of the components (a) to (d), The coating composition as described in 2. 26. 26.
- the ionic liquid (f) contains an anion selected from the group consisting of halogen, carboxylate, sulfate, sulfonate, thiocyanate, aluminate, borate, phosphate, phosphinate, amide, antimonate, imide and methide. 27.
- the antistatic improver (g) comprises an acidic phosphate ester (g-1), a carbodiimide compound (g-2), and a vinyl ether compound (g-3). And at least one selected from the group, and the blending amount of the antistatic improver (g) is in the range of 0.02 to 30 when the mass of the ionic liquid (f) is 1. 28.
- the coating composition as described in any one of 25 to 27 above. 29.
- the adherend of the coating composition is a soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel sheet; a polyolefin resin modified with a polar group-containing compound or a copolymer of an olefin and a polar group-containing compound; 29.
- the coating composition as described in any one of 17 to 28 above, which is magnesium; acrylonitrile-butadiene-styrene copolymer; polyester resin; or acrylic resin.
- An ink-jet ink comprising the coating composition as described in any one of 17 to 29 above. 32. 32. The inkjet ink as described in 31 above, further comprising a colorant. 33. 30. A primer layer provided on an ink jet recording medium, comprising the coating composition according to any one of 17 to 29. 34. A printed matter obtained by performing inkjet printing on an inkjet recording medium using the inkjet ink described in 31 or 32 above.
- the adhesive composition and coating composition of the present invention contain the components (a), (b), (c), (d) and (e) in a specific quantitative relationship, they are polar resins. , Ceramics, metals, etc., specifically soft and hard vinyl chloride resins; polystyrene; polycarbonate; glass; aluminum; steel plates (for example, cold rolled steel plates, hot rolled steel plates, etc.); polyolefins modified with polar group-containing compounds Resin or copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer; polyester resin; or excellent adhesion to layers of acrylic resin, transparency, surface smoothness Excellent balance of performance, flexibility and impact resistance.
- polar resins Ceramics, metals, etc., specifically soft and hard vinyl chloride resins
- polystyrene polycarbonate
- glass aluminum
- steel plates for example, cold rolled steel plates, hot rolled steel plates, etc.
- the adhesive method of the present invention comprises a layer (A) of an adhesive composition containing the components (a), (b), (c), (d) and (e) in a specific quantitative relationship, and a soft And rigid vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; polyolefin resin modified with a polar group-containing compound or copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer; Since it is a method of laminating polyester resin; or acrylic resin layers (B1) and (B2) in a specific process order, the adhesion of the three layers becomes strong.
- a laminate according to one aspect of the present invention is an adhesive composition layer or paint containing the components (a), (b), (c), (d) and (e) in a specific quantitative relationship.
- a laminate according to another aspect of the present invention is an adhesive composition layer or paint containing the components (a), (b), (c), (d) and (e) in a specific quantitative relationship.
- the coating composition of the present invention is useful for ink jet inks because it has the above-mentioned properties and has a low viscosity.
- the coating composition of the present invention is excellent in adhesiveness to various substrates, it is useful for a primer layer provided on an ink jet recording medium.
- a printed matter printed using the ink-jet ink has excellent image coloring properties, and has excellent impact resistance and flexibility, and thus has excellent image robustness.
- Epoxy Resin The component (a) of the layer of the adhesive composition of the present invention and the coating composition (hereinafter, both may be simply referred to as the composition) is an epoxy resin.
- the epoxy resin (a) can be used without particular limitation as long as it is a compound containing one or more epoxy groups in the molecule.
- the compound containing an epoxy group an alicyclic epoxy compound having a cyclohexene oxide or cyclopentene oxide structure in the molecule, a glycidyl group-containing compound, and the like can be preferably used.
- alicyclic epoxy compound examples include, for example, dicyclopentadiene dioxide, limonene dioxide, (3,4-epoxycyclohexyl) methyl-3,4-epoxycyclohexanecarboxylate, 3-vinylcyclohexene oxide, bis (2,3-epoxycyclopentyl) ether, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, (3,4-epoxycyclohexyl) methyl alcohol, ( 3,4-epoxy-6-methylcyclohexyl) methyl-3,4-epoxy-6-methylcyclohexanecarboxylate, ethylene glycol bis (3,4-epoxycyclohexyl) ether, 3,4-epoxycyclohexyl Carboxylic acid ethylene glycol diester, (3,4-epoxycyclohexyl Car
- an alicyclic epoxy group containing copolymer etc. can be mentioned.
- glycidyl group-containing compound that can be used as the epoxy resin (a) include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and 1,4-butanediol diglycidyl.
- polymerizable unsaturated monomers used to produce the alicyclic epoxy group-containing copolymer or the glycidyl group-containing copolymer include methyl (meth) acrylate, ethyl (meth) acrylate, n- Propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl acrylate, n-octyl (meth) acrylate, lauryl (meth) ) acrylate, tridecyl (meth) acrylate, C 1 ⁇ 24 alkyl (meth) acrylate and stearyl (meth) acrylate; glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclo
- esters and ethylenically unsaturated groups (acryloyl, methacryloyl, vinyl, etc.) containing unsaturated monomers (eg 2-isocyanatoethyl (meth) acrylate, m-isopropenyl- ⁇ , ⁇ -dimethylbenzyl)
- unsaturated monomers eg 2-isocyanatoethyl (meth) acrylate, m-isopropenyl- ⁇ , ⁇ -dimethylbenzyl
- These compounds can be used alone or in combination of two or more.
- “(meth) acrylate” means acrylate or methacrylate
- the epoxy resin (a) is preferably in the molecular weight range of 100 to 10,000 from the viewpoint of cationic polymerization reactivity.
- a preferred epoxy resin (a) is a liquid epoxy resin (a-1). That is, it is a linear aliphatic liquid epoxy resin represented by the following general formula (a-1).
- the epoxy resin has a low viscosity, and the viscosity of the entire composition can be reduced by using this epoxy resin.
- n in the above formula is an integer of 2 to 10, preferably an integer of 4 to 10.
- other epoxy resins may be used in combination with the specific epoxy resin (a-1).
- the other epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, alicyclic epoxy resins, hydrogenated bisphenol A type epoxy resins, hydrogenated bisphenol F type epoxy resins, and the like.
- the usage ratio when these other epoxy resins are used in combination is set to be 20% by weight or less of the total amount with the specific epoxy resin (a-1). That is, when the amount exceeds 20% by weight, the transmittance and moisture resistance tend to decrease.
- 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate represented by the following formula (a-2) is also preferable.
- Oxetane compound Component (b) of the composition of the present invention is an oxetane compound.
- the oxetane compound (b) is a compound other than the epoxy resin (a) and has the following formula
- A represents a divalent hydrocarbon group having 1 to 23 carbon atoms which may contain a different atom such as an oxygen atom, and the like.
- a in the formula is, for example, a linear, branched or cyclic alkylene group (particularly methylene, ethylene, propylene, butylene, cyclohexylene group, etc.)
- a polyalkyleneoxy group having 4 to 30 carbon atoms, preferably 4 to 8 carbon atoms eg, poly (ethyleneoxy), poly (propyleneoxy) groups, etc.
- a phenylene group e.g, poly (ethyleneoxy), poly (propyleneoxy) groups, etc.
- oxetane compound examples include the following compounds having 1 to 4 oxetane rings.
- the compounds having an oxetane ring used in the present invention are those having 1 to 4 oxetane rings.
- the cured film of the composition loses flexibility and may be cracked by bending.
- various compounds having 1 to 4 oxetane rings can be used. Examples of the compound having one oxetane ring include compounds represented by the following general formula (1).
- R 1 represents a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group, such as an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, An aryl group, a furyl group or a thienyl group.
- R 2 represents an alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group or butyl group, 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 2-methyl- 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group and the like alkenyl group having 2 to 6 carbon atoms, phenyl group, benzyl group, fluorobenzyl group, methoxybenzyl group, phenoxyethyl group, etc.
- examples of the compound having two oxetane rings include a compound represented by the following general formula (2).
- R 1 is the same group as that in the general formula (1).
- R 3 is, for example, a linear or branched alkylene group such as an ethylene group, a propylene group or a butylene group, or a linear or branched poly (alkyleneoxy) such as a poly (ethyleneoxy) group or a poly (propyleneoxy) group. ) Group, propenylene group, methylpropenylene group or butenylene group or other linear or branched unsaturated hydrocarbon group, carbonyl group, alkylene group containing carbonyl group, alkylene group containing carboxyl group, or alkylene containing carbamoyl group Group.
- R 3 is also a polyvalent group selected from the groups represented by the following formulas (3), (4) and (5).
- R 4 is a carbon atom such as a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, a propoxy group or a butoxy group.
- a C 1-4 alkoxy group, a halogen atom such as a chlorine atom or a bromine atom, a nitro group, a cyano group, a mercapto group, a lower alkyl carboxyl group, a carboxyl group, or a carbamoyl group.
- R 5 is an oxygen atom, a sulfur atom, a methylene group, NH, SO, SO 2 , C (CF 3 ) 2 or C (CH 3 ) 2 .
- R 6 is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, or an aryl group.
- n is an integer of 0 to 2000.
- R 7 is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, or an aryl group.
- R 7 is also a group selected from the group represented by the following formula (6).
- R 8 is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group, or an aryl group.
- m is an integer of 0 to 100.
- Specific examples of the compound having two oxetane rings include compounds represented by the following formulas (7) and (8).
- the compound represented by the formula (7) is a compound in which R 1 is an ethyl group and R 3 is a carboxyl group in the formula (2).
- the compound represented by the formula (8) is a compound in which, in the general formula (2), R 1 is an ethyl group, R 3 is the formula (5), R 6 and R 7 are methyl groups, and n is 1.
- R 1 is the same group as that in the general formula (1).
- Examples of the compound having 3 to 4 oxetane rings include compounds represented by the following general formula (10).
- R 1 is the same group as that in the general formula (1).
- R 9 is, for example, a branched alkylene group having 1 to 12 carbon atoms such as groups represented by the following formulas (11) to (13), or a branched poly (alkyleneoxy group such as a group represented by the following formula (14). ) Group or a branched polysiloxy group such as a group represented by the following formula (15). j is 3 or 4.
- R 10 is a lower alkyl group such as a methyl group, an ethyl group or a propyl group.
- examples of the compound having 1 to 4 oxetane rings other than those described above include a compound represented by the following formula (17).
- R 8 is the same group as in the formula (6).
- R 11 is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, or a trialkylsilyl group, and r is 1 to 4.
- Preferred examples of the oxetane compound used in the present invention include the following compounds.
- p 20 to 200.
- q 15 to 100.
- s is 20 to 200.
- each group represented by the same symbol existing in one molecule may be the same as or different from each other.
- di- [1-ethyl (3-oxetanyl) represented by the following formula (25) is preferable from the viewpoints of the curing reaction rate, reduction of curing shrinkage, toughness, and low viscosity of the blended system. )] Methyl ether.
- the di [1-ethyl (3-oxetanyl)] methyl ether represented by the above formula (25) includes, for example, OXT-221 manufactured by Toagosei Co., Ltd.
- Vinyl ether compound Component (c) of the composition of the present invention is a vinyl ether compound.
- the vinyl ether compound (c) include ethyl vinyl ether, isobutyl vinyl ether, n-butyl vinyl ether, tert-butyl vinyl ether, n-amyl vinyl ether, i-amyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, 2-ethylhexyl vinyl ether.
- 1,4-cyclohexanedimethanol divinyl ether glycerol monovinyl ether, 1,4-butanediol monovinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, neopentyl glycol divinyl ether , Pentaerythritol divinyl ether, pentaerythritol tetravinyl ether, trimethylolpropane divinyl ether, trimethylolpropane trivinyl ether, 1,4-dihydroxycyclohexane monovinyl ether, 1,4-dihydroxycyclohexane divinyl ether, 1,4-dihydroxymethylcyclohexane monovinyl ether Mono-polyvinyl ethers of polyhydric alcohols such as 1,4-dihydroxymethylcyclohexane divinyl ether
- polyalkylene glycol mono-divinyl ethers such as diethylene glycol divinyl ether, tetraethylene glycol divinyl ether, triethylene glycol divinyl ether, diethylene glycol monobutyl monovinyl ether; and other vinyl ethers such as glycidyl vinyl ether and ethylene glycol vinyl ether methacrylate; Examples thereof include hydroxybutyl vinyl ether.
- the component (d) used in the present invention is a modifier.
- the modifier (d) include a polyol (d-1) having a hydroxyl value of 40 to 330 mgKOH / g; and a polyol (d-) having a hydroxyl value of 40 to 330 mgKOH / g and an acid value of 2 to 20 mgKOH / g. 2); modified rubber (d-3); at least one selected from the group consisting of compound (d-4) having an epoxy equivalent of 150 to 700 g / mol.
- the hydroxyl value of component (d) is determined by the adherend (soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate (eg, SPCC); polyolefin resin modified with a polar group-containing compound. Or a copolymer of an olefin and a polar group-containing compound; magnesium; an acrylonitrile-butadiene-styrene copolymer; a polyester resin; or an acrylic resin) (hereinafter sometimes referred to as a specific adherend (B)) Contributes to improved adhesive strength.
- adherend soft and hard vinyl chloride resin
- polystyrene polycarbonate
- glass glass
- aluminum steel plate
- SPCC steel plate
- examples of (i) polyol (d-1) having a hydroxyl value of 40 to 330 mg KOH / g include aromatic, aliphatic, polybutadiene, castor oil, polyisoprene, and the like. As long as it is any type, the selective adhesion to the specific adherend (B) is good.
- the hydroxyl value is preferably 40 to 330 mgKOH / g from the viewpoint of the selective adhesive strength, and more preferably 150 to 300 mgKOH / g.
- the polyol of component (d) can be used as a mixture of two or more if necessary.
- the “castor oil” is an oil containing a triester compound of ricinoleic acid and glycerin. Usually, it is a natural fat or oil or a processed natural fat or oil, but it may be a synthetic fat or oil if it contains the above compounds.
- the ricinoleic acid constituting the triester compound contained in this castor oil is preferably contained in an amount of 90 mol% or more of the fatty acids constituting the whole triester compound.
- the castor oil may be a processed product such as a hydrogenated product (usually hydrogenated to an intercarbon unsaturated bond in the ricinoleic acid skeleton). Usually, castor oil contains 90 mol% or more (including 100 mol%) of the above-described triester compound (in the case of a hydrogenated product, a hydrogenated product of the triester compound).
- the “castor oil-based polyol” is an ester compound of ricinoleic acid and / or hydrogenated ricinoleic acid and a polyhydric alcohol. If it has this structure, it may be a polyol obtained by using castor oil as a starting material, or a polyol obtained by using a raw material other than castor oil as a starting material. This polyhydric alcohol is not particularly limited.
- Castor oil-based polyols include polyols derived from castor oil and polyols obtained by modifying castor oil.
- the polyol derived from castor oil is a glycerin ester in which part of the ricinoleic acid is replaced with oleic acid, and ricinoleic acid obtained by saponifying castor oil is esterified with trimethylolpropane or other short molecular polyols.
- fatty acid ester polyols derived from castor oil such as a mixture of these and castor oil.
- polyols obtained by modifying castor oil include vegetable oil-modified polyols and modified polyols having an aromatic skeleton (such as bisphenol A).
- a vegetable oil-modified polyol is obtained by replacing a part of glycerin ester ricinoleic acid with a fatty acid obtained from other plants, for example, higher fatty acids such as linoleic acid, linolenic acid, oleic acid obtained from soybean oil, rapeseed oil, olive oil, etc. It is obtained.
- castor oil-based polyol (d-1-1) having a component (i) hydroxyl value of 40 to 330 mgKOH / g is preferable from the viewpoint of the effect of the present invention. Further, (i) an aromatic castor oil-based polyol (d-1) having a hydroxyl value of 40 to 330 mgKOH / g in terms of improving the toughness (impact resistance), flexibility, and adhesion to different materials of the adhesive layer. -1-1) is preferred. More preferably, it is 150 to 240 mg KOH / g.
- the component (d-1-1-1) is a modified polyol derived from castor oil having an aromatic skeleton (for example, bisphenol A).
- the component (d-1-1-1) is commercially available, and examples thereof include “URIC AC series” (Ito Oil Co., Ltd.).
- an adduct obtained by adding polyalkylene glycol and bisphenol A to ricinoleic acid has preferable adhesion to the specific adherend (B), and can be represented by, for example, the following formula (26).
- n represents an average number of 2 to 5.
- Modified polyols derived from castor oil represented by the formula (26) are, for example, trade names URIC AC-005 (hydroxyl value 194 to 214 mg KOH / mg, viscosity 700 to 1500 mPa ⁇ s / 25 ° C.), AC-006 ( Hydroxyl value 168 to 187 mgKOH / mg, viscosity 3000 to 5000 mPa ⁇ s / 25 ° C., AC-008 (hydroxyl value 180 mgKOH / mg, viscosity 1600 mPa ⁇ s / 25 ° C.), AC-009 (hydroxyl value 225 mgKOH / mg, viscosity 1500 mPa -It can obtain from Ito Oil Co., Ltd. as s / 25 degreeC.
- polybutadiene-based polyol used in the present invention examples include homopolymers such as 1,2-polybutadiene polyol and 1,4-polybutadiene polyol, poly (pentadiene / butadiene) polyol, poly (butadiene / styrene) polyol, poly ( Examples thereof include copolymers such as butadiene / acrylonitrile) polyols, and hydrogenated polybutadiene-based polyols obtained by adding hydrogen to these polyols.
- Polybutadiene-based polyols are commercially available.
- the hydroxyl value of the (d-1-2) polybutadiene-based polyol is preferably 40 to 330 mgKOH / g, more preferably 40 to 110 mgKOH / g.
- the weight average molecular weight (GPC method) of the polybutadiene-based polyol is preferably 50 to 3000, and more preferably 800 to 1500.
- Examples of such component (d-1-3) include Polyip (registered trademark) (hydroxyl-terminated liquid polyisoprene) manufactured by Idemitsu. “Poly ip (registered trademark)” (hydroxyl value 46.6 mg KOH / mg, Mn 2500) is a polyisoprene type liquid polymer having a highly reactive hydroxyl group at the molecular end.
- An example of the hydrogenated product is Epole (registered trademark) (hydroxyl-terminated liquid polyolefin) manufactured by Idemitsu.
- Epol® hydroxyl value 50.5 mg KOH / mg, Mn 2500
- the (i) epoxy polyol resin (d-1-4) having a hydroxyl value of 40 to 330 mg KOH / g used in the present invention is obtained by reacting an epoxy resin with an active hydrogen compound.
- epoxy resin used here examples include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis ( Orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4- Hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobis Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as enol, oxybisphenol, phenol novolak,
- biphenol methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol (bisphenol AD), isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A
- bisphenol-type epoxy resins such as polyglycidyl ether compounds such as 1,3-bis (4-hydroxycumylbenzene) and 1,4-bis (4-hydroxycumylbenzene) It is preferable because an excellent coating film can be formed.
- An epoxy polyol resin (d-1-4) having a hydroxyl value of 40 to 330 mgKOH / g is obtained by reacting an epoxy group of the above epoxy resin with an active hydrogen compound such as a carboxylic acid compound, a polyol or an amino compound. It is
- carboxylic acid compound examples include acetic acid, propionic acid, 2,2-dimethylolpropionic acid, 12-hydroxystearic acid, lactic acid, butyric acid, octylic acid, ricinoleic acid, lauric acid, benzoic acid, toluic acid, cinnamic acid, phenyl Aliphatic, aromatic or cycloaliphatic monocarboxylic acids such as acetic acid and cyclohexanecarboxylic acid, maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, adipic acid, dimer acid, phthalic acid, isophthalic acid, terephthalic acid, Examples include hexahydro acid and hydroxypolycarboxylic acid.
- polyol examples include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methyl-1,3-propylene glycol, 2,2-dimethyl-1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2,4-trimethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 1,2-octanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, glycerin, trimethylolpropane, pentaerythritol
- amino compounds examples include dialkylamine compounds such as dibutylamine and dioctylamine; alkanolamine compounds such as methylethanolamine, butylethanolamine, diethanolamine, diisopropanolamine, and dimethylaminopropylethanolamine; morpholine, piperidine, 4-methylpiperazine And heterocyclic amine compounds such as
- alkanolamine compounds such as diethanolamine are preferable.
- the epoxy resin can be chain-extended with a compound having two or more active hydrogen groups such as monoethanolamine and monoisopropanolamine.
- a normal method of adding the active hydrogen compound to the epoxy resin can be employed.
- a known catalyst such as a tertiary amine compound or a phosphonium salt.
- a method in which both are heated to 60 to 200 ° C. and reacted for 3 to 10 hours can be used.
- a preferable hydroxyl value of the epoxy polyol resin (d-1-4) having a hydroxyl value of 40 to 330 mgKOH / g is 100 to 140 mgKOH / g from the viewpoint of the effect of the present invention.
- epoxy polyol resin (d-1-4) having a hydroxyl value of 40 to 330 mgKOH / g EPICLON U-125-60BT (hydroxyl value 100 to 140 mgKOH / g) manufactured by DIC Corporation may be mentioned.
- the polyol (d-2) having a hydroxyl value of 40 to 330 mg KOH / g and (ii) an acid value of 2 to 20 mg KOH / g may be aromatic, aliphatic or castor oil-based. However, by satisfying the hydroxyl value of (i) and the acid value of (ii), the selective adhesion force (particularly the adhesion force between different materials) to the specific adherend (B), which is a feature of the present invention, is improved.
- the hydroxyl value of (i) is more preferably 230 to 300 mgKOH / g.
- the acid value of (ii) is more preferably 4 to 15 mg KOH / g.
- a castor oil-based polyol (d-2-1) having a hydroxyl value of 40 to 330 mgKOH / g and (ii) an acid value of 2 to 20 mgKOH / g is a polyol derived from castor oil. As disclosed in JP-A-2005-89712, it contains a castor oil-based polyol derived from ricinoleic acid, an acidic phosphate ester compound having a total carbon number of 12 or more, and, if necessary, terpene phenols Polyol compositions can also be used. These can be obtained from Ito Refinery under the trade names URIC H-1262 and H2151U, for example.
- the Ito Oil URIC H-1262 is a polyol containing a castor oil-based polyol and an acidic phosphate ester compound having a total carbon number of 12 or more (viscosity: 3,500 to 8,500 mPa ⁇ s / 25 ° C., hydroxyl value: 240 to 290 (unit mgKOH / g), acid value: 4 to 15 (unit mgKOH / g)), excellent adhesion to the layer of the specific adherend (B), especially for metal adhesion and hydrolysis resistance Excellent.
- the Ito Oil URIC H-2151U is a polyol containing a castor oil-based polyol, an acidic phosphate compound having 12 or more carbon atoms and terpene phenols (viscosity: 3,500 to 8,500 mPa ⁇ s / 25). ° C, hydroxyl value: 240 to 290 (unit mgKOH / g), acid value: 4 to 15 (unit mgKOH / g)), excellent adhesion to the layer of the specific adherend (B), particularly metal adhesion Excellent in resistance and hydrolysis resistance.
- the modified rubber (d-3) will be described.
- Examples of the modified rubber (d-3) used in the present invention include (d-3-1) liquid carboxylated polyisoprene and (d-3-2) carboxylated polybutadiene.
- the carboxylated polyisoprene (d-3-1) used in the present invention is mainly used when the composition of the present invention is bonded to a metal substrate or a glass substrate. It functions to improve the wettability of the substrate surface and improve the adhesive strength.
- Examples of the component (d-3-1) include LIR-420 manufactured by Kuraray as maleated polyisoprene.
- the carboxylated polybutadiene (d-3-2) used in the present invention is mainly used for bonding the composition of the present invention to a metal substrate or a glass substrate. It functions to improve the wettability of the surface and improve the adhesive strength.
- Component (d-3-2) is a liquid which is transparent at room temperature and has a main chain microstructure of polybutadiene of vinyl 1,2-bond type, trans 1,4-bond type, cis 1,4-bond type. It is a polymer.
- the vinyl 1,2-bond is preferably 30% by weight or less, and if the vinyl 1,2-bond exceeds 30% by weight, the storage stability of the resulting composition is deteriorated.
- the cis 1,4-bond is preferably 40% by weight or more. If the cis 1,4-bond is less than 40% by weight, the adhesiveness of the resulting composition is lowered, which is not preferable.
- the carboxylated polybutadiene (d-3-2) component is obtained by reacting liquid polybutadiene with a carboxyl group-introducing compound, and the ratio of 1,3-butadiene and carboxyl group-introducing compound constituting the liquid polybutadiene is 1,3. -80 to 98% by weight of butadiene and 2 to 20% by weight of the carboxyl group-introducing compound are preferred.
- the liquid polybutadiene used in the reaction preferably has a number average molecular weight of 500 to 10,000, more preferably 1,000 to 7,000, and a wide molecular weight distribution.
- the liquid polybutadiene more preferably has an iodine value measured according to DIN 53241, iodine of 30 to 500 g / 100 g of substance.
- the liquid polybutadiene preferably has a molecular structure of 70 to 90% cis-double bonds, 10 to 30% trans-double bonds and 0 to 3% vinyl double bonds.
- an ethylenically unsaturated dicarboxy compound for example, an ethylenically unsaturated dicarboxylic acid, its anhydride or monoester
- the compound include maleic acid, fumaric acid, itaconic acid, 3,6-tetrahydrophthalic acid, itaconic anhydride, 1,2-dimethylmaleic anhydride, monomethyl maleate or monoethyl maleate.
- maleic anhydride is preferable because of safety, economy and reactivity. (Maleed polybutadiene is preferred.)
- Production of a polybutadiene / maleic anhydride-addition product comprising polybutadiene and maleic anhydride can be carried out by a known method.
- the acid value of maleated liquid polybutadiene according to DIN ISO 3682 is preferably 50 to 120 (mgKOH / g), more preferably 70 to 90 (mgKOH / g).
- the acid value is less than 50 (mgKOH / g)
- the adhesiveness of the resulting composition is lowered
- it exceeds 120 (mgKOH / g) the viscosity of the obtained composition is increased and workability is lowered.
- the maleation rate of the maleated liquid polybutadiene is related to the viscosity, but is preferably 6 to 20%, more preferably 6 to 15%, and still more preferably 7 to 10%.
- the viscosity (20 ° C.) of maleated liquid polybutadiene measured by DIN 53214 is preferably 3 to 16 Pa ⁇ s, more preferably 5 to 13 Pa ⁇ s, and further preferably 6 to 9 Pa ⁇ s.
- maleated liquid polybutadiene has a vinyl-double bond of 30% or less, and those having a cis-double bond in the above range have higher flexibility than liquid polybutadiene in which the cis-double bond is less than the above lower limit. And has a high maleation rate (acid value) as described above. Therefore, since the composition obtained is rich in adhesiveness and sufficiently polarized, the composition of the present invention can be made more flexible, the flexibility can be easily adjusted, and the decoration is excellent. Liquid polybutadiene having a cis-double bond less than the above lower limit rapidly increases in viscosity as the maleation rate increases, but those having a cis-double bond in the above range have a small increase in viscosity. Since the viscosity is low as in the above range, the reactivity is increased and workability is improved. Moreover, the composition obtained is excellent in terms of decorating properties.
- Examples of commercially available maleated liquid polybutadiene include POLYVEST OC 800S (registered trademark) and 1200S manufactured by Degussa.
- One form of the compound (d-4) having an epoxy equivalent of 150 to 700 g / mol used in the present invention is a polyepoxy compound (d-4-1) having an epoxy equivalent of 150 to 250 g / mol. .
- Examples of the polyepoxy compound (d-4-1) having an epoxy equivalent of 150 to 250 g / mol in the composition of the present invention include mononuclear polyhydric phenols such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol.
- Examples of the polyepoxy compound (d-4-1) having an epoxy equivalent of 150 to 250 g / mol used in the present invention include biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropyl Ridenbisphenol (bisphenol A), isopropylidenebis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1, Polyphenols of bisphenol compounds such as 1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, terpene diphenol Glycidyl Jill ether is more preferable in terms of the metal adhesion.
- polyglycidyl ethers of bisphenol compounds having an epoxy equivalent of 150 to 250 g / mol examples include Adeka Resin EP-4100E (Asahi Denka Kogyo; bisphenol A diglycidyl ether, epoxy equivalent 190).
- Another form of the compound (d-4) having an epoxy equivalent of 150 to 700 g / mol used in the present invention is a polyolefin polymer (d-4-2) having an epoxy equivalent of 500 to 700 g / mol. It is.
- a polyolefin polymer having a hydroxyl group at one end and having an epoxy group introduced is preferred. More preferably, it is liquid.
- a specific example of the polymer (d-4) having an epoxy equivalent of 150 to 700 g / mol is Kuraray L-207 (same as KRATON LIQUID TM L-207 POLYMER).
- L-207 has a fully saturated skeleton (epoxidized ethylene / propylene / ethylene / butylene-OH structure) having an epoxy equivalent of 590 g / mol, a hydroxyl equivalent of 7000 g / mol, and a glass transition temperature of ⁇ 53 ° C. It is a coalescence and is preferable from the viewpoint of metal adhesion as a reason for use in the present invention.
- composition of the present invention comprises (e) a cationic photopolymerization initiator as an essential component.
- the photocationic polymerization initiator used in the composition of the present invention is not particularly limited, and various types can be used.
- these initiators include onium salts such as iodonium salts, diazonium salts, and sulfonium salts.
- onium salts such as iodonium salts, diazonium salts, and sulfonium salts.
- aromatic diazonium salts, aromatic sulfonium salts (for example, triarylsulfonium salts), aromatic iodonium salts (for example, diaryliodonium salts), aromatic sulfoxonium salts, metallocene compounds, iron arene compounds, and the like can be used. .
- the photocationic polymerization initiator is a salt represented by A + B ⁇ that generates a cationically active species by light irradiation.
- the cation A + is preferably an aromatic iodonium ion or an aromatic sulfonium ion.
- Aromatic iodonium ions have the formula: Ar 1 -I + -Ar 2 As shown, the two groups Ar 1 and Ar 2 bonded to I + are independently an aromatic group, and an optionally substituted phenyl group is particularly preferable.
- aromatic sulfonium ion has the formula:
- Ar 1 , Ar 2 and Ar 3 bonded around S + are each independently an aryl group, particularly preferably a phenyl group which may have a substituent.
- the anion B ⁇ includes at least an initiator which is a B (aryl) 4 ⁇ ion such as SbF 6 ⁇ or B (C 6 F 5 ) 4 — .
- B (aryl) 4 - The, B (C 6 F 5) 4 - in addition to, for example, B (C 6 F 4 OCF 3 ) 4 -, B (C 6 F 4 CF 3) 4 - , etc. can be mentioned Can do.
- Specific examples include compounds represented by the following formula.
- an initiator in which the anion B ⁇ is SbF 6 ⁇ or B (aryl) 4 ⁇ ion has a high curing rate.
- the anion B ⁇ may contain an initiator having an anion other than SbF 6 ⁇ and B (aryl) 4 ⁇ ions. These have the advantage that the curing speed is slow but the adhesive strength is increased, and they can be used in combination with an initiator in which B ⁇ is SbF 6 ⁇ and B (aryl) 4 ⁇ ions.
- the anion B ⁇ include PF 6 ⁇ , AsF 6 ⁇ and BF 4 ⁇ .
- Specific examples of the compound include salts in which SbF 6 ⁇ is replaced with PF 6 ⁇ , AsF 6 ⁇ , BF 4 ⁇ or the like in the above-described compound.
- VPS-1001 Polycondensate of 4,4′-azobis (4-cyanovaleric acid) and ⁇ , ⁇ -bis (3-aminopropyl) polydimethylsiloxane (manufactured by Wako Pure Chemical Industries, Ltd.)
- WPI-113 (50% propylene carbonate): iodonium hexafluorophosphate (manufactured by Wako Pure Chemical Industries, Ltd.) (onium salt type)
- WPI-116 (50% propylene carbonate): iodonium hexafluroantimonate (manufactured by Wako Pure Chemical Industries, Ltd.)
- WPI-170 Iodonium hexaflurophosphate (Wako Pure Chemical Industries, Ltd.)
- SP-170 sulfonium / hexafluoroantimony polymerization initiator (manufactured by Adeka)
- the composition of the present invention can contain an ionic liquid (f) as an antistatic material.
- the ionic liquid (f) is a salt composed of a cation and an anion and is a liquid.
- the ionic liquid (f) used in the present invention preferably contains at least one cation selected from the group consisting of imidazolium, pyridinium, pyrrolidinium, phosphonium, ammonium and sulfonium. Examples of the cation are as follows.
- the ionic liquid (f) used in the present invention includes an anion selected from the group consisting of halogen, carboxylate, sulfate, sulfonate, thiocyanate, aluminate, borate, phosphate, phosphinate, amide, antimonate, imide and methide. Those are preferred. Examples of the anion are as follows.
- the ionic liquid is preferably water-soluble.
- preferred ionic liquids are combinations of cations and anions, such as (1-1) and (10-1), (1-1) and (10-4), (1-1) and (11-1 ), (1-2) and (8-3), (1-2) and (10-1), (1-2) and (10-2), (1-2) and (10-4), (1-2) and (11-1), (1-6) and (7-11), (1-6) and (8-3), (1-6) and (8-5), (1 -6) and (8-6), (1-6) and (9-1), (1-6) and (9-2), (1-6) and (9-3), (1-6) ) And (10-1), (1-6) and (10-4), (1-6) and (10-7), (1-6) and (11-1), (1-6) (12-5), (1-6) and (12-6), (1-8) and (8-2), (1-8) and (8-5), (1- ) And (8-6), (1-8) and (9-1), (1-8) and (10-4), (1-12) and (10-4), (1-13) (10-4), (1-17) and (10-4), (2-1) and (9-1), (2-1) and (
- an ionic liquid having an ion pair of (1-2) and (10-2) is more preferable, 1-2) and (8-3) when using ionic liquids having an ion pair is particularly high adhesive strength of the specific and the adherend (B) of, and preferably from the viewpoint of excellent antistatic property.
- the paint of the present invention can further contain an antistatic improver (g) as required.
- the antistatic improver (g) include at least one selected from the group consisting of an acidic phosphate ester (g-1) and a carbodiimide compound (g-2).
- any acidic phosphate ester generally used as an additive for plastics can be used.
- any acidic phosphate ester generally used as an additive for plastics can be used.
- phosphoric acids include phosphoric acid, metaphosphoric acid, orthophosphoric acid, phosphorous acid, phosphonic acid, pyrophosphoric acid, diphosphinic acid, diphosphoric acid, and diphosphonic acid.
- the group that substitutes active hydrogen include an alkyl group, an aryl group, an alkenyl group, and a hydroxyalkyl group (all of which have 1 to 30 carbon atoms).
- Examples of the above include monoalkyl esters, monoaryl esters, dialkyl esters, diaryl esters, monoalkyl esters of phosphorous acid, and trialkyl esters of pyrophosphoric acid. Of these, preferred are those represented by the formula (g-1-1).
- R 1 is a monovalent hydrocarbon group having 1 to 30 carbon atoms, n is 1 or 2, and when n is 2, R 1 may be the same or different.
- the alkyl group having 1 to 30 carbon atoms represented by R 1 includes methyl, ethyl, n- and i-propyl, n-, i-, sec- and t-butyl.
- the acidic phosphate ester is an acidic phosphate having the above R 1 having 8 to 30 carbon atoms, and particularly preferable ones are monolauryl ester of phosphoric acid, monostearyl ester of phosphoric acid, and phosphoric acid. Distearyl ester, or a combination thereof.
- the acidic phosphate ester is, for example, a method of hydrolyzing a corresponding trialkyl phosphate or a corresponding triester or tetraester of phosphoric acid, a method of hydrolyzing after reacting phosphorus oxychloride with a corresponding alkanol, or It can be synthesized by a known method such as a method of reacting phosphorus pentoxide with the corresponding alkanol.
- carbodiimide compound (g-2) in the present invention a compound having two or more carbodiimide groups (—N ⁇ C ⁇ N—) in the molecule is preferably used, and known polycarbodiimides can be used.
- generated by carrying out the decarboxylation condensation reaction of diisocyanate in presence of a carbodiimidization catalyst can also be used.
- examples of such compounds include those obtained by subjecting the following diisocyanates to a decarboxylation condensation reaction.
- Diisocyanates include 4,4′-diphenylmethane diisocyanate, 3,3′-dimethoxy-4,4′-diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 4,4′-diphenyl ether diisocyanate, 3,3′-dimethyl-4,4′-diphenyl ether diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, isophorone diisocyanate, 4,4′- One of dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, or a mixture thereof can be used.
- the carbodiimidization catalysts include 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene-1-oxide, 1-ethyl- Phosphorene oxides such as 2-phospholene-1-oxide or their 3-phospholene isomers can be used.
- Carbodilite V-01, 03, 05, 07, 09 is preferable because it is excellent in antistatic improvement.
- Optional component (h) Colorant When the coating composition of the present invention is used as an inkjet ink or primer, it preferably contains (h) a colorant.
- the colorant that can be used in the present invention is not particularly limited, but pigments and oil-soluble dyes that are excellent in weather resistance and excellent in color reproducibility are preferable, and are arbitrarily selected from known colorants such as soluble dyes. Can be used.
- the colorant that can be suitably used when the coating composition of the present invention is used as an inkjet ink or primer is prohibited from polymerization in a polymerization reaction that is a curing reaction from the viewpoint of not reducing the sensitivity of the curing reaction by actinic radiation. It is preferable to select a compound that does not function as an agent.
- ⁇ Pigment> Although it does not necessarily limit as a pigment which can be used for this invention, for example, the organic or inorganic pigment of the following number described in a color index can be used.
- red or magenta pigments include Pigment Red 3, 5, 19, 22, 31, 38, 43, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49: 1, 53: 1.
- the oil-soluble dye that can be used in the present invention means a dye that is substantially insoluble in water. Specifically, the solubility in water at 25 ° C. (the mass of the dye that can be dissolved in 100 g of water) is 1 g or less, preferably 0.5 g or less, more preferably 0.1 g or less. Therefore, the oil-soluble dye means a so-called water-insoluble pigment or oil-soluble dye, and among these, an oil-soluble dye is preferable.
- any yellow dye can be used.
- phenols, naphthols, anilines, pyrazolones, pyridones, aryl or heteryl azo dyes having open-chain active methylene compounds as coupling components for example, azomethine dyes having open-chain active methylene compounds as coupling components;
- methine dyes such as benzylidene dyes and monomethine oxonol dyes
- quinone dyes such as naphthoquinone dyes and anthraquinone dyes
- other dye species such as quinophthalone dyes, nitro / nitroso dyes, and acridines.
- dyes and acridinone dyes for example, phenols, naphthols, anilines, pyrazolones, pyridones, aryl or heteryl azo dyes having open-chain active methylene compounds as coupling components;
- methine dyes such as
- any magenta dye can be used.
- any cyan dye can be used.
- indoaniline dyes indophenol dyes or azomethine dyes having pyrrolotriazoles as coupling components
- polymethine dyes such as cyanine dyes, oxonol dyes, merocyanine dyes
- carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes Phthalocyanine dyes
- anthraquinone dyes for example, aryl or heteryl azo dyes having phenols, naphthols and anilines as coupling components
- indigo / thioindigo dyes indigo / thioindigo dyes
- Each of the above dyes may exhibit yellow, magenta, and cyan colors only after a part of chromophore (chromogenic atomic group) is dissociated.
- the counter cation may be an alkali metal or ammonium.
- Such inorganic cations may be used, and organic cations such as pyridinium and quaternary ammonium salts may be used, and furthermore, polymer cations having such a partial structure may be used.
- Oil-soluble dye may be used alone or in combination of several kinds.
- a disperse dye can be used as long as it is soluble in a water-immiscible organic solvent.
- the disperse dye generally includes a water-soluble dye, but in the present invention, the disperse dye is preferably used as long as it is soluble in a water-immiscible organic solvent.
- the disperse dye include C.I. I.
- the colorant that can be used in the present invention is used as an ink or a primer, it is preferable that the colorant is appropriately dispersed in the ink after being added.
- a dispersion device such as a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, or a paint shaker can be used.
- colorants may be used by appropriately selecting one kind or two or more kinds according to the purpose of use.
- the coating composition of the present invention when used as an inkjet ink or primer, when using a colorant such as a pigment that remains solid in the coating composition, the average particle size of the colorant particles Selection of colorant, dispersant, dispersion medium and dispersion so that the diameter is preferably 0.005 to 0.5 ⁇ m, more preferably 0.01 to 0.45 ⁇ m, and still more preferably 0.015 to 0.4 ⁇ m. It is preferable to set conditions and filtration conditions. This particle size control is preferable because clogging of the head nozzle can be suppressed and ink storage stability, ink transparency, and curing sensitivity can be maintained.
- the content of the colorant in the coating composition of the present invention is appropriately selected depending on the color and the purpose of use, but is generally preferably 0.01 to 30% by mass with respect to the total mass of the coating. .
- the paint of the present invention preferably contains (g) a colorant and (i) a dispersant.
- the (i) dispersant is preferably an acidic dispersant.
- An acidic dispersant is a dispersant having an acidic functional group.
- the acidic dispersant preferably has an acid value of 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, and further preferably 40 mgKOH / g or more.
- the acidic dispersant preferably has an acid value greater than the amine value.
- the amine value indicates the total amount of 1, 2, and tertiary amines, and is expressed in mg of KOH equivalent to hydrochloric acid required to neutralize 1 g of the sample.
- the acid value is the number of mg of KOH required to neutralize free fatty acid, resin acid, etc. contained in 1 g of a sample.
- the dispersant is not particularly limited as long as it is an acidic dispersant. However, it is preferable to use a polymer dispersant, and it is more preferable to use a polymer dispersant having an acid value larger than the amine value.
- the difference between the acid value and the amine value of the dispersant is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, and further preferably 20 mgKOH / g or more.
- DisperBYK-101 (acid value: 30 mgKOH / g, amine value: 0 mgKOH / g), DisperBYK-102 (acid value: 101 mgKOH / g, amine value: 0 mgKOH) / G), DisperBYK-103 (acid value: 101 mgKOH / g, amine value: 0 mgKOH / g), DisperBYK-106 (acid value: 132 mgKOH / g, amine value: 74 mgKOH / g), DisperBYK-111 (acid value: 129 mgKOH) / G, amine value: 0 mgKOH / g) (above, manufactured by BYK Chemie), EFKA4010 (acid value: 10-15 mgKOH / g, amine value: 4-8 mgKOH / g) (above, manufactured by Fuka Additive) Polymer
- a dispersant may be used alone or in a plurality of types.
- other known dispersants can be used in combination.
- DisperBYK-161 (amine value: 11 mgKOH / g, acid value: 0 mgKOH / g)
- DisperBYK-162 (amine value: 13 mgKOH / g, acid value: 0 mgKOH / g)
- DisperBYK-163 (amine value: 10 mgKOH / g, acid value: 0 mgKOH / g)
- DisperBYK-164 amine value: 18 mgKOH / g, acid value: 0 mgKOH / g
- DisperBYK-166 (amine value: 20 mgKOH / g, acid value: 0 mgKOH / g)
- DisperBYK-167 (amine value: 13 mgKOH / g, acid value: 0 mgKOH / g)
- DisperBYK-168 (amine value: 10
- the content of the dispersant in the paint of the present invention is appropriately selected depending on the purpose of use, but is preferably 0.01 to 50% by mass, and preferably 0.1 to 30% by mass with respect to the mass of the colorant. More preferred is 1 to 10% by mass. It is preferable that the added amount of the dispersant is 0.01% by mass or more because the dispersibility of the pigment is excellent and the dispersion stability is good. Further, it is preferable that the amount of the dispersant added is 50% by mass or less because the stability with time of the ink is good.
- composition ratio of the composition In the composition of the present invention, (a) the epoxy resin is blended in an amount of 10 to 30% by mass from the viewpoints of adhesion and high hardness. More preferably, it is 15 to 25% by mass.
- the compounding amount of the component (a) is less than 10% by mass, the adhesive strength and hardness are deteriorated.
- the compounding amount of component (a) exceeds 30% by mass, the shrinkage rate is large, and the adhesive strength and impact resistance are deteriorated.
- the oxetane compound is blended in an amount of 25 to 55% by mass from the viewpoints of curing reaction rate, impact characteristics, and toughness. More preferably, it is 30 to 50% by mass.
- the compounding amount of component (b) is less than 25% by mass, the adhesive strength and hardness deteriorate.
- the compounding amount of the component (b) exceeds 55% by mass, the shrinkage rate is large and the impact is deteriorated.
- the vinyl ether compound (c) is blended in an amount of 25 to 55% by mass from the viewpoint of low viscosity and low shrinkage. More preferably, it is 30 to 53% by mass.
- the amount of component (c) is less than 25% by mass, the shrinkage reduction effect and the viscosity reduction effect are deteriorated. If it exceeds 55% by mass, the adhesive strength deteriorates.
- the modifier (d) is blended in an amount of 1 to 15% by mass from the viewpoints of adhesiveness and low shrinkage. More preferably, it is 5 to 10% by mass.
- the blending amount of component (d) is less than 1% by mass, the shrinkage reduction effect and the adhesive strength improvement effect are deteriorated.
- it exceeds 15% by mass the transparency and the adhesive strength deteriorate. (However, the total of the components (a) to (d) is 100% by mass)
- the cationic photopolymerization initiator is the component (a) to (d) described above from the viewpoint of practical photocuring time (irradiation intensity of 500 mJ / cm 2 and irradiation for 10 seconds or less). 3 to 15 parts by mass with respect to 100 parts by mass in total. Furthermore, from the viewpoint of practical photocuring time (irradiation intensity of 500 mJ / cm 2 for 3 seconds or less), the amount is preferably 5 to 10 parts by mass. If the amount of component (e) is less than 3 parts by mass, it will not cure. If it exceeds 15 parts by mass, the shrinkage will worsen.
- the blending amount of the component (f) ionic liquid is preferably 0.5 to 10 parts by mass, and preferably 2 to 7 parts by mass with respect to 100 parts by mass of the components (a) to (d). Further preferred. Further, the blending amount of the antistatic improver (g) is preferably in the range of 0.02 to 30 and more preferably 0.03 to 20 when the mass of the ionic liquid (f) is 1. 0.04 to 3 is particularly preferable.
- composition of the present invention if necessary, a functional filler or the like generally used as a filler can be added and blended within a range not impairing the object of the present invention.
- Examples of imparting rigidity include talc and mica, and these are used singly or in combination of two or more.
- thermal conductivity imparting examples include barium sulfate and magnesium oxide, and these are used alone or in combination of two or more.
- Examples of imparting thermal expansion include thermal expansion microcapsules.
- Examples of the leveling property imparting include a silicone leveling agent.
- the viscosity of the composition of the present invention at 25 ° C. is not particularly limited, but is preferably 3,000 mPa ⁇ s or less, more preferably 100 to 2,000 mPa ⁇ s. If the viscosity is within this range, stable storage stability that does not separate with time changes is obtained, bubbles are not easily generated, and smooth surface properties can be obtained. ⁇ The viscosity can be measured with a B-type viscometer.
- the composition of the present invention comprises a soft and hard vinyl chloride resin as an adherend; polystyrene; polycarbonate; glass; aluminum; steel sheet; a polyolefin resin modified with a polar group-containing compound or an olefin and a copolymer of a polar group-containing compound.
- Adhesive compositions having good adhesion to these adherends are not disclosed in the prior art. Moreover, it is very excellent in the adhesiveness (adhesion between different materials) when different materials are used for B1 and B2 among the adherends.
- the different materials specifically include hard vinyl chloride resin and glass, soft vinyl chloride resin and glass, polystyrene resin and aluminum, polycarbonate resin and aluminum, acrylonitrile-butadiene-styrene copolymer (ABS) and glass, Glass and aluminum, magnesium and polycarbonate resin, steel plate and acrylic resin (for example, polymethyl methacrylate (PMMA)), polyester (for example, polyethylene terephthalate) and acrylonitrile-butadiene-styrene copolymer (ABS), acrylic resin (for example, polymethacrylic acid) Methyl (PMMA)) and acrylonitrile-butadiene-styrene copolymer (ABS).
- PMMA polymethyl methacrylate
- the polyolefin resin modified with a polar group-containing compound is a polyolefin into which polar groups such as —OH, —NO 2 , —CO, —NH 2 , —NH, —OCH 3 , —SO 3 H and the like are introduced.
- polar groups such as —OH, —NO 2 , —CO, —NH 2 , —NH, —OCH 3 , —SO 3 H and the like are introduced.
- examples thereof include polyolefin resins grafted with at least one selected from maleic anhydride and glycidyl methacrylate, and specific examples include polyethylene and polypropylene grafted with maleic anhydride, and polyethylene and polypropylene grafted with glycidyl methacrylate. .
- Copolymers of olefins and polar group-containing compounds include, for example, copolymers of ethylene and vinyl acetate (EVA), copolymers of ethylene and (meth) acrylic acid (EAA, EMA, etc.), ethylene and A copolymer (EEA etc.) with (meth) acrylic acid ester is mentioned.
- the bonding method of the present invention In the bonding method of the present invention, as the step I, the components (a) to (e) and, if necessary, other fillers are mixed in any order according to the blending ratio, and the adhesive of the present invention.
- the composition is prepared, and then, as Step II, the adhesive composition is laminated on the layer (B1) of the specific adherend to form the adhesive composition layer (A).
- Step II the adhesive composition is laminated on the layer (B1) of the specific adherend to form the adhesive composition layer (A).
- a step of further laminating the layer (A) of the composition and the layer (B2) of the specific adherend According to the bonding method of the present invention, the bonding of the three layers (B1)-(A)-(B2) becomes strong.
- the thickness of the layer (A) of the adhesive composition or the layer (A) of the coating composition (cured coating film) is not particularly limited, but is about 2 to 50 ⁇ m, preferably about 5 to 30 ⁇ m, and more preferably about 8 to 20 ⁇ m. .
- the coating thickness and the film thickness after curing are not significantly different because there is little shrinkage during curing.
- This coating film thickness It is excellent in transparency, can reduce the strength of warping of the resin molded body due to cure shrinkage, and can prevent the surface hardness from being lowered due to uncured binder resin components.
- Coating methods include spin coating, (doctor) knife coating, micro gravure coating, direct gravure coating, offset gravure, reverse gravure, reverse roll coating, (Meyer) bar coating, and die coating
- a method such as spray coating or dip coating can be preferably applied.
- a manual spinner ASS-301 type manufactured by Able Co., Ltd.
- ASS-301 type manufactured by Able Co., Ltd. can be cited as an apparatus for spin coating.
- components (b) and (c) are added as reactive diluents to component (a) in a container equipped with a stirrer.
- the component (b) is added to the component (a) and sufficiently stirred at room temperature. If the viscosity is too high, stirring may be performed while heating at 100 ° C. or lower. If it exceeds 100 ° C., the vapor generation of the component (b) becomes remarkable, which is not preferable in the working environment.
- the component (e) is added and sufficiently stirred so that there is no undissolved residue.
- the composition obtained by stirring is rapidly processed or stored in a cool and dark place.
- the laminate of the present invention is prepared by preparing the adhesive composition or paint composition of the present invention as described above, and laminating the adhesive composition or paint composition on the layer (B1) of the specific adherend. And (B1)-(A), which is obtained by forming the layer (A) of the adhesive composition or coating composition.
- the laminated body of this invention laminates
- the laminate of the present invention has good adhesion between the layers (B1) and (B2) of the specific adherend and the layer (A) of the adhesive composition, and has transparency, surface smoothness, flexibility and resistance. Excellent balance of impact.
- the layer (A) of the adhesive composition or the coating composition also acts advantageously as the primer layer of (B1).
- the primer layer can further contribute to adhesion to a paint applied thereon depending on the application.
- the layer of the specific adherend and the layer of the adhesive composition can be alternately laminated a plurality of times, and this is also within the scope of the laminate referred to in the present invention.
- the coating composition of the present invention is excellent in adhesion to the adherend comprising the substrate (B), has a low viscosity, and is excellent in color development, impact resistance and flexibility of an image. Is suitable.
- the composition of the inkjet ink is not particularly limited.
- known additives usually used in ink jet inks such as colorants, dispersants, surfactants, sensitizers, anti-fading agents, and conductive salts can be added.
- the colorant and the dispersant are as described above.
- the coating composition of the present invention is excellent in adhesion to the adherend comprising the base material (B), and also excellent in adhesion to commercially available inkjet inks.
- the ink jet ink primer is suitable.
- the primer layer for inkjet ink can be provided by an inkjet recording apparatus.
- the thickness of the primer layer for inkjet ink is not particularly limited, but is, for example, 20 to 150 ⁇ m, preferably 10 to 40 ⁇ m, particularly preferably 15 ⁇ m to 35 ⁇ m.
- the well-known inkjet recording device which can achieve the target resolution can be selected arbitrarily and can be used.
- the printed matter of the present invention is obtained by curing the ink-jet ink of the present invention.
- the printed matter of the present invention is excellent in the color developability of the image, and is excellent in the fastness of the image because the impact resistance and the flexibility are greatly improved.
- Modifier (d-1-2) Polybutadiene polyol manufactured by Idemitsu Kosan Co., Ltd., Poly bd R-15HT Viscosity: 1.5 Pa ⁇ s / 30 ° C., hydroxyl value: 102.7 mg KOH / g (D-1-1) Aromatic castor oil-based polyol, manufactured by Ito Oil Co., Ltd., URIC (trademark) AC-006, a polyol derived from castor oil represented by the above formula (26), viscosity: 0.7 to 1.5 Pa ⁇ s / 25 ° C., hydroxyl value: 194 to 214 mg KOH / g (D-1-3) Polyisoprene polyol manufactured by Idemitsu Kosan Co., Ltd.
- Epol (trademark) hydroxyl-terminated liquid polyolefin (viscosity (Pa ⁇ s / 30 ° C) 75, hydroxyl value (mgKOH / g) 50.5, number average Molecular weight 2500) (D-3-1) Maleated polyisoprene Kuraray LIR-420 (acid value (mgKOH / g) 40) (D-3-2) Maleic acid-modified polybutadiene SARTOMER Ricon130MA8 (viscosity (Pa ⁇ s / 30 ° C) 6.5, acid value (mgKOH / g) 46, number average molecular weight 2700) (D-3-2) Maleic acid-modified polybutadiene POLYVEST TM OC 800 S manufactured by EVONIK (1,4-cis double bond in polybutadiene: 75%, 1,4-trans double bond: 24%, vinyl bond: 1%, maleation ratio: 7.5 %, Number average molecular weight: 3300
- the characteristics of each polyol were measured as follows.
- -Viscosity measurement method The viscometer is measured using a single cylindrical rotational viscometer (B type TVC--5) according to JIS K7117-1. 1.
- a 500ml beaker (standard) is used for the measuring instrument.
- the standard rotor is selected from two types: M1 to M4 rotors for low and medium viscosity and H1 to H7 rotors for medium and high viscosity.
- Hydroxyl value measurement method Hydroxyl value is included in 1g of sample. This is the number of mg of potassium hydroxide required to acetylate the OH group. According to JIS K 1557-1, OH groups in the sample are acetylated using acetic anhydride, and acetic acid not used is titrated with potassium hydroxide solution.
- A Amount of 0.5 mol / l potassium hydroxide ethanol solution used for the blank test (ml)
- B 0.5mol / l potassium hydroxide ethanol solution used for titration (ml)
- f Factor
- -Acid value measuring method It represents with the mg number of potassium hydroxide required to neutralize the acidic component contained in 1g of sample oils.
- End-point pH measurement Take 10 mL of buffer stock solution B in a 200-mL beaker, add 100 mL of titration solvent, immerse the electrode, and use the pH that changes within 0.1 pH within 30 seconds as the buffer end point.
- Measurement of acid value 1. Weigh accurately 20 g of sample into a 200 mL beaker. 2. Add 125mL of toluene / 2-propanol / pure water mixed solvent and titrate with 0.1mol / L potassium hydroxide titrant.
- Component (e) Component Photocationic polymerization initiator WPI-113 (50% propylene carbonate): iodonium hexafluorophosphate (Wako Pure Chemical Industries, Ltd.)
- Ionic liquid (i) Basionic LQ 01 (1-ethyl-3-methyl-1H-imidazolium ethyl sulfate, manufactured by BASF, having the ion pair of (1-2) and (8-3) Ionic liquid) (Ii) Basicic AC 09 (1-ethyl-3-methyl-imidazolium tetrachloroaluminate, an ionic liquid having an ion pair of (1-2) and (10-2)) manufactured by BASF (Iii) Basion VS 01 (1-ethyl-3-methyl-imidazolium thiocyanate, an ionic liquid having an ion pair of (1-2) and (10-1)) manufactured by BASF (Iv) manufactured by Lion Akzo Co., Ltd., TMAC-100 (tetramethylammonium chloride (ionic liquid having ion pairs (5-10) and (7-2))
- Component (g-2) Carbodiimide compound Carbodilite V-05 manufactured by Nisshinbo Chemical Co., Ltd., NCO group 8.2%
- Examples 1 to 21 and Comparative Examples 1 to 10 In the blending ratios (parts by mass) shown in Tables 1 to 9 below, the component (a) is placed in a container equipped with a stirrer, then the component (b) is added, and the mixture is sufficiently stirred at room temperature. After adding c) and (d) and stirring, when the liquid temperature reached room temperature, the component (e) was added, and the mixture was sufficiently stirred so as not to remain undissolved, thereby obtaining a composition. The viscosity (mPa ⁇ s) at 25 ° C. of the obtained composition was measured. That is, using a handy type digital viscometer TVC-7 type viscometer (Toki Sangyo Co., Ltd.), the viscosity at 25 ° C. was measured using an appropriate rotor (No. 0 to No. 5) according to the viscosity. The results are also shown in Tables 1 to 9.
- a composition was applied onto each specific adherend (B1) shown in Tables 1 to 9 (dimensions: 150 mm ⁇ 25 mm ⁇ thickness 1 mm) by spin coating (coating thickness 15 to 20 ⁇ m).
- a laminate was prepared by irradiating and curing ultraviolet rays with energy of 500 mJ / cm 2 under air.
- a thermal polymerization initiator if necessary, 0 to 0.05 part by mass of 6% naphthenic cobalt is added to the composition and cured by heat treatment at 100 ° C. for 30 minutes to prepare a laminate. did.
- Each specific adherend (B1) used is as follows. ⁇ Hard vinyl chloride resin PVC (Riken Technos, trade name Riken PVC Compound RE-3844) -Soft vinyl chloride resin PVC (manufactured by Riken Technos, trade name Leonyl BZL6060N) ⁇ Polystyrene PS (Toyo Styrol GP G100C, manufactured by Toyo Styrene Co., Ltd.) ⁇ Polycarbonate PC (trade name Panlite L-1225L, manufactured by Teijin Chemicals Ltd.) ⁇ Acrylonitrile-butadiene-styrene copolymer ABS (manufactured by UMG, trade name UMG ABS EX114) ⁇ Glass (slide glass for microscope preparation) ⁇ Aluminum (H5052, Al-Mg) Magnesium (Osaka Fuji Kogyo Co., Ltd., AZ31B, Mg content 91% or more) ⁇ Steel (SPCC: Cold rolled steel) ⁇ PET: Unitika Unit
- the obtained laminate was subjected to the following cross-cut tape test.
- Adhesion test cross-cut tape test
- the measurement was performed as follows in accordance with the cross cut tape test method described in Japanese Industrial Standard K5400.
- Impact resistance test Test method Apply the composition to a steel plate of 25mm width and 1mm thickness by spin coating to a thickness of 15-20 ⁇ m. After curing, drop a 1kgw spherical weight from 1m height and evaluate it according to the following criteria Went. ⁇ : not peeled ⁇ : partly peeled / cracked ⁇ : whole face peeled / cracked
- Flexibility test method The composition was applied to a steel sheet of 25 mm width and 1 mm thickness by a spin coating method to a thickness of 15 to 20 ⁇ m, and after curing, a 90-degree bending test was performed and the following criteria were evaluated. ⁇ : not peeled ⁇ : partly peeled / cracked ⁇ : whole face peeled / cracked
- the composition was applied to a steel sheet having a width of 25 mm and a thickness of 1 mm by a spin coating method to a thickness of 15 to 20 ⁇ m, and the degree of shrinkage was visually evaluated based on the following criteria.
- ⁇ The surface is smooth and does not shrink
- ⁇ The surface shrinks
- Transparency test In order to evaluate transparency, the haze of the molded articles (base glass) of Examples and Comparative Examples was measured using a haze meter (NDH2000: Nippon Denshoku) based on JIS-K7136: 2000. . In the evaluation, “ ⁇ ” indicates that the measured value is less than 1.0%, “ ⁇ ” indicates that the measured value is 1.0% or more and less than 2.0%, and “x” indicates 2.0% or more.
- the measurement surface was a coating surface.
- the surface resistance was applied to a PC (polycarbonate) substrate (dimensions: 150 mm ⁇ 25 mm ⁇ thickness 1 mm) as a sample by spin coating (coating thickness 10 ⁇ m).
- the surface resistivity ( ⁇ / sq.) was measured with an applied voltage of 500 V in accordance with ASTM D257 using a resistivity meter Hi-Lester UP (MCP-HT450 type).
- Ink-jet ink colorability After the following pigment is mixed with a dispersant, 15 parts by mass are added to and dispersed in 85 parts by mass of the coating composition, and the mixture is stirred with a high-speed water-cooled stirrer and spin coated onto a polycarbonate substrate. After coating to a thickness of about 30 ⁇ m, the color development was evaluated by UV irradiation.
- Pigment-1 (f) Solsperse 36000 with respect to 80 parts by mass of Pigment-1 (f) IRGALITE BLUE GLVO (Cyan Pigment, Ciba Specialty Chemicals (CSC), surface acid amount: 18.0, surface base amount: 34.0) (Dispersant, manufactured by LUBRIZOL, acid value: 45 mgKOH / g, amine value: 0 mgKOH / g) was blended in an amount of 20 parts by mass to obtain Pigment-1.
- Pigment-1 was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 4 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.
- Pigment-2 (f) Tipaque CR60-2 (white pigment (titanium oxide), manufactured by Ishihara Sangyo Co., Ltd., surface acid amount: 8, surface base amount: 25) with respect to 90 parts by mass, (g) Solsperse 36000 (dispersant, LUBRIZOL Pigment-2 was obtained by blending 10 parts by mass of an acid value of 45 mg KOH / g and an amine value of 0 mg KOH / g. Pigment-2 was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 4 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm. In the color development evaluation, the printed sample was visually confirmed, and the color development was evaluated according to the following criteria. ⁇ : No problem in color developability ⁇ : Some problem in color developability, practical problem ⁇ : Clearly in color developability, unsuitable for practical use
- the composition contains the components (a), (b), (c), (d) and (e) in a specific quantitative amount. Since it is contained in a relationship, it exhibits excellent adhesion, impact resistance, flexibility, surface shrinkage, and transparency to polar resins, ceramics, metals, and the like. Moreover, in the example which mix
- Comparative Example 2 since the blending amount of the component (b) is less than the lower limit specified in the present invention and the blending amount of the component (d) exceeds the upper limit defined in the present invention, adhesiveness, transparency, viscosity Worsened.
- Comparative Example 3 since the blending amount of the component (a) is less than the lower limit specified in the present invention and the blending amount of the component (c) exceeds the upper limit defined in the present invention, adhesiveness, impact resistance, Flexibility, surface shrinkage, and transparency deteriorated.
- Comparative Example 4 the compounding amount of the component (a) exceeds the upper limit specified in the present invention, and the compounding amount of the component (b) is less than the lower limit specified in the present invention.
- the compounding quantity of the component (c) was less than the minimum prescribed
- the paint composition used in the ink color development test for ink jet in Examples and a paint composition not containing a pigment was used. Also good printing was made.
- the ink supply system was composed of an original tank, supply piping, an ink supply tank immediately before the inkjet head, a filter, and a piezo-type inkjet head, and heat insulation and heating were performed from the ink supply tank to the inkjet head portion. Temperature sensors were provided near the ink supply tank and the nozzle of the ink jet head, respectively, and temperature control was performed so that the nozzle portion was always 45 ° C. ⁇ 2 ° C.
- the piezo-type inkjet head was driven so that multi-size dots of 8 to 30 pl could be ejected at a resolution of 720 ⁇ 720 dpi.
- UV light was condensed to an exposure surface illuminance of 1,630 mW / cm 2 , and the exposure system, main scanning speed, and ejection frequency were adjusted so that irradiation started 0.1 seconds after ink landed on the recording medium. . Further, the integrated light amount irradiated to the image was set to 4,500 mJ / cm 2 .
- a HAN250NL high-cure mercury lamp manufactured by GS Yuasa Corporation was used as the ultraviolet lamp.
- dpi represents the number of dots per 2.54 cm.
- an ester film E5000 film thickness 125 ⁇ m, manufactured by Toyobo Co., Ltd.
- the coating composition of the present invention can also be used as an ink used in an ink jet recording apparatus. It is also effective as a primer.
- the primer composition of the present invention having a low viscosity is useful because the primer is usually often applied by an ink jet recording apparatus.
- the adhesive composition or paint composition of the present invention comprises a soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel sheet; a polyolefin resin modified with a polar group-containing compound or an olefin and a polar group-containing compound.
- Polymer Magnesium; Acrylonitrile-butadiene-styrene copolymer; Polyester resin; or Acrylic resin.
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Abstract
Description
本発明のインクジェット用インクは長期保存安定性に優れ、画像の発色性にも優れる。
また本発明は、前記接着剤組成物と前記各層との接着方法に関する。
さらに本発明は、前記接着剤組成物または塗料組成物と前記各層との積層体に関する。
その他に本発明は、該塗料を含有する、インクジェット記録媒体上に設けられたプライマー層と、該インクジェット用インクを用いて印刷された印刷物にも関する。
また、プラスチックの接着剤として活性エネルギー線開始ラジカル重合により硬化する、多官能アクリレート又は不飽和ポリエステルも接着性は充分なものではなかった。
その他にガラスや金属材料の接着剤や塗料としての活性エネルギー線開始ラジカル重合により硬化する、多官能アクリレート又は不飽和ポリエステルは、やはり接着性の点で充分なものではなかった。
一方、インクジェット方式は、安価な装置で、且つ、必要とされる画像部のみにインクを吐出し被記録媒体上に直接画像形成を行うため、インクを効率良く使用でき、ランニングコストが安い。さらに、騒音が少なく、画像記録方式として優れている。
また、特許文献3には、(a)オリゴ/樹脂成分と;
(b)(i)ペンダントアルコキシル化官能性を含み、主鎖アルコキシル化官能性を含まない1つ以上の複素環式放射線硬化性モノマーおよび/またはアルコキシル化モノマーを含む、0.1~50質量パーセントの接着促進放射線硬化性成分と、
(ii)主鎖アルコキシル化官能性を含む、約10質量パーセント以下の任意選択のアルコキシル化放射線硬化性モノマーとを含む放射線硬化性反応性希釈剤と、
を含むインクジェット可能な放射線硬化性インクジェットインク組成物が開示されている。
また、特許文献4には、合成樹脂製基材フィルムの少なくとも片面にインクジェットインキ受容層を有するフィルムであって、該受容層が疎水性ポリウレタン系樹脂及び親水性ポリウレタン系樹脂を含有し、かつ該疎水性ポリウレタン系樹脂と該親水性ポリウレタン系樹脂の含有量の質量比が、該疎水性ポリウレタン系樹脂100質量部に対し該親水性ポリウレタン系樹脂が20~400質量部であるインクジェット印刷用フィルムが開示されている。
しかしながら特許文献3および4に記載の技術、あるいはその他の従来の技術では、塗料の長期保存安定性、各種基材、例えば、軟質および硬質塩化ビニル樹脂;スチレン系樹脂;ポリカーボネート系樹脂;ガラス;アルミニウム;鋼板;ポリオレフィン系樹脂;極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体;マグネシウム;アクリロニトリル-ブタジエン-スチレン共重合体;ポリエステル系樹脂;またはアクリル系樹脂の層との接着性が不十分であり、画像の発色性も不十分であり、さらに耐衝撃性、柔軟性にも改善の余地があった。
本発明のその他の目的は、長期保存安定性、各種基材、例えば、軟質および硬質塩化ビニル樹脂;スチレン系樹脂;ポリカーボネート系樹脂;ガラス;アルミニウム;鋼板;ポリオレフィン系樹脂;極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体;マグネシウム;アクリロニトリル-ブタジエン-スチレン共重合体;ポリエステル系樹脂;またはアクリル系樹脂の層との接着性、、画像の発色性、耐衝撃性および柔軟性に優れる塗料、インクジェット用インク、該塗料を含有する、インクジェット記録媒体上に設けられたプライマー層、並びに、該インクジェット用インクを用いて印刷された印刷物を提供することにある。
1.(a)エポキシ樹脂 10~30質量%
(b)オキセタン化合物 25~55質量%
(c)ビニルエーテル化合物 25~55質量%
(d)変性剤 1~15質量%
(ただし、前記成分(a)~(d)の合計は100質量%である)
および
(e)光カチオン重合開始剤 前記成分(a)~(d)の合計100質量部に対し3~15質量部
を含有する接着剤組成物。
2.前記成分(d)が、水酸基価40~330mgKOH/gのポリオール(d-1);および水酸基価40~330mgKOH/gであり、かつ酸価が2~20mgKOH/gであるポリオール(d-2);変性ゴム(d-3);エポキシ当量が150~700g/モルである化合物(d-4)からなる群から選択された少なくとも1種であることを特徴とする前記1に記載の接着剤組成物。
3.前記成分(d-1)が、水酸基価40~330mgKOH/gのヒマシ油系ポリオール(d-1-1);水酸基価40~330mgKOH/gのポリブタジエン系ポリオール(d-1-2);および水酸基価40~330mgKOH/gのポリイソプレン系ポリオールまたはその水素添加物(d-1-3)からなる群から選択された少なくとも1種であることを特徴とする前記2に記載の接着剤組成物。
4.前記成分(d-1)が、水酸基価40~330mgKOH/gの芳香族系ヒマシ油系ポリオール(d-1-1-1)であることを特徴とする前記3に記載の接着剤組成物。
5.前記成分(d-2)が、水酸基価40~330mgKOH/gであり、かつ酸価が2~20mgKOH/gであるヒマシ油系ポリオール(d-2-1)であることを特徴とする前記3に記載の接着剤組成物。
6.前記成分(d-3)が酸変性ポリブタジエンまたは酸変性ポリイソプレンであることを特徴とする前記3に記載の接着剤組成物。
7.前記成分(d-4)がエポキシ当量が150~250g/モルであるポリエポキシ化合物(d-4-1)であることを特徴とする前記3に記載の接着剤組成物。
8.前記成分(d-4)がエポキシ当量が500~700g/モルである飽和骨格を持つ重合体(d-4-2)であることを特徴とする前記3に記載の接着剤組成物。
9.さらに(f)帯電防止材料としてのイオン液体を、前記成分(a)~(d)の合計100質量に対し0.5~10質量部含有してなることを特徴とする前記1~8いずれかに記載の接着剤組成物。
10.前記イオン液体(f)が、イミダゾリウム、ピリジニウム、ピロリジニウム、フォスフォニウム、アンモニウムおよびスルホニウムからなる群から選ばれる少なくとも1種のカチオンを含むことを特徴とする前記9に記載の接着剤組成物。
11.前記イオン液体(f)が、ハロゲン、カルボキシレート、サルフェート、スルホネート、チオシアネート、アルミネート、ボレート、ホスフェート、ホスフィネート、アミド、アンチモネート、イミドおよびメチドからなる群から選ばれるアニオンを含むことを特徴とする前記10に記載の接着剤組成物。
12.さらに帯電防止向上剤(g)を含み、前記帯電防止向上剤(g)が、酸性リン酸エステル(g-1)およびカルボジイミド化合物(g-2)からなる群から選ばれる少なくとも1種であり、かつ、前記帯電防止向上剤(g)の配合量が、前記イオン液体(f)の質量を1としたときに、0.02~30の範囲であることを特徴とする前記9~11のいずれかに記載の接着剤組成物。
13.前記接着剤組成物の被着体が、軟質および硬質塩化ビニル樹脂;ポリスチレン;ポリカーボネート;ガラス;アルミニウム;鋼板;極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体;マグネシウム;アクリロニトリル-ブタジエン-スチレン共重合体;ポリエステル系樹脂;またはアクリル系樹脂であることを特徴とする前記1~12のいずれかに記載の接着剤組成物。
14.工程I:
(a)エポキシ樹脂 10~30質量%
(b)オキセタン化合物 25~55質量%
(c)ビニルエーテル化合物 25~55質量%
(d)変性剤 1~15質量%
(ただし、前記成分(a)~(d)の合計は100質量%である)
および
(e)光カチオン重合開始剤 前記成分(a)~(d)の合計100質量部に対し3~15質量部
を任意の順に混合し、接着剤組成物を調製する工程、
工程II:
軟質および硬質塩化ビニル樹脂;ポリスチレン;ポリカーボネート;ガラス;アルミニウム;鋼板;極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体;マグネシウム;アクリロニトリル-ブタジエン-スチレン共重合体;ポリエステル系樹脂;またはアクリル系樹脂の層(B1)の表面に前記工程Iで得られた接着剤組成物を積層し、接着剤組成物の層(A)を形成する工程、
工程III:
前記工程IIで得られた積層体の接着剤組成物の層(A)と、軟質および硬質塩化ビニル樹脂;ポリスチレン;ポリカーボネート;ガラス;アルミニウム;鋼板;極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体;マグネシウム;アクリロニトリル-ブタジエン-スチレン共重合体;ポリエステル系樹脂;またはアクリル系樹脂の層(B2)をさらに積層する工程、
を工程I、工程IIおよび工程IIIのこの順で行うことを特徴とする接着方法。
15.(a)エポキシ樹脂 10~30質量%
(b)オキセタン化合物 25~55質量%
(c)ビニルエーテル化合物 25~55質量%
(d)変性剤 1~15質量%
(ただし、前記成分(a)~(d)の合計は100質量%である)
および
(e)光カチオン重合開始剤 前記成分(a)~(d)の合計100質量部に対し3~15質量部
を含有する接着剤組成物の層(A)と、
(ただし、前記成分(a)~(d)の合計は100質量%である)
軟質および硬質塩化ビニル樹脂;ポリスチレン;ポリカーボネート;ガラス;アルミニウム;鋼板;極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体;マグネシウム;アクリロニトリル-ブタジエン-スチレン共重合体;ポリエステル系樹脂;またはアクリル系樹脂の層(B1)と
を前記層(A)および層(B1)が接するようにして形成された積層体。
16.軟質および硬質塩化ビニル樹脂;ポリスチレン;ポリカーボネート;ガラス;アルミニウム;鋼板;極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体;マグネシウム;アクリロニトリル-ブタジエン-スチレン共重合体;ポリエステル系樹脂;またはアクリル系樹脂の層(B1)と、
(a)エポキシ樹脂 10~30質量%
(b)オキセタン化合物 25~55質量%
(c)ビニルエーテル化合物 25~55質量%
(d)変性剤 1~15質量%
(ただし、前記成分(a)~(d)の合計は100質量%である)
および
(e)光カチオン重合開始剤 前記成分(a)~(d)の合計100質量部に対し3~15質量部
を含有する接着剤組成物の層(A)と、
軟質および硬質塩化ビニル樹脂;ポリスチレン;ポリカーボネート;ガラス;アルミニウム;鋼板;極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体;マグネシウム;アクリロニトリル-ブタジエン-スチレン共重合体;ポリエステル系樹脂;またはアクリル系樹脂の層(B2)と、
を前記層(B1)、層(A)および層(B2)の3層がこの順で接するようにして形成された積層体。
17.(a)エポキシ樹脂 10~30質量%
(b)オキセタン化合物 25~55質量%
(c)ビニルエーテル化合物 25~55質量%
(d)変性剤 1~15質量%
(ただし、前記成分(a)~(d)の合計は100質量%である)
および
(e)光カチオン重合開始剤 前記成分(a)~(d)の合計100質量部に対し3~15質量部
を含有する塗料組成物。
18.前記成分(d)が、水酸基価40~330mgKOH/gのポリオール(d-1);および水酸基価40~330mgKOH/gであり、かつ酸価が2~20mgKOH/gであるポリオール(d-2);変性ゴム(d-3);エポキシ当量が150~700g/モルである化合物(d-4)からなる群から選択された少なくとも1種であることを特徴とする前記17に記載の塗料組成物。
19.前記成分(d-1)が、水酸基価40~330mgKOH/gのヒマシ油系ポリオール(d-1-1);水酸基価40~330mgKOH/gのポリブタジエン系ポリオール(d-1-2);および水酸基価40~330mgKOH/gのポリイソプレン系ポリオールまたはその水素添加物(d-1-3)からなる群から選択された少なくとも1種であることを特徴とする前記18に記載の塗料組成物。
20.前記成分(d-1)が、水酸基価40~330mgKOH/gの芳香族系ヒマシ油系ポリオール(d-1-1-1)であることを特徴とする前記19に記載の塗料組成物。
21.前記成分(d-2)が、水酸基価40~330mgKOH/gであり、かつ酸価が2~20mgKOH/gであるヒマシ油系ポリオール(d-2-1)であることを特徴とする前記19に記載の塗料組成物。
22.前記成分(d-3)が酸変性ポリブタジエンまたは酸変性ポリイソプレンであることを特徴とする前記19に記載の塗料組成物。
23.前記成分(d-4)がエポキシ当量が150~250g/モルであるポリエポキシ化合物(d-4-1)であることを特徴とする前記19に記載の塗料組成物。
24.前記成分(d-4)がエポキシ当量が500~700g/モルである飽和骨格を持つ重合体(d-4-2)であることを特徴とする前記19に記載の塗料組成物。
25.さらに(f)帯電防止材料としてのイオン液体を、前記成分(a)~(d)の合計100質量に対し0.5~10質量部含有してなることを特徴とする前記17~24いずれかに記載の塗料組成物。
26.前記イオン液体(f)が、イミダゾリウム、ピリジニウム、ピロリジニウム、フォスフォニウム、アンモニウムおよびスルホニウムからなる群から選ばれる少なくとも1種のカチオンを含むことを特徴とする前記25に記載の塗料組成物。
27.前記イオン液体(f)が、ハロゲン、カルボキシレート、サルフェート、スルホネート、チオシアネート、アルミネート、ボレート、ホスフェート、ホスフィネート、アミド、アンチモネート、イミドおよびメチドからなる群から選ばれるアニオンを含むことを特徴とする前記26に記載の塗料組成物。
28.さらに帯電防止向上剤(g)を含み、前記帯電防止向上剤(g)が、酸性リン酸エステル(g-1)、カルボジイミド化合物(g-2)、およびビニルエーテル系化合物(g-3)からなる群から選ばれる少なくとも1種であり、かつ、前記帯電防止向上剤(g)の配合量が、前記イオン液体(f)の質量を1としたときに、0.02~30の範囲であることを特徴とする前記25~27のいずれかに記載の塗料組成物。
29.前記塗料組成物の被着体が、軟質および硬質塩化ビニル樹脂;ポリスチレン;ポリカーボネート;ガラス;アルミニウム;鋼板;極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体;マグネシウム;アクリロニトリル-ブタジエン-スチレン共重合体;ポリエステル系樹脂;またはアクリル系樹脂であることを特徴とする前記17~28のいずれかに記載の塗料組成物。
30.(a)エポキシ樹脂 10~30質量%
(b)オキセタン化合物 25~55質量%
(c)ビニルエーテル化合物 25~55質量%
(d)変性剤 1~15質量%
(ただし、前記成分(a)~(d)の合計は100質量%である)
および
(e)光カチオン重合開始剤 前記成分(a)~(d)の合計100質量部に対し3~15質量部
を含有する塗料組成物の層(A)と、
(ただし、前記成分(a)~(d)の合計は100質量%である)
軟質および硬質塩化ビニル樹脂;ポリスチレン;ポリカーボネート;ガラス;アルミニウム;鋼板;極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体;マグネシウム;アクリロニトリル-ブタジエン-スチレン共重合体;ポリエステル系樹脂;またはアクリル系樹脂の層(B1)と
を前記層(A)および層(B1)が接するようにして形成された積層体。
31.前記17~29のいずれかに記載の塗料組成物を含有することを特徴とするインクジェット用インク。
32.さらに着色剤を含有することを特徴とする前記31に記載のインクジェット用インク。
33.前記17~29のいずれかに記載の塗料組成物を含有することを特徴とする、インクジェット記録媒体上に設けられたプライマー層。
34.インクジェット記録媒体上に、前記31または32に記載のインクジェット用インクを用いてインクジェット印刷してなる印刷物。
本発明の接着方法は、前記成分(a)、(b)、(c)、(d)および(e)を特定の量的関係でもって含有する接着剤組成物の層(A)と、軟質および硬質塩化ビニル樹脂;ポリスチレン;ポリカーボネート;ガラス;アルミニウム;鋼板;極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体;マグネシウム;アクリロニトリル-ブタジエン-スチレン共重合体;ポリエステル系樹脂;またはアクリル系樹脂の層(B1)および(B2)とを特定の工程順で積層する方法であるので、3層の接着が強固となる。
本発明の一つの見地の積層体は、前記成分(a)、(b)、(c)、(d)および(e)を特定の量的関係でもって含有する接着剤組成物の層または塗料組成物の層(A)と、軟質および硬質塩化ビニル樹脂;ポリスチレン;ポリカーボネート;ガラス;アルミニウム;鋼板;極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体;マグネシウム;アクリロニトリル-ブタジエン-スチレン共重合体;ポリエステル系樹脂;またはアクリル系樹脂の層(B1)との積層体である。接着剤組成物の層または塗料組成物の層(A)は、透明性、表面平滑性、柔軟性、耐衝撃性のバランスに優れるので、前記層(B1)のプライマー層として有利に作用する。
本発明の別の見地の積層体は、前記成分(a)、(b)、(c)、(d)および(e)を特定の量的関係でもって含有する接着剤組成物の層または塗料組成物の層(A)と、軟質および硬質塩化ビニル樹脂;ポリスチレン;ポリカーボネート;ガラス;アルミニウム;鋼板;極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体;マグネシウム;アクリロニトリル-ブタジエン-スチレン共重合体;ポリエステル系樹脂;またはアクリル系樹脂の層(B1)および(B2)との積層体であるので、層(A)、(B1)および(B2)間の接着性に優れる。また、透明性、表面平滑性、柔軟性、耐衝撃性のバランスに優れる。
また、本発明の塗料組成物は、上記の各特性を有するとともに、低粘度であるのでインクジェット用インクに有用である。また、本発明の塗料組成物は、各種基材への接着性に優れることから、インクジェット記録媒体上に設けられたプライマー層に有用である。また該インクジェット用インクを用いて印刷された印刷物は、画像の発色性に優れ、耐衝撃性および柔軟性も大幅に改善されていることから、画像の堅牢性にも優れる。
(a)エポキシ樹脂
本発明の接着剤組成物の層および塗料組成物(以下、両者をまとめて単に組成物ということがある)の成分(a)は、エポキシ樹脂である。
本発明の組成物の成分(b)は、オキセタン化合物である。
好ましい形態において、本発明で使用するオキセタン環を有する化合物は、オキセタン環を1~4個有するものである。オキセタン環を5個以上有する化合物を使用すると、組成物の硬化膜に柔軟性が失われ、折り曲げでヒビ割れを起こすことがある。本発明で使用するオキセタン環を有する化合物は、オキセタン環を1~4個有する化合物であれば、種々のものが使用できる。1個のオキセタン環を有する化合物としては、下記一般式(1)で示される化合物等が挙げられる。
本発明の組成物の成分(c)は、ビニルエーテル化合物である。
ビニルエーテル化合物(c)としては、例えば、エチルビニルエーテル、イソブチルビニルエーテル、n-ブチルビニルエーテル、tert-ブチルビニルエーテル、n-アミルビニルエーテル、i-アミルビニルエーテル、n-ヘキシルビニルエーテル、n-オクチルビニルエーテル、2-エチルヘキシルビニルエーテル、オクタデシルビニルエーテル、n-ドデシルビニルエーテル、ステアリルビニルエーテル、オレイルビニルエーテルなどのアルキルまたはアルケニルアルコールのビニルエーテル類;例えば、シクロヘキシルビニルエーテル、2-メチルシクロヘキシルビニルエーテル、シクロヘキシルメチルビニルエーテル、ベンジルビニルエーテルなどの脂肪族環または芳香族環を有するモノアルコールのビニルエーテル類;
本発明で用いられる成分(d)は、変性剤である。
変性剤(d)としては、例えば水酸基価40~330mgKOH/gのポリオール(d-1);および水酸基価40~330mgKOH/gであり、かつ酸価が2~20mgKOH/gであるポリオール(d-2);変性ゴム(d-3);エポキシ当量が150~700g/モルである化合物(d-4)からなる群から選択された少なくとも1種が挙げられる。
(i)水酸基価は40~330mgKOH/gであるのが上記選択的接着力の点で好ましく、150~300mgKOH/gであるのがさらに好ましい。
(i)水酸基価40~330mgKOH/gのヒマシ油系ポリオール(d-1-1)
(i)水酸基価40~330mgKOH/gのポリブタジエン系ポリオール(d-1-2)
(i)水酸基価40~330mgKOH/gのポリイソプレン系ポリオールまたはその水素添加物(d-1-3)
(i)水酸基価40~330mgKOH/gのエポキシポリオール樹脂(d-1-4)
が挙げられる。
さらに、接着層の強靭性(耐衝撃性)、柔軟性、及び異材質との接着性を向上させる点で(i)水酸基価40~330mgKOH/gの芳香族系ヒマシ油系ポリオール(d-1-1-1)が好ましい。より好ましくは、150~240mgKOH/gである。
ポリブタジエン系ポリオールは市販されており、例えば、出光興産(株)製の「Poly bd R-15HT(水酸基価102.7mgKOH/mg、Mw1200)」、「Poly bd R-45HT(水酸基価46.6mgKOH/mg、Mw2800)」等が挙げられる。
また、本発明の効果の点から(d-1-2)ポリブタジエン系ポリオールの水酸基価は40~330mgKOH/gであるのが好ましく、40~110mgKOH/gであるのがさらに好ましい。
(d-1-2)ポリブタジエン系ポリオールの重量平均分子量(GPC法)は、50~3000であるのが好ましく、800~1500であるのがさらに好ましい。
水素添加物としては、出光社のエポール(登録商標)(水酸基末端液状ポリオレフィン)が挙げられる。「エポール(登録商標)」(水酸基価50.5mgKOH/mg、Mn2500)は、「Poly ip(登録商標)」に水添して得られる液状のポリオレフィンである。分子内に二重結合はほとんど残っていない。
(i)の水酸基価は、230~300mgKOH/gであるのがさらに好ましい。
(ii)の酸価は、4~15mgKOH/gであるのがさらに好ましい。
(i)水酸基価40~330mgKOH/gであり、かつ(ii)酸価が2~20mgKOH/gであるポリオール(d-2)としては、
(i)水酸基価40~330mgKOH/gであり、かつ(ii)酸価が2~20mgKOH/gであるヒマシ油系ポリオール(d-2-1)
が例示される。
また、上記伊藤製油 URIC H-2151Uは、ヒマシ油系ポリオールと全炭素数が12以上の酸性リン酸エステル化合物とテルペンフェノール類を含有するポリオール (粘度:3,500~8,500mPa・s/25℃、水酸基価:240~290(単位mgKOH/g)、酸価:4~15(単位mgKOH/g))であり、特定被着体(B)の層との接着性に優れ、特に金属接着性・耐加水分解性に優れる。
本発明で使用される変性ゴム(d-3)としては、(d-3-1)液状のカルボキシル化ポリイソプレン及び(d-3-2)カルボキシル化ポリブタジエンが挙げられる。
本発明で使用されるカルボキシル化ポリイソプレン(d-3-1)は、本発明の組成物を金属基材やガラス基材と接着させる際に、主として基材表面のぬれ性を向上させ、接着力を向上させる機能を果たす。
成分(d-3-1)としては、例えばマレイン化ポリイソプレンとしてクラレ社製のLIR-420が挙げられる。
本発明で使用されるカルボキシル化ポリブタジエン(d-3-2)は、本発明の組成物を金属基材やガラス基材と接着させる際に、主として基材表面のぬれ性を向上させ、接着力を向上させる機能を果たす。
成分(d-3-2)は、ポリブタジエンにおける主鎖のミクロ構造がビニル1,2-結合型、トランス1,4-結合型、シス1,4-結合型からなる、室温において透明な液状の重合体である。ここで、ビニル1,2-結合は30重量%以下であることが好ましく、ビニル1,2-結合が30重量%を超えては、得られる組成物の貯蔵安定性が悪化するため好ましくない。また、シス1,4-結合は、40重量%以上であることが好ましく、シス1,4-結合が40重量%未満では、得られる組成物の接着性が低下するため好ましくない。
シス-二重結合が上記下限未満である液状ポリブタジエンはマレイン化率上昇と共に急激に粘度が上昇するが、シス-二重結合が上記範囲にあるものは粘度上昇が少ない。粘度が上記範囲のように低いことから、反応性が高くなり作業性が向上する。また、得られる組成物は加飾性の点で優れる。
本発明の組成物は、(e)光カチオン重合開始剤を必須成分とする。
Ar1-I+-Ar2
で表されるように、I+に結合している基Ar1およびAr2が独立して2つとも芳香族基が好ましく、特に置換基を有していてもよいフェニル基が好ましい。
VPS-1001:4,4'-アゾビス(4-シアノ吉草酸)とα,ω-ビス(3-アミノプロピル)ポリジメチルシロキサンの重縮合物(和光純薬社製)
WPI-113(50%プロピレンカーボネート):ヨードニウムヘキサフルオリン酸塩(和光純薬社製)(オニウム塩系)
WPI-116(50%プロピレンカーボネート):ヨードニウムヘキサフルロアンチモン酸塩(和光純薬社製)
WPI-170:ヨードニウムヘキサフルロホスフェート(和光純薬社製)
SP-170:スルホニウム・ヘキサフロロアンチモン系重合開始剤(アデカ社製)
本発明に用いられるイオン液体(f)としては、イミダゾリウム、ピリジニウム、ピロリジニウム、フォスフォニウム、アンモニウムおよびスルホニウムからなる群から選ばれる少なくとも1種のカチオンを含むものが好ましい。カチオンとしては以下に例示される。
本発明において、好ましいイオン液体はカチオンとアニオンの組み合わせとして、例えば(1-1)と(10-1)、(1-1)と(10-4)、(1-1)と(11-1)、(1-2)と(8-3)、(1-2)と(10-1)、(1-2)と(10-2)、(1-2)と(10-4)、(1-2)と(11-1)、(1-6)と(7-11)、(1-6)と(8-3)、(1-6)と(8-5)、(1-6)と(8-6)、(1-6)と(9-1)、(1-6)と(9-2)、(1-6)と(9-3)、(1-6)と(10-1)、(1-6)と(10-4)、(1-6)と(10-7)、(1-6)と(11-1)、(1-6)と(12-5)、(1-6)と(12-6)、(1-8)と(8-2)、(1-8)と(8-5)、(1-8)と(8-6)、(1-8)と(9-1)、(1-8)と(10-4)、(1-12)と(10-4)、(1-13)と(10-4)、(1-17)と(10-4)、(2-1)と(9-1)、(2-1)と(9-2)、(3-1)と(8-2)、(3-1)と(8-3)、(3-1)と(11-1)、(3-5)と(8-3)、(3-6)と(10-4)、(3-8)と(9-2)、(5-8)と(12-5)、(5-9)と(10-4)のイオン対を有するイオン液体が挙げられ、中でも本発明の効果(特定被着体(B)に対する接着性と帯電防止性を兼ね備える)を良好に発現するという観点から、(1-2)と(8-3)、(1-2)と(10-1)、(1-2)と(10-2)のイオン対を有するイオン液体がさらに好ましく、(1-2)と(8-3)のイオン対を有するイオン液体を使用した場合がとくに特定被着体(B)との接着力が高く、かつ、帯電防止性に優れる点で好ましい。
このような化合物としては、以下のジイソシアネートを脱炭酸縮合反応させたものが挙げられる。
ジイソシアネートとしては、4,4’-ジフェニルメタンジイソシアネート、3,3’-ジメトキシ-4,4’-ジフェニルメタンジイソシアネート、3,3’-ジメチル-4,4’-ジフェニルメタンジイソシアネート、4,4’-ジフェニルエーテルジイソシアネート、3,3’-ジメチル-4,4’-ジフェニルエーテルジイソシアネート、2,4-トリレンジイソシアネート、2,6-トリレンジイソシアネート、1-メトキシフェニル-2,4-ジイソシアネート、イソホロンジイソシアネート、4,4’-ジシクロヘキシルメタンジイソシアネート、テトラメチルキシリレンジイソシアネートの内の一種、または、これらの混合物を使用することができる。
本発明の塗料組成物をインクジェット用インクあるいはプライマーとして使用する場合には、(h)着色剤を含有することが好ましい。
本発明に用いることができる着色剤としては、特に制限はないが、耐候性に優れ、色再現性に富んだ顔料及び油溶性染料が好ましく、溶解性染料等の公知の着色剤から任意に選択して使用することができる。本発明の塗料組成物をインクジェット用インクあるいはプライマーとして使用する場合に好適に使用し得る着色剤は、活性放射線による硬化反応の感度を低下させないという観点からは、硬化反応である重合反応において重合禁止剤として機能しない化合物を選択することが好ましい。
本発明に使用できる顔料としては、特に限定されるわけではないが、例えばカラーインデックスに記載される下記の番号の有機又は無機顔料が使用できる。
赤或いはマゼンタ顔料としては、Pigment Red 3,5,19,22,31,38,43,48:1,48:2,48:3,48:4,48:5,49:1,53:1,57:1,57:2,58:4,63:1,81,81:1,81:2,81:3,81:4,88,104,108,112,122,123,144,146,149,166,168,169,170,177,178,179,184,185,208,216,226,257、Pigment Violet 3,19,23,29,30,37,50,88、Pigment Orange 13,16,20,36、
青又はシアン顔料としては、Pigment Blue 1,15,15:1,15:2,15:3,15:4,15:6,16,17-1,22,27,28,29,36,60、
緑顔料としては、Pigment Green 7,26,36,50、
黄顔料としては、Pigment Yellow 1,3,12,13,14,17,34,35,37,55,74,81,83,93,94,95,97,108,109,110,137,138,139,153,154,155,157,166,167,168,180,185,193、
黒顔料としては、Pigment Black 7,28,26、
白色顔料としては、PigmentWhite 6,18,21
などが目的に応じて使用できる。
以下に、本発明で使用することのできる油溶性染料について説明する。
本発明で使用することのできる油溶性染料とは、水に実質的に不溶な染料を意味する。具体的には、25℃での水への溶解度(水100gに溶解できる染料の質量)が1g以下であり、好ましくは0.5g以下、より好ましくは0.1g以下であるものを指す。したがって、油溶性染料とは、所謂水に不溶性の顔料や油溶性色素を意味し、これらの中でも油溶性色素が好ましい。
これらの中で特に好ましいものは、Nubian Black PC-0850、Oil Black HBB、Oil Yellow 129、Oil Yellow 105、Oil Pink 312、Oil Red 5B、Oil Scarlet 308、Vali Fast Blue 2606、Oil Blue BOS(オリエント化学(株)製)、Aizen Spilon Blue GNH(保土ヶ谷化学(株)製)、NeopenYellow 075、Neopen Mazenta SE1378、Neopen Blue 808、Neopen Blue FF4012、Neopen Cyan FF4238(BASF社製)等である。
本発明においては、油溶性染料は1種単独で用いてもよく、また、数種類を混合して用いてもよい。
本発明においては、水非混和性有機溶媒に溶解する範囲で分散染料を用いることもできる。分散染料は一般に水溶性の染料も包含するが、本発明においては水非混和性有機溶媒に溶解する範囲で用いることが好ましい。分散染料の好ましい具体例としては、C.I.ディスパースイエロー 5,42,54,64,79,82,83,93,99,100,119,122,124,126,160,184:1,186,198,199,201,204,224及び237;C.I.ディスパーズオレンジ 13,29,31:1,33,49,54,55,66,73,118,119及び163;C.I.ディスパーズレッド 54,60,72,73,86,88,91,92,93,111,126,127,134,135,143,145,152,153,154,159,164,167:1,177,181,204,206,207,221,239,240,258,277,278,283,311,323,343,348,356及び362;C.I.ディスパーズバイオレット 33;C.I.ディスパーズブルー 56,60,73,87,113,128,143,148,154,158,165,165:1,165:2,176,183,185,197,198,201,214,224,225,257,266,267,287,354,358,365及び368;並びにC.I.ディスパーズグリーン 6:1及び9;等が挙げられる。
本発明の塗料組成物中における着色剤の含有量は色、及び使用目的により適宜選択されるが、一般的には、塗料全体の質量に対し、0.01~30質量%であることが好ましい。
本発明において、(g)着色剤の分散を行う際に(i)分散剤を添加することが好ましい。すなわち、本発明の塗料は、(g)着色剤及び(i)分散剤を含有することが好ましい。
本発明において、前記(i)分散剤は、酸性分散剤であることが好ましい。
酸性分散剤とは酸性の官能基を有する分散剤である。
酸性分散剤は、酸価が10mgKOH/g以上であることが好ましく、20mgKOH/g以上であることがより好ましく、40mgKOH/g以上であることがさらに好ましい。また、酸性分散剤は、酸価がアミン価より大きいことが好ましい。
ここで、アミン価とは、1、2、3級アミンの総量を示すもので、試料1gを中和するのに要する塩酸に当量のKOHのmg数で表わしたものである。また、酸価とは、試料1g中に含有する遊離脂肪酸、樹脂酸などを中和するのに必要なKOHのmg数である。
分散剤としては、酸性分散剤であれば、特に限定はされないが、高分子分散剤を使用することが好ましく、酸価がアミン価より大きい高分子分散剤を使用することがより好ましい。
また、本発明において、分散剤の酸価とアミン価の差は5mgKOH/g以上であることが好ましく、10mgKOH/g以上であることがより好ましく、20mgKOH/g以上であることがさらに好ましい。
また、その他の公知の分散剤を併用することもできる。具体的には、DisperBYK-161(アミン価:11mgKOH/g、酸価:0mgKOH/g)、DisperBYK-162(アミン価:13mgKOH/g、酸価:0mgKOH/g)、DisperBYK-163(アミン価:10mgKOH/g、酸価:0mgKOH/g)、DisperBYK-164(アミン価:18mgKOH/g、酸価:0mgKOH/g)、DisperBYK-166(アミン価:20mgKOH/g、酸価:0mgKOH/g)、DisperBYK-167(アミン価:13mgKOH/g、酸価:0mgKOH/g)、DisperBYK-168(アミン価:10mgKOH/g、酸価:0mgKOH/g)、DisperBYK-182(アミン価:13mgKOH/g、酸価:0mgKOH/g)(以上、BYKケミー社製)、EFKA4046(アミン価:17~21mgKOH/g、酸価:0mgKOH/g)、EFKA4060(アミン価:6~10mgKOH/g、酸価:0mgKOH/g)、EFKA4080(アミン価:3.6~4.1mgKOH/g、酸価:0mgKOH/g)、EFKA4800(アミン価:37~43mgKOH/g、酸価:0mgKOH/g)、EFKA7462(アミン価:8mgKOH/g、酸価:0mgKOH/g)(以上、エフカアディティブ社製)、ソルスパース13240(塩基性分散剤)、ソルスパース13940(塩基性分散剤)、ソルスパース24000(アミン価:47mgKOH/g、酸価:24mgKOH/g)、ソルスパース28000(塩基性分散剤)、ソルスパース32000(アミン価:180mgKOH/g、酸価:15mgKOH/g)などの各種ソルスパース分散剤(以上、ゼネカ社製)、ディスパロン DA-234(アミン価:20mgKOH/g、酸価:16mgKOH/g)、ディスパロン DA-325(アミン価:20mgKOH/g、酸価:14mgKOH/g)(以上、楠本化成社製)が挙げられる。
分散剤の添加量が0.01質量%以上であると、顔料の分散性に優れ、分散安定性が良好であるので好ましい。また分散剤の添加量が50質量%以下であると、インクの経時安定性が良好であるので好ましい。
本発明の組成物において、(a)エポキシ樹脂は、接着性、高硬度性の観点から、10~30質量%配合される。さらに好ましくは15~25質量%である。成分(a)の配合量が10質量%未満では、接着力と硬さが悪化する。成分(a)の配合量が30質量%を超えると収縮率が大きく、接着力と耐衝撃性が悪化する。
(ただし、前記成分(a)~(d)の合計は100質量%である)
レべリング性付与としては、例えば、シリコーン系レべリング剤等が挙げられる。
また、上記被着体のうちでB1とB2に異なる材質を使用した場合の接着性(異材質間の接着性)に極めて優れる。
異材質間とは、具体的には、硬質塩化ビニル樹脂とガラス、軟質塩化ビニル樹脂とガラス、ポリスチレン系樹脂とアルミニウム、ポリカーボネート樹脂とアルミニウム、アクリロニトリル-ブタジエン-スチレン共重合体(ABS)とガラス、ガラスとアルミニウム、マグネシウムとポリカーボネート樹脂、鋼板とアクリル樹脂(例えばポリメタクリル酸メチル(PMMA))、ポリエステル(例えばポリエチレンテレフタレート)とアクリロニトリル-ブタジエン-スチレン共重合体(ABS)、アクリル樹脂(例えばポリメタクリル酸メチル(PMMA))とアクリロニトリル-ブタジエン-スチレン共重合体(ABS)が挙げられる。
なお、極性基含有化合物で変性されたポリオレフィン樹脂は、-OH、-NO2、-CO、-NH2、-NH、-OCH3、-SO3H等の極性基が導入されたポリオレフィンであり、例えば無水マレイン酸、グリシジルメタクリレートから選ばれた少なくとも1種をグラフトしたポリオレフィン樹脂が挙げられ、具体的には、無水マレイン酸をグラフトしたポリエチレンやポリプロピレン、グリシジルメタクリレートをグラフトしたポリエチレンやポリプロピレンが挙げられる。また、オレフィンと極性基含有化合物との共重合体は、例えばエチレンと酢酸ビニルとの共重合体(EVA)、エチレンと(メタ)アクリル酸との共重合体(EAA、EMA等)、エチレンと(メタ)アクリル酸エステルとの共重合体(EEA等)が挙げられる。
本発明の接着方法は、工程Iとして、前記成分(a)~(e)、必要に応じて他の充填材を、任意の順番で、前記の配合割合にしたがって混合し、本発明の接着剤組成物を調製し、続いて工程IIとして、特定被着体の層(B1)上に接着剤組成物を積層し、接着剤組成物の層(A)を形成し、工程IIIとして、接着剤組成物の層(A)と特定被着体の層(B2)とをさらに積層する工程を有する。このような本発明の接着方法によれば、前記(B1)-(A)-(B2)の3層の接着が強固となる。
その他の成分を添加する場合は、最後に添加し、十分に攪拌する。
攪拌して得られた組成物は、速やかに加工するか、冷暗所に保存する。
本発明の積層体は、前記のようにして本発明の接着剤組成物または塗料組成物を調製し、これを特定被着体の層(B1)上に接着剤組成物または塗料組成物を積層し、接着剤組成物または塗料組成物の層(A)を形成して得られ、(B1)-(A)からなる積層体である。
また、別の形態によれば、本発明の積層体は、特定被着体の層(B1)上に接着剤組成物を積層し、接着剤組成物の層(A)を形成し、さらに層(A)上に特定被着体の層(B2)を積層して得られ、(B1)-(A)-(B2)からなる積層体である。
本発明の積層体は、特定被着体の層(B1)および(B2)と接着剤組成物の層(A)との接着性が良好であり、透明性、表面平滑性、柔軟性、耐衝撃性のバランスに優れる。
また、(B1)-(A)からなる積層体では、接着剤組成物または塗料組成物の層(A)が、(B1)のプライマー層としても有利に作用する。該プライマー層は、例えば、用途に応じてさらにその上に塗布される塗料に対する接着性に寄与することができる。
なお、上記以外にも、特定被着体の層と接着剤組成物の層とは複数回交互に積層することもでき、これも本発明でいう積層体の範囲内である。
インクジェット用インクの組成は、とくに制限されない。例えば、着色剤、分散剤、界面活性剤、増感剤、褪色防止剤、導電性塩類等のインクジェット用インクに通常用いられる公知の添加剤を添加することができる。例えば着色剤、分散剤については、前記で例示したとおりである。
(a)エポキシ樹脂
前記式(a-2)で表される3,4-エポキシシクロヘキシルメチル-3,4-エポキシシクロヘキサンカルボキシレート(ダイセル化学社製、セロキサイド2021P)
前記構造式(25)で表されるジ〔1-エチル(3-オキセタニル)〕メチルエーテル(東亞合成社製のOXT-221)
(i)トリエチレングリコールジビニルエーテル、DVE-3(BASF社製)、25℃粘度=2.6mPa・s
(ii)1,4-シクロヘキサンジメタノールジビニルエーテル(CHDM)、BASF社製、
(d-1-2)ポリブタジエン系ポリオール
出光興産社製、Poly bd R-15HT
粘度:1.5Pa・s/30℃、水酸基価:102.7mgKOH/g
(d-1-1-1)芳香族系ヒマシ油系ポリオール
伊藤製油社製、URIC(商標)AC-006、前記式(26)で表されるヒマシ油由来のポリオール、粘度:0.7~1.5Pa・s/25℃、水酸基価:194~214mgKOH/g
(d-1-3)ポリイソプレン系ポリオール
出光興産社製、Poly ip(登録商標)分子末端に反応性の高い水酸基を備えたポリイソプレンタイプの液状ポリマー(水酸基価46.6mgKOH/mg、数平均分子量Mn=2500)
(d-2-1)ヒマシ油系ポリオール
伊藤製油 URIC H-1262
ヒマシ油系ポリオールと全炭素数が12以上の酸性リン酸エステル化合物を含むポリオール 粘度:3,500~8,500Pa・s/25℃、酸価:4~15(単位mgKOH/g)、水酸基価:240~290(単位mgKOH/g)
(d-2-1)ヒマシ油系ポリオール
伊藤製油 URIC H-2151U
ヒマシ油系ポリオールと全炭素数が12以上の酸性リン酸エステル化合物とテルペンフェノール類を含有するポリオール 粘度:3,500~8,500Pa・s/25℃、酸価:4~15(単位mgKOH/g)、水酸基価:240~290(単位mgKOH/g)
(d-1-3)ポリイソプレン系ポリオールの水素添加物
出光興産社製 エポール(商標)水酸基末端液状ポリオレフィン
(粘度(Pa・s/30℃)75、水酸基価(mgKOH/g) 50.5、数平均分子量2500)
(d-3-1)マレイン化ポリイソプレン
株式会社 クラレ LIR-420 (酸価(mgKOH/g) 40)
(d-3-2)マレイン酸変性ポリブタジエン
SARTOMER社製 Ricon130MA8 (粘度(Pa・s/30℃)6.5、酸価(mgKOH/g) 46、数平均分子量2700)
(d-3-2)マレイン酸変性ポリブタジエン
EVONIK社製 POLYVEST(商標) OC 800 S (ポリブタジエンにおける1,4-シス二重結合:75%、1,4-トランス二重結合:24%、ビニル結合:1%、マレイン化率:7.5%、数平均分子量:3300(GPC)、重量平均分子量:13,600(GPC)、粘度(20℃):6~9Pa・s(DIN53214にて測定)、酸価:70~90mgKOH/g、ヨウ素価:380~420g/100g、(チグラー-ナッタ触媒で重合))
(d-1-4)エポキシポリオール樹脂
DIC株式会社 EPICLON(商標)U-125-60BT
(粘度(Pa・s/30℃)70、水酸基価(mgKOH/g) 120)
(d-4-1)エポキシ当量が150~250g/モルであるポリエポキシ化合物
アデカレジンEP-4100E(旭電化工業 製;ビスフェノールAジグリシジルエーテル、エポキシ当量190)
(d-4-2)エポキシ当量が500~700g/モルである飽和骨格を持つ重合体
クラレ社製L-207(KRATON LIQUID(商標)L-207POLYMERに同じ) (エポキシ当量が590g/モルで、水酸基当量は7000g/モル、ガラス転移温度-53℃、完全飽和骨格(エポキシ化エチレン・プロピレン-エチレン・ブチレン-OH構造)を持つ重合体)
・粘度測定方法
粘度計は、JIS K7117-1に従って、単一円筒型回転粘度計(B形TVC--5 )を用いて測定。
1.測定器に500mlビーカ(標準)を使用。
2.標準ロータは、低・中粘度用としてのM1~M4ロータ、中・高粘度用としてのH1~H7ロータの2種から選択
・水酸基価測定方法
水酸基価とは、試料1g中に含まれるOH基をアセチル化するために要する水酸化カリウムのmg数である。JIS K 1557-1に準じて、無水酢酸を用いて試料中のOH基をアセチル化し、使われなかった酢酸を水酸化カリウム溶液で滴定する。
B:滴定に用いた0.5mol/l水酸化カリウムエタノール溶液の量(ml)
f:ファクター
試料油1gに含まれる酸性成分を中和するのに要する水酸化カリウムのmg数で表す。 JIS K 1557-5に準じて、
(1)終点pHの測定
200mLビーカに緩衝貯蔵液Bを10mL採取し、滴定溶剤を100mL加えて電極を浸け、30秒間で0.1pH以内の変化となったpHを緩衝の終点とする。
(2)酸価の測定
1.試料20gを200mLビーカに正確に秤量する。
2.トルエン・2-プロパノール・純水混合溶剤125mLを加え、0.1mol/L水酸化カリウム滴定液で滴定する。
(1)の結果 11.72 pHを終点として設定し、次式で酸価を求める。また、同手順でブランクを求める。
酸価(mgKOH/g)=(D-B)×K×F×M/S
D:滴定値(mL)
B:ブランク(0.085mL)
K:KOHの分子量(56.1)
F:滴定液のファクタ(1.000)
M:滴定液のモル濃度(0.1mol/L)
S:試料採取量(g)
WPI-113(50%プロピレンカーボネート):ヨードニウムヘキサフルオリン酸塩(和光純薬社製)
(i)BASF社製、Basionic LQ 01(1-エチル-3-メチル-1H-イミダゾリウムエチルスルファート、前記(1-2)と(8-3)のイオン対を有するイオン液体)
(ii)BASF社製、Basionic AC 09(1-エチル-3-メチル-イミダゾリウテトラクロロアルミネート、前記(1-2)と(10-2)のイオン対を有するイオン液体)
(iii)BASF社製、Basionic VS 01(1-エチル-3-メチル-イミダゾリウチオシアネート、前記(1-2)と(10-1)のイオン対を有するイオン液体)
(iv)ライオン・アクゾ株式会社製、TMAC-100(テトラメチルアンモニウムクロライド(前記(5-10)と(7-2)のイオン対を有するイオン液体)
(i)(株)ADEKA製アデカスタブAX-71、モノステアリルリン酸及びジステアリルリン酸混合物
(ii)大八化学工業(株)製モノラウリルリン酸
日清紡ケミカル(株)製カルボジライトV-05、NCO基8.2%
下記表1~9に示す配合割合(質量部)において、攪拌機を備えた容器中に成分(a)を入れ、続いて成分(b)を添加し、常温で十分に攪拌し、その後、成分(c)、(d)を加え攪拌後、液温が常温になった時点で、成分(e)を添加して、溶け残りがないように十分攪拌し、組成物を得た。得られた組成物の25℃における粘度(mPa・s)を測定した。 すなわち、ハンディタイプのデジタル粘度計TVC-7形粘度計(東機産業社)を用いて、粘度に合わせた適当なロータ(0号~5号)を用いて、25℃粘度を測定した。結果を表1~9に併せて示す。
・硬質塩化ビニル樹脂PVC(リケンテクノス社製、商品名Riken PVC Compound RE-3844)
・軟質塩化ビニル樹脂PVC(リケンテクノス社製、商品名Leonyl BZL6060N)
・ポリスチレンPS(東洋スチレン社製、商品名トーヨースチロールGP G100C)
・ポリカーボネートPC(帝人化成社製、商品名パンライトL-1225L)
・アクリロニトリル-ブタジエン-スチレン共重合体ABS(UMG社製、商品名UMG ABS EX114)
・ガラス(顕微鏡プレパラート用スライドグラス)
・アルミニウム(H5052、Al-Mg系)
・マグネシウム(大阪富士工業社製、AZ31B、Mg含有量91%以上)
・鋼板(SPCC:冷間圧延鋼板)
・PET:ユニチカ ユニチカポリエステル樹脂MA-2103
・PMMA:三菱レイヨン アクリペット VH
(密着性試験:碁盤目テープ試験)
日本工業規格K5400に記載されている碁盤目テープ試験法に準拠して以下のように測定を行った。
碁盤目テープ試験(Cross-cut Test、塗布厚15~20μm(スピンコート法)):試験面(組成物の層(A)側)にカッターナイフを用いて、1×1mm四方の碁盤目の切り傷を入れる。カッターガイドを使用する。碁盤目の数は、縦10個×横10個=100個入れる。碁盤目を入れた所にセロハンテープを強く圧着させ、テープの端を45°の角度で急速に引き剥がし、碁盤目の状態(剥離しないで残った碁盤目の個数)を見る。
結果を併せて表1~9に示す。
異材質間の接着試験を次に示すようなせん断接着力測定により行った。結果を表に示す。
寸法150mm×1mm厚×25mm巾の特定被着体(B1)上に、スピンコート法で上記組成物を塗布し(塗布厚15~20μm)、組成物の層(A)を形成し、さらにその上に、表に示す、上記(B1)と同じ寸法の各特定被着体(B2)を圧着させ、透明な層側からUV照射(波長:325nm、積算照射強さ:50mJ/cm2)してUV硬化させ、積層体を調製した後、特定被着体(B2)を、組成物の層(A)の接合面と平行な方向に引張り、破断時の引張強さ(MPa)を測定した。
結果を表に示す。なお表では、上記(B1)-(A)-(B2)からなる積層体を、(B1)vs(B2)のように示した。例えば、(B1)が硬質PVCであり、(B2)がガラスである場合は、「硬質PVC vsガラス」のように示した。
試験方法:25mm巾、1mm厚の鋼板にスピンコート法で15~20μmの厚みで組成物を塗布し、硬化後1m高さから1kgwの球状である重りを落下し以下の基準で評価を行った。
○:剥離しない
△:一部剥離・割れ
×:全面剥離・割れ
試験方法:25mm巾、1mm厚の鋼板にスピンコート法で15~20μmの厚みで組成物を塗布し、硬化後90度折り曲げ試験を行い以下の基準で評価を行った。
○:剥離しない
△:一部剥離・割れ
×:全面剥離・割れ
試験方法:25mm巾、1mm厚の鋼板にスピンコート法で15~20μmの厚みで組成物を塗布し、目視により収縮度合いを以下の基準で評価を行った。
○:表面が平滑で収縮しない
×:表面が収縮する
透明性を評価するため、JIS-K7136: 2000に基づいて実施例及び比較例の成形体(基材ガラス)のヘーズを、ヘーズメーター(NDH2000:日本電色社) を用いて測定した。評価は、測定値が1.0%未満であったものを「◎」、1.0%以上2.0%未満であったものを「○」、2.0%以上「×」とした。なお、測定面は、塗膜面とした。
表面抵抗は、サンプルとしてPC(ポリカーボネート)基材(寸法:150mm×25mm×厚さ1mm)上に、スピンコート法により組成物を塗布し(塗布厚10μm)、三菱化学(株)製 高抵抗率計ハイレスターUP(MCP―HT450型)にて、ASTM D257に準じて印加電圧500Vにて表面抵抗率(Ω/sq.)を測定した。各サンプルの抵抗率は5枚の測定値の平均値(n=5)とした。
以下の顔料を分散剤と混合した後、上記塗料組成物85質量部に対し、15質量部加え分散させ、高速水冷式撹拌機により撹拌し、ポリカーボネート基材上にスピンコート法で約30μmの厚さに塗布した後、UV照射して発色性を評価した。
顔料-1 (f)IRGALITE BLUE GLVO(シアン顔料、チバスペシャリティーケミカルズ(CSC)社製、表面酸量:18.0、表面塩基量:34.0)の80質量部に対し、(g)Solsperse36000(分散剤、LUBRIZOL社製、酸価:45mgKOH/g、アミン価:0mgKOH/g)を20質量部配合して、顔料-1を得た。なお、顔料-1の調製は分散機モーターミルM50(アイガー社製)に入れて、直径0.65mmのジルコニアビーズを用い、周速9m/sで4時間分散を行った。
顔料-2 (f)Tipaque CR60-2(ホワイト顔料(酸化チタン)、石原産業社製、表面酸量:8、表面塩基量:25)90質量部に対し、(g)Solsperse36000(分散剤、LUBRIZOL社製、酸価:45mgKOH/g、アミン価:0mgKOH/g)を10質量部配合して、顔料-2を得た。なお、顔料-2の調製は分散機モーターミルM50(アイガー社製)に入れて、直径0.65mmのジルコニアビーズを用い、周速9m/sで4時間分散を行った。
発色性評価は、印字サンプルを目視で確認して、発色性を以下の基準に従って評価した。
○:発色性に問題なし
△:若干発色性に問題があり、実用上問題あり
×:明らかに発色性に問題があり、実用には向かない
前記実施例および比較例と同様に塗料を調製し、表に示す被着体上に塗料を厚さ約20μmとして塗布し、硬化させ、積層体を調製した。この積層体上にインクジェット用インク(UVインクシアン(SPC-0371C、ミマキエンジニアリング社製、5%未満ピグメントブルー15、80~90%アクリル酸エステル、5~15%他)またはUVインクライトシアン(SPC-0371LC-2、ミマキエンジニアリング社製、1%未満ピグメントブルー15、80~90%アクリル酸エステル、10~20%他))をスピンコート法で約30μm厚でコートし、乾燥後、前記の碁盤目テープ試験を行った。結果を表1~9に示す。
長期保存安定性評価は、塗料をアズワン社製 グッドボーイ褐色瓶(400nm以下の紫外線透過率は0.3%以下、容量250mL)に入れて23℃の暗所に保存し、168時間後の粘度を測定して、以下の基準に従って評価した。
○:粘度上昇が5%未満で問題なし
△:粘度上昇が10%未満だが、実用上問題あり
×:粘度上昇が10%以上、実用には向かない
結果を表1~9に示す。
一方、比較例1は、成分(d)を配合していないので、接着性、耐衝撃性、柔軟性、表面収縮が悪化した。
比較例2は、成分(b)の配合量が本発明で規定する下限未満であり、成分(d)の配合量が本発明で規定する上限を超えているので、接着性、透明性、粘度が悪化した。
比較例3は、成分(a)の配合量が本発明で規定する下限未満であり、成分(c)の配合量が本発明で規定する上限を超えているので、接着性、耐衝撃性、柔軟性、表面収縮、透明性が悪化した。
比較例4は、成分(a)の配合量が本発明で規定する上限を超え、成分(b)の配合量が本発明で規定する下限未満であるので、接着性、耐衝撃性、柔軟性、表面収縮、透明性が悪化した。
比較例5は、成分(b)の配合量が本発明で規定する下限未満であるので、接着性、耐衝撃性、柔軟性、表面収縮、透明性が悪化した。
比較例6は、成分(a)の配合量が本発明で規定する下限未満であり、成分(b)の配合量が本発明で規定する上限を超えているので、接着性、耐衝撃性、柔軟性、表面収縮、透明性が悪化した。
比較例7は、成分(c)の配合量が本発明で規定する下限未満であるので、接着性、耐衝撃性、柔軟性、表面収縮、透明性が悪化した。
比較例8は、成分(c)の配合量が本発明で規定する上限を超えているので、接着性、耐衝撃性、柔軟性、表面収縮、透明性が悪化した。
比較例9は、成分(e)を配合していないので、硬化せず、試験の実施が不可であった。
比較例10は、成分(e)の配合量が本発明で規定する上限を超えているので、接着性、耐衝撃性、柔軟性、表面収縮、透明性が悪化した。
比較例1~10はいずれもインクジェット用インクおよびプライマー層としての性能が不十分であった。
インク供給系は、元タンク、供給配管、インクジェットヘッド直前のインク供給タンク、フィルター、ピエゾ型のインクジェットヘッドから成り、インク供給タンクからインクジェットヘッド部分までを断熱及び加温を行った。温度センサーは、インク供給タンク及びインクジェットヘッドのノズル付近にそれぞれ設け、ノズル部分が常に45℃±2℃となるよう、温度制御を行った。ピエゾ型のインクジェットヘッドは、8~30plのマルチサイズドットを720×720dpiの解像度で射出できるよう駆動した。着弾後はUV光を露光面照度1,630mW/cm2、に集光し、被記録媒体上にインク着弾した0.1秒後に照射が始まるよう露光系、主走査速度及び射出周波数を調整した。また、画像に照射される積算光量を4,500mJ/cm2となるようにした。紫外線ランプには、HAN250NL ハイキュア水銀ランプ(ジーエス・ユアサ コーポレーション社製)を使用した。なお、本発明でいうdpiとは、2.54cm当たりのドット数を表す。被記録媒体として、エステルフィルムE5000(膜厚125μm、東洋紡社製)を用いた。
本発明の塗料組成物は、インクジェット記録装置で使用されるインクとしても使用できる。プライマーとしても有効である。プライマーも通常インクジェット記録装置で塗布されることが多いので低粘度である本発明の塗料組成物は有用である。
Claims (34)
- (a)エポキシ樹脂 10~30質量%
(b)オキセタン化合物 25~55質量%
(c)ビニルエーテル化合物 25~55質量%
(d)変性剤 1~15質量%
(ただし、前記成分(a)~(d)の合計は100質量%である)
および
(e)光カチオン重合開始剤 前記成分(a)~(d)の合計100質量部に対し3~15質量部
を含有する接着剤組成物。 - 前記成分(d)が、水酸基価40~330mgKOH/gのポリオール(d-1);および水酸基価40~330mgKOH/gであり、かつ酸価が2~20mgKOH/gであるポリオール(d-2);変性ゴム(d-3);エポキシ当量が150~700g/モルである化合物(d-4)からなる群から選択された少なくとも1種であることを特徴とする請求項1に記載の接着剤組成物。
- 前記成分(d-1)が、水酸基価40~330mgKOH/gのヒマシ油系ポリオール(d-1-1);水酸基価40~330mgKOH/gのポリブタジエン系ポリオール(d-1-2);および水酸基価40~330mgKOH/gのポリイソプレン系ポリオールまたはその水素添加物(d-1-3)からなる群から選択された少なくとも1種であることを特徴とする請求項2に記載の接着剤組成物。
- 前記成分(d-1)が、水酸基価40~330mgKOH/gの芳香族系ヒマシ油系ポリオール(d-1-1-1)であることを特徴とする請求項3に記載の接着剤組成物。
- 前記成分(d-2)が、水酸基価40~330mgKOH/gであり、かつ酸価が2~20mgKOH/gであるヒマシ油系ポリオール(d-2-1)であることを特徴とする請求項3に記載の接着剤組成物。
- 前記成分(d-3)が酸変性ポリブタジエンまたは酸変性ポリイソプレンであることを特徴とする請求項3に記載の接着剤組成物。
- 前記成分(d-4)がエポキシ当量が150~250g/モルであるポリエポキシ化合物(d-4-1)であることを特徴とする請求項3に記載の接着剤組成物。
- 前記成分(d-4)がエポキシ当量が500~700g/モルである飽和骨格を持つ重合体(d-4-2)であることを特徴とする請求項3に記載の接着剤組成物。
- さらに(f)帯電防止材料としてのイオン液体を、前記成分(a)~(d)の合計100質量に対し0.5~10質量部含有してなることを特徴とする請求項1~8いずれかに記載の接着剤組成物。
- 前記イオン液体(f)が、イミダゾリウム、ピリジニウム、ピロリジニウム、フォスフォニウム、アンモニウムおよびスルホニウムからなる群から選ばれる少なくとも1種のカチオンを含むことを特徴とする請求項9に記載の接着剤組成物。
- 前記イオン液体(f)が、ハロゲン、カルボキシレート、サルフェート、スルホネート、チオシアネート、アルミネート、ボレート、ホスフェート、ホスフィネート、アミド、アンチモネート、イミドおよびメチドからなる群から選ばれるアニオンを含むことを特徴とする請求項10に記載の接着剤組成物。
- さらに帯電防止向上剤(g)を含み、前記帯電防止向上剤(g)が、酸性リン酸エステル(g-1)およびカルボジイミド化合物(g-2)からなる群から選ばれる少なくとも1種であり、かつ、前記帯電防止向上剤(g)の配合量が、前記イオン液体(f)の質量を1としたときに、0.02~30の範囲であることを特徴とする請求項9~11のいずれかに記載の接着剤組成物。
- 前記接着剤組成物の被着体が、軟質および硬質塩化ビニル樹脂;ポリスチレン;ポリカーボネート;ガラス;アルミニウム;鋼板;極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体;マグネシウム;アクリロニトリル-ブタジエン-スチレン共重合体;ポリエステル系樹脂;またはアクリル系樹脂であることを特徴とする請求項1~12のいずれかに記載の接着剤組成物。
- 工程I:
(a)エポキシ樹脂 10~30質量%
(b)オキセタン化合物 25~55質量%
(c)ビニルエーテル化合物 25~55質量%
(d)変性剤 1~15質量%
(ただし、前記成分(a)~(d)の合計は100質量%である)
および
(e)光カチオン重合開始剤 前記成分(a)~(d)の合計100質量部に対し3~15質量部
を任意の順に混合し、接着剤組成物を調製する工程、
工程II:
軟質および硬質塩化ビニル樹脂;ポリスチレン;ポリカーボネート;ガラス;アルミニウム;鋼板;極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体;マグネシウム;アクリロニトリル-ブタジエン-スチレン共重合体;ポリエステル系樹脂;またはアクリル系樹脂の層(B1)の表面に前記工程Iで得られた接着剤組成物を積層し、接着剤組成物の層(A)を形成する工程、
工程III:
前記工程IIで得られた積層体の接着剤組成物の層(A)と、軟質および硬質塩化ビニル樹脂;ポリスチレン;ポリカーボネート;ガラス;アルミニウム;鋼板;極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体;マグネシウム;アクリロニトリル-ブタジエン-スチレン共重合体;ポリエステル系樹脂;またはアクリル系樹脂の層(B2)をさらに積層する工程、
を工程I、工程IIおよび工程IIIのこの順で行うことを特徴とする接着方法。 - (a)エポキシ樹脂 10~30質量%
(b)オキセタン化合物 25~55質量%
(c)ビニルエーテル化合物 25~55質量%
(d)変性剤 1~15質量%
(ただし、前記成分(a)~(d)の合計は100質量%である)
および
(e)光カチオン重合開始剤 前記成分(a)~(d)の合計100質量部に対し3~15質量部
を含有する接着剤組成物の層(A)と、
(ただし、前記成分(a)~(d)の合計は100質量%である)
軟質および硬質塩化ビニル樹脂;ポリスチレン;ポリカーボネート;ガラス;アルミニウム;鋼板;極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体;マグネシウム;アクリロニトリル-ブタジエン-スチレン共重合体;ポリエステル系樹脂;またはアクリル系樹脂の層(B1)と
を前記層(A)および層(B1)が接するようにして形成された積層体。 - 軟質および硬質塩化ビニル樹脂;ポリスチレン;ポリカーボネート;ガラス;アルミニウム;鋼板;極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体;マグネシウム;アクリロニトリル-ブタジエン-スチレン共重合体;ポリエステル系樹脂;またはアクリル系樹脂の層(B1)と、
(a)エポキシ樹脂 10~30質量%
(b)オキセタン化合物 25~55質量%
(c)ビニルエーテル化合物 25~55質量%
(d)変性剤 1~15質量%
(ただし、前記成分(a)~(d)の合計は100質量%である)
および
(e)光カチオン重合開始剤 前記成分(a)~(d)の合計100質量部に対し3~15質量部
を含有する接着剤組成物の層(A)と、
軟質および硬質塩化ビニル樹脂;ポリスチレン;ポリカーボネート;ガラス;アルミニウム;鋼板;極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体;マグネシウム;アクリロニトリル-ブタジエン-スチレン共重合体;ポリエステル系樹脂;またはアクリル系樹脂の層(B2)と、
を前記層(B1)、層(A)および層(B2)の3層がこの順で接するようにして形成された積層体。 - (a)エポキシ樹脂 10~30質量%
(b)オキセタン化合物 25~55質量%
(c)ビニルエーテル化合物 25~55質量%
(d)変性剤 1~15質量%
(ただし、前記成分(a)~(d)の合計は100質量%である)
および
(e)光カチオン重合開始剤 前記成分(a)~(d)の合計100質量部に対し3~15質量部
を含有する塗料組成物。 - 前記成分(d)が、水酸基価40~330mgKOH/gのポリオール(d-1);および水酸基価40~330mgKOH/gであり、かつ酸価が2~20mgKOH/gであるポリオール(d-2);変性ゴム(d-3);エポキシ当量が150~700g/モルである化合物(d-4)からなる群から選択された少なくとも1種であることを特徴とする請求項17に記載の塗料組成物。
- 前記成分(d-1)が、水酸基価40~330mgKOH/gのヒマシ油系ポリオール(d-1-1);水酸基価40~330mgKOH/gのポリブタジエン系ポリオール(d-1-2);および水酸基価40~330mgKOH/gのポリイソプレン系ポリオールまたはその水素添加物(d-1-3)からなる群から選択された少なくとも1種であることを特徴とする請求項18に記載の塗料組成物。
- 前記成分(d-1)が、水酸基価40~330mgKOH/gの芳香族系ヒマシ油系ポリオール(d-1-1-1)であることを特徴とする請求項19に記載の塗料組成物。
- 前記成分(d-2)が、水酸基価40~330mgKOH/gであり、かつ酸価が2~20mgKOH/gであるヒマシ油系ポリオール(d-2-1)であることを特徴とする請求項19に記載の塗料組成物。
- 前記成分(d-3)が酸変性ポリブタジエンまたは酸変性ポリイソプレンであることを特徴とする請求項19に記載の塗料組成物。
- 前記成分(d-4)がエポキシ当量が150~250g/モルであるポリエポキシ化合物(d-4-1)であることを特徴とする請求項19に記載の塗料組成物。
- 前記成分(d-4)がエポキシ当量が500~700g/モルである飽和骨格を持つ重合体(d-4-2)であることを特徴とする請求項19に記載の塗料組成物。
- さらに(f)帯電防止材料としてのイオン液体を、前記成分(a)~(d)の合計100質量に対し0.5~10質量部含有してなることを特徴とする請求項17~24いずれかに記載の塗料組成物。
- 前記イオン液体(f)が、イミダゾリウム、ピリジニウム、ピロリジニウム、フォスフォニウム、アンモニウムおよびスルホニウムからなる群から選ばれる少なくとも1種のカチオンを含むことを特徴とする請求項25に記載の塗料組成物。
- 前記イオン液体(f)が、ハロゲン、カルボキシレート、サルフェート、スルホネート、チオシアネート、アルミネート、ボレート、ホスフェート、ホスフィネート、アミド、アンチモネート、イミドおよびメチドからなる群から選ばれるアニオンを含むことを特徴とする請求項26に記載の塗料組成物。
- さらに帯電防止向上剤(g)を含み、前記帯電防止向上剤(g)が、酸性リン酸エステル(g-1)、カルボジイミド化合物(g-2)、およびビニルエーテル系化合物(g-3)からなる群から選ばれる少なくとも1種であり、かつ、前記帯電防止向上剤(g)の配合量が、前記イオン液体(f)の質量を1としたときに、0.02~30の範囲であることを特徴とする請求項25~27のいずれかに記載の塗料組成物。
- 前記塗料組成物の被着体が、軟質および硬質塩化ビニル樹脂;ポリスチレン;ポリカーボネート;ガラス;アルミニウム;鋼板;極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体;マグネシウム;アクリロニトリル-ブタジエン-スチレン共重合体;ポリエステル系樹脂;またはアクリル系樹脂であることを特徴とする請求項17~28のいずれかに記載の塗料組成物。
- (a)エポキシ樹脂 10~30質量%
(b)オキセタン化合物 25~55質量%
(c)ビニルエーテル化合物 25~55質量%
(d)変性剤 1~15質量%
(ただし、前記成分(a)~(d)の合計は100質量%である)
および
(e)光カチオン重合開始剤 前記成分(a)~(d)の合計100質量部に対し3~15質量部
を含有する塗料組成物の層(A)と、
(ただし、前記成分(a)~(d)の合計は100質量%である)
軟質および硬質塩化ビニル樹脂;ポリスチレン;ポリカーボネート;ガラス;アルミニウム;鋼板;極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体;マグネシウム;アクリロニトリル-ブタジエン-スチレン共重合体;ポリエステル系樹脂;またはアクリル系樹脂の層(B1)と
を前記層(A)および層(B1)が接するようにして形成された積層体。 - 請求項17~29のいずれかに記載の塗料組成物を含有することを特徴とするインクジェット用インク。
- さらに着色剤を含有することを特徴とする請求項31に記載のインクジェット用インク。
- 請求項17~29のいずれかに記載の塗料組成物を含有することを特徴とする、インクジェット記録媒体上に設けられたプライマー層。
- インクジェット記録媒体上に、請求項31または32に記載のインクジェット用インクを用いてインクジェット印刷してなる印刷物。
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Also Published As
Publication number | Publication date |
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CN103025839A (zh) | 2013-04-03 |
EP2623575A1 (en) | 2013-08-07 |
JPWO2012042665A1 (ja) | 2014-02-03 |
KR20130016460A (ko) | 2013-02-15 |
US20130177719A1 (en) | 2013-07-11 |
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