WO2024252933A1 - 合成皮革の製造方法、合成皮革の製造装置 - Google Patents

合成皮革の製造方法、合成皮革の製造装置 Download PDF

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Publication number
WO2024252933A1
WO2024252933A1 PCT/JP2024/018930 JP2024018930W WO2024252933A1 WO 2024252933 A1 WO2024252933 A1 WO 2024252933A1 JP 2024018930 W JP2024018930 W JP 2024018930W WO 2024252933 A1 WO2024252933 A1 WO 2024252933A1
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WIPO (PCT)
Prior art keywords
synthetic leather
layer
pigment
inkjet
urethane resin
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Ceased
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PCT/JP2024/018930
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English (en)
French (fr)
Japanese (ja)
Inventor
浩之 五十嵐
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DIC Corp
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DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Priority to JP2024550720A priority Critical patent/JP7622912B1/ja
Publication of WO2024252933A1 publication Critical patent/WO2024252933A1/ja
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • 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
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • 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
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes

Definitions

  • urethane resins Due to its mechanical strength and good texture, urethane resins are widely used in synthetic leather (including artificial leather), coating agents, adhesives, gloves, clothing, etc.
  • solvent-based urethane resin compositions containing N,N-dimethylformamide (DMF) have been the mainstream of such urethane resin compositions.
  • DMF N,N-dimethylformamide
  • urethane resin aqueous dispersions polyurethane dispersions
  • Synthetic leather is made by applying a synthetic resin onto a base material to reproduce the texture of natural leather.
  • Synthetic leather has at least a base material and a layer called a skin layer, and may also have a microporous layer called an intermediate layer between the base material and the skin layer to achieve a luxurious texture and feel.
  • an adhesive layer may be formed between each layer.
  • a surface treatment layer or decorative layer may be formed on top of the skin layer to create a texture or gloss, or to add color and patterns.
  • the most common method for producing synthetic leather using an aqueous urethane resin dispersion is to use release paper to maintain the smoothness of the surface, to protect the synthetic leather surface from dirt and dust, and to impart a design (such as a textured or grained pattern) to imitate natural leather (see, for example, Patent Document 1).
  • a urethane resin composition paint for the surface layer is applied to the release paper and dried and solidified, and then the urethane resin composition paint for the intermediate layer that has been subjected to the foaming treatment is applied on top of that and dried and solidified.
  • the coated surface of the intermediate layer is then heat-pressed to a substrate such as a base fabric, and the release paper is peeled off after cooling.
  • the release paper is disposable, which poses potential issues in terms of cost and environmental impact.
  • both the surface layer and the middle layer need to be painted, and there are problems with the large amount of paint that is not used after manufacturing, and waste liquid from cleaning the manufacturing equipment and machinery used.
  • the problem that the present invention aims to solve is to provide a method for producing synthetic leather that does not use release paper.
  • the problem that this invention aims to solve is to provide a manufacturing method for synthetic leather for vehicle seats that eliminates the sewing process.
  • the present invention solves the above problems by providing a method for producing synthetic leather including a skin layer, the method including a step of forming the skin layer by an inkjet method, and a synthetic leather production device that includes a substrate transport means or an inkjet head moving means, an inkjet head, and a dryer, and forms the skin layer by the inkjet method.
  • the inkjet method is known as a method for forming images by ejecting tiny droplets onto a substrate. Furthermore, inkjet ejection is only possible with low-viscosity ink. For this reason, it is not possible to eject synthetic leather paint, which has an extremely high viscosity compared to inkjet ink, and it has generally been thought that the inkjet method cannot be used to manufacture synthetic leather.
  • synthetic leather paint which is originally highly viscous, can be adjusted to a viscosity that can be inkjet-discharged.
  • synthetic leather can be produced without using release paper, and that waste paint and washing waste liquid can be reduced compared to applying paint.
  • the inventors also realized that if an aqueous urethane resin dispersion containing a pigment is inkjet-discharged onto a substrate such as a base fabric, decoration can be performed simultaneously with layer formation, and defects associated with the additional formation of a decorative layer do not occur.
  • the inventors conducted research and discovered that even if the synthetic leather ink is adjusted to a viscosity suitable for inkjet ejection, it is possible to obtain synthetic leather by applying the ink to a substrate such as a base fabric using the inkjet method and drying the ink.
  • the inventors realized that by polymerizing an active energy ray-curable paint containing urethane acrylate, it is possible to obtain synthetic leather similar to that obtained by applying a paint for synthetic leather. They also realized that such an active energy ray-curable paint containing urethane acrylate can also be adjusted to a viscosity that allows it to be ejected by inkjet.
  • the inventors have discovered that if an active energy ray-curable paint containing urethane acrylate is ink-jet-discharged onto a substrate such as a base fabric and then polymerized and dried, synthetic leather can be produced without using release paper, and furthermore, waste paint and washing liquid can be reduced compared to coating with paint, and VOCs can be reduced compared to solvent-based paints.
  • the inventors have also discovered that if an active energy ray-curable paint containing a pigment and urethane acrylate is ink-jet-discharged onto a substrate such as a base fabric and then polymerized and dried, decoration can be performed simultaneously with layer formation, and defects associated with the additional formation of a decorative layer do not occur.
  • the inventors realized that by forming synthetic leather directly onto the cushioning material for vehicle seats, it is possible to eliminate the conventional process of cutting and sewing a separately manufactured synthetic leather sheet and then covering the cushioning material for vehicle seats, thereby making it possible to significantly reduce the number of processes and waste, thereby reducing the environmental burden.
  • An example of the configuration of the present invention that solves the above problem is as follows.
  • Item 1 A method for producing synthetic leather including a skin layer, the method including forming the skin layer by an inkjet method.
  • Item 2 A method for producing a synthetic leather according to Item 1, comprising the step of applying an aqueous urethane resin dispersion containing at least a urethane resin composition and water by an inkjet method and then drying the applied dispersion to form the surface layer.
  • Item 3 The method for producing synthetic leather according to Item 2, wherein the urethane resin composition has an anionic group and/or a nonionic group.
  • Item 4 The method for producing synthetic leather according to item 2 or 3, wherein the urethane resin aqueous dispersion further contains a pigment.
  • Item 5 The method for producing synthetic leather according to Item 4, wherein the pigment is carbon black or titanium oxide.
  • Item 6 The method for producing synthetic leather according to any one of items 1 to 5, wherein the synthetic leather further comprises a fibrous substrate, and the form of the fibrous substrate is one selected from the group consisting of nonwoven fabric, knitted fabric, and woven fabric.
  • Item 7 The method for producing synthetic leather according to any one of items 1 to 6, further comprising a step of forming a surface treatment layer on the surface of the skin layer using a surface treatment agent.
  • Item 8 The method for producing synthetic leather according to any one of items 1 to 7, wherein the synthetic leather further includes an intermediate layer, and the method includes a step of forming the intermediate layer by an inkjet method.
  • a synthetic leather manufacturing device that includes a substrate transport means or an inkjet head moving means, an inkjet head, and a dryer, and forms a skin layer using an inkjet method.
  • the manufacturing method and manufacturing device of the present invention make it possible to produce synthetic leather without using release paper, thereby reducing waste.
  • FIG. 1 is a schematic diagram showing one embodiment of the method for producing synthetic leather of the present invention.
  • FIG. 2 is a schematic diagram showing one embodiment of the method for producing the synthetic leather of the present invention.
  • FIG. 3 is a schematic diagram showing one embodiment of the synthetic leather obtained by the method for producing a synthetic leather of the present invention.
  • FIG. 4 is a schematic diagram showing another embodiment of the synthetic leather obtained by the method for producing a synthetic leather of the present invention.
  • FIG. 5 is a schematic diagram showing one embodiment of the method for producing the synthetic leather of the present invention.
  • the method for producing synthetic leather according to the present embodiment is a method for producing synthetic leather including a skin layer, and includes a step of forming the skin layer by an inkjet method.
  • FIG. 3 is a schematic diagram showing one embodiment of synthetic leather obtained by the synthetic leather manufacturing method of the present invention.
  • the synthetic leather 150 obtained by the manufacturing method of the present invention includes a skin layer 130.
  • the synthetic leather 150 is preferably one in which the skin layer 130 is laminated on the fibrous substrate 100, and it is also preferable that the synthetic leather 150 includes an intermediate layer 120 between the fibrous substrate 100 and the skin layer 130, and it is also preferable that the synthetic leather 150 includes a primer layer 110 between the fibrous substrate 100 and the skin layer 130 or between the fibrous substrate 100 and the intermediate layer 120.
  • the synthetic leather 150 is also preferably one that has a surface treatment layer on the skin layer 130.
  • FIG. 1 is a schematic diagram of one embodiment of the manufacturing method of the present invention.
  • a fibrous substrate 100 is conveyed from a substrate roll 70.
  • a laminate in which a primer layer 110 and an intermediate layer 120 are laminated on the fibrous substrate 100 may be conveyed as the substrate.
  • a skin layer forming liquid 32 is discharged from a skin layer inkjet head 31 installed at the destination of the fibrous substrate 100, and dried by a skin layer dryer 33 as necessary. If necessary, it is confirmed that the film thickness is an arbitrary thickness by a skin layer thickness meter 34, and the synthetic leather 150 is wound on a product winding roll 80 via a guide roll 50 as necessary.
  • each process is performed inline as in the present invention, compared with the conventional synthetic leather manufacturing method, it leads to a reduction in the number of processes, and it is possible to reduce the overall CO 2 emission in the synthetic leather manufacturing. Furthermore, the synthetic leather manufacturing can be fully automated, and small-scale production and timely and appropriate production are also easy.
  • the skin layer 130 is formed on the fibrous base material 100 or the intermediate layer 120, and has the function of reproducing the texture of natural leather.
  • the skin layer 130 is formed by an inkjet method.
  • the surface layer 130 is preferably made of a material containing a component having a urethane skeleton in order to give the surface layer 130 the texture of synthetic leather.
  • the step of forming the surface layer 130 by the inkjet method in the present invention is the surface layer forming step in Fig. 1, which is a step in which the coating method of the surface layer forming liquid 32, which is a paint that becomes the surface layer when dried, is the inkjet method.
  • the surface layer 130 may be formed on the fibrous substrate 100, the intermediate layer 120, or another layer (for example, an adhesive layer, a primer layer 110, etc.). Note that the laminate in which the intermediate layer 120, the primer layer 110, etc. are laminated on the fibrous substrate 100 may be collectively referred to as the substrate.
  • the step of forming the surface layer by the inkjet method may be carried out only once, or may be carried out two or more times to obtain the required film thickness.
  • the surface skin layer forming liquid 32 which becomes the surface skin layer 130 when dried, is preferably a paint containing a component having a urethane skeleton in order to produce the texture of synthetic leather, more preferably an active energy ray curable paint containing a urethane resin aqueous dispersion or a urethane acrylate, and even more preferably an urethane resin aqueous dispersion.
  • the inkjet method is a method in which a liquid, also known as ink, is passed through an inkjet head and ejected from the inkjet head onto a substrate in the form of fine droplets, thereby making it possible to apply the liquid onto a substrate.
  • the inkjet method in the present invention is not particularly limited, but examples thereof include a continuous jet type (charge control type, spray type, etc.), an on-demand type (piezo type, thermal type, electrostatic suction type, etc.), and the like.
  • the step of forming the skin layer by the inkjet method is the skin layer forming step in Fig. 1, and specifically, for example, it is a step of supplying a skin layer forming liquid 32 to an inkjet head 31 located on the transported fibrous substrate 100, adjusting the temperature as necessary, and then discharging and applying the skin layer forming liquid 32 onto the fibrous substrate 100 by the inkjet method.
  • the skin layer 130 may be formed on the fibrous substrate 100, on the intermediate layer 120, or on other layers (for example, an adhesive layer or a primer layer 110).
  • synthetic leather By forming the surface layer using the inkjet method, synthetic leather can be manufactured without using disposable release paper, which reduces waste and also reduces waste liquid in all processes, including the washing process, compared to conventional manufacturing methods. Also, by using multiple colors of surface layer forming liquids, decoration can be performed at the same time.
  • the fibrous substrate to be transported may already have an intermediate layer formed by a conventional wet method.
  • the skin layer formation process may be carried out on the fibrous substrate 100, or the layered product in which the intermediate layer is formed on the fibrous substrate may be transported as the fibrous substrate 100 and the skin layer formation process may be carried out on the laminate.
  • the fibrous base material may be transported by a so-called roll-to-roll method, in which the rolled fibrous base material is wound using a product winding roll 80 and a guide roll 50, or by a so-called sheet-feed method, in which fibrous base material cut to a certain size is transported one by one. From the viewpoint of manufacturing efficiency, however, it is preferable to use a roll-to-roll method in which all processes can be in-line. In addition, the roll-to-roll method may be a method in which the fibrous base material is transported continuously, or a step-feed method in which the fibrous base material is transported intermittently.
  • the inkjet heads may be arranged in a line head configuration with multiple inkjet heads aligned across the width of the fibrous substrate, or in a serial head configuration where one or multiple inkjet heads are mounted on a carriage that is driven left and right to eject ink. From the standpoint of manufacturing efficiency, however, it is preferable to use a line head configuration that allows high-speed coating. Furthermore, in order to eject ink in large quantities efficiently, multiple inkjet heads arranged in a line head configuration may be used.
  • the amount of the liquid for forming the epidermal layer to be discharged is preferably 15 to 5000 pL, and more preferably 15 to 2500 pL, in order to efficiently ensure the film thickness.
  • the amount of the liquid to be discharged can be adjusted by selecting the type of inkjet head to be used, but it can also be fine-tuned by the drive waveform when driving the inkjet head, and the physical properties of the ink, such as viscosity and surface tension.
  • the epidermal layer forming liquid 32 is preferably subjected to a degassing process before being supplied to the inkjet head.
  • the dissolved oxygen concentration in the epidermal layer forming liquid is preferably 8.0 ppm or less, and more preferably 5.0 ppm or less, before being supplied to the inkjet head.
  • the degassing process is preferably carried out through a degassing module installed before the path leading to the inkjet head. This degassing process improves the stability of the inkjet discharge, allowing stable application for a long period of time.
  • the epidermis layer forming liquid 32 is preferably subjected to a filtering process in which the liquid is passed through a filter that removes coarse particles and the like. Specifically, it is preferable for the liquid to be passed through a filter of 50 ⁇ m or less.
  • the filtering process is preferably carried out through a capsule filter or the like that is installed before the path leading to the inkjet head. This filtering process makes it difficult for the nozzle of the inkjet head to become clogged, allowing for stable application for long periods of time.
  • the epidermis layer forming liquid 32 can be supplied to the inkjet head by a pump, by a head difference, or by adjusting the negative pressure.
  • the temperature of the epidermal layer forming liquid 32 may be adjusted by heating the inkjet head, by heating the supply path for supplying the epidermal layer forming liquid 32, or by heating the tank for the epidermal layer forming liquid 32, but it is preferable to heat the inkjet head for stable temperature adjustment.
  • the inkjet head may be heated by a temperature regulator installed outside the inkjet head or by a temperature regulator built into the inkjet head.
  • the temperature is adjusted to a viscosity that allows stable ejection of the skin layer forming liquid 32. In order to reduce the effect of temperature rise caused by long-term operation, the adjusted temperature is preferably 20 to 60° C., and more preferably 25 to 50° C.
  • the inkjet head is located close to the substrate, and more specifically, the distance between the substrate and the ejection surface of the inkjet head is preferably 10 mm or less.
  • the distance between the substrate and the ejection surface of the inkjet head is preferably 0.6 mm or more, and more preferably 1.0 mm or more. More specifically, it is preferably 0.6 to 10 mm, more preferably 1.0 to 10 mm, and even more preferably 1.0 to 5.0 mm.
  • the viscosity of the epidermis layer forming liquid 32 is not particularly limited, but is preferably a viscosity that can be ejected by inkjet, and the ejection viscosity (for example, when adjusted to 25°C using a temperature regulator, the viscosity at 25°C) is preferably 5 to 500 mPa ⁇ s, more preferably 8 to 200 mPa ⁇ s, and even more preferably 8 to 100 mPa ⁇ s.
  • the surface tension of the epidermis layer forming liquid 32 is not particularly limited, but is preferably a surface tension that allows for inkjet ejection, and is preferably 15 to 50 mN/m at 25°C, and more preferably 20 to 40 mN/m.
  • the thickness of the skin layer after drying is not particularly limited as long as it is an appropriate thickness for synthetic leather, but it is preferably 0.5 to 100 ⁇ m, more preferably 5 to 70 ⁇ m, and even more preferably 20 to 50 ⁇ m.
  • the above-mentioned surface layer drying process is not particularly limited and can be carried out using a known dryer, for example, drying with a heat roll, drying in an oven, drying with an air dryer, or drying by irradiation with near-infrared rays or the like.
  • the drying process may be curing drying by irradiation with ultraviolet rays or by irradiation with electron beams.
  • the thickness meter is not particularly limited, and any known thickness meter can be used, such as an electromagnetic thickness meter, an eddy current thickness meter, an ultrasonic thickness meter, a reflection spectroscopic thickness meter, or a fluorescent X-ray thickness meter. It is preferable to use a reflection spectroscopic thickness meter or a fluorescent X-ray thickness meter, which are non-contact thickness meters advantageous for in-line measurement. However, if in-line measurement is not performed, the film thickness can be determined from a cross-sectional photograph of the synthetic leather 150 taken with an electron microscope. Any method that can determine the film thickness can be applied, and there are no particular limitations.
  • the surface layer forming liquid 32 is preferably a urethane resin water dispersion.
  • the urethane resin water dispersion contains at least a urethane resin composition and water.
  • a urethane resin composition is a general term for a polymeric compound having a urethane bond (-NHCOO-), and is generally produced by reacting (crosslinking/curing reaction) a polyol with a polyisocyanate.
  • the urethane resin composition is dispersible in water, and examples of the urethane resin composition that can be used include a urethane resin composition having hydrophilic groups such as anionic groups, cationic groups, and nonionic groups; a urethane resin composition forcibly dispersed in water with an emulsifier, and the like. These urethane resin compositions may be used alone or in combination of two or more kinds. Among these, it is preferable that the urethane resin composition has an anionic group and/or a nonionic group.
  • the method for obtaining the urethane resin composition having an anionic group can be, for example, a method using one or more compounds selected from the group consisting of compounds having a carboxyl group and compounds having a sulfonyl group as a raw material.
  • Examples of the compound having a carboxyl group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpropionic acid, and 2,2-valeric acid. These compounds may be used alone or in combination of two or more.
  • Examples of the compound having a sulfonyl group include 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,6-diaminobenzenesulfonic acid, and N-(2-aminoethyl)-2-aminoethylsulfonic acid. These compounds may be used alone or in combination of two or more.
  • the carboxyl and sulfonyl groups may be partially or completely neutralized with a basic compound in the resin composition.
  • a basic compound examples include organic amines such as ammonia, triethylamine, pyridine, and morpholine; alkanolamines such as monoethanolamine and dimethylethanolamine; and metal base compounds containing sodium, potassium, lithium, calcium, and the like.
  • the urethane resin composition having a cationic group for example, one or more compounds having an amino group can be used as raw materials.
  • the compound having an amino group for example, compounds having primary and secondary amino groups such as triethylenetetramine and diethylenetriamine; compounds having a tertiary amino group such as N-alkyldialkanolamines such as N-methyldiethanolamine and N-ethyldiethanolamine, and N-alkyldiaminoalkylamines such as N-methyldiaminoethylamine and N-ethyldiaminoethylamine, etc. can be used. These compounds may be used alone or in combination of two or more kinds.
  • the urethane resin composition having a nonionic group for example, one or more compounds having an oxyethylene structure can be used as raw materials.
  • polyether polyols having an oxyethylene structure such as polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, etc. can be used. These compounds may be used alone or in combination of two or more.
  • urethane resin composition examples include the raw materials used to produce the urethane resin composition having hydrophilic groups described above, such as polyisocyanate (a1), polyol (a2), and, if necessary, a reaction product of a chain extender (a3). These reactions can be carried out using known urethane reactions.
  • polyisocyanate (a1) for example, aromatic polyisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimidized diphenylmethane polyisocyanate; aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dimer acid diisocyanate, and norbornene diisocyanate can be used. These polyisocyanates may be used alone or in combination of two or more.
  • polyether polyol for example, polyether polyol, polyester polyol, polyacrylic polyol, polycarbonate polyol, polybutadiene polyol, etc.
  • polyacrylic polyol for example, polyether polyol, polyester polyol, polyacrylic polyol, polycarbonate polyol, polybutadiene polyol, etc.
  • polycarbonate polyol for example, polybutadiene polyol, etc.
  • polybutadiene polyol etc.
  • these polyols may be used alone or in combination of two or more kinds.
  • the number average molecular weight of the polyol (a2) is preferably in the range of 500 to 100,000, more preferably in the range of 800 to 50,000, and even more preferably in the range of 800 to 2,500, from the viewpoint of the mechanical strength of the resulting film.
  • the number average molecular weight of the polyol (a2) is a value measured by gel permeation column chromatography (GPC).
  • the chain extender (a3) is, for example, one having a number average molecular weight in the range of 50 to 450, specifically, ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, hydride, Chain extenders having an amino group such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, saccharose, methylene glycol,
  • the amount used is preferably in the range of 0.5 to 30% by mass of the total mass of the polyisocyanate (a1), the polyol (a2), and the chain extender (a3), in order to further improve the mechanical strength of the coating.
  • the method for producing the urethane resin water dispersion includes, for example, a method in which the raw materials used to produce the urethane resin composition having a hydrophilic group are reacted with the polyisocyanate (a1), the polyol (a2), and the hydrophilic group-containing urethane prepolymer (a4) is produced (hereinafter, may be abbreviated as "prepolymer step"), and then the urethane prepolymer (a4) is dispersed in water (hereinafter, may be abbreviated as "emulsification step"), and if necessary, the urethane prepolymer (a4) is reacted with the chain extender (a3) (hereinafter, may be abbreviated as "chain extension step”); and a method in which the polyisocyanate (a1), the polyol (a2), the raw materials used to produce the hydrophilic group-containing urethane resin composition, and if necessary, the chain extender (a3) are charged all
  • the prepolymerization process can also be carried out without a solvent.
  • the prepolymerization process was generally carried out in an organic solvent such as methyl ethyl ketone or acetone, but a desolvation process was required to evaporate the organic solvent after the emulsification process, which required several days of production at actual production sites. It was also difficult to completely evaporate the organic solvent in the desolvation process, and in many cases a small amount of organic solvent remained, making it difficult to fully comply with environmental requirements.
  • the prepolymerization process can be carried out without a solvent, which makes it possible to obtain a urethane resin aqueous dispersion that is completely free of organic solvent, and also makes it possible to reduce the labor required for the production process.
  • the reaction in the prepolymerization process can be carried out, for example, at 50 to 120°C for 1 to 10 hours.
  • the prepolymer process can be carried out using a reactor equipped with an agitator; kneaders such as kneaders, continuous kneaders, taper rolls, single-screw extruders, twin-screw extruders, triple-screw extruders, universal mixers, plastomills, and Bodeta-type kneaders; rotary dispersion mixers such as TK Homomixer, Filmix, Ebara Milder, Clearmix, Ultra-Turrax, Cavitron, and Biomixer; ultrasonic dispersion equipment; and equipment that has no moving parts, such as in-line mixers, and can mix using the flow of the fluid itself.
  • kneaders such as kneaders, continuous kneaders, taper rolls, single-screw extruders, twin-screw extruders, triple-screw extruders, universal mixers, plasto
  • the emulsification process is preferably carried out at a temperature at which water does not evaporate, for example in the range of 10 to 90°C.
  • the emulsification process can be carried out using the same equipment as the prepolymer process.
  • it is preferable to use a kneader since it is possible to stably obtain an aqueous dispersion of a urethane resin composition having a small amount of oxyethylene groups introduced and an average particle size equivalent to that of the conventional method, which is caused by reacting a chain extender, and it is also possible to easily obtain an aqueous dispersion of a urethane resin having a high content of the urethane resin composition.
  • the chain extension process is a process in which the isocyanate groups of the urethane prepolymer (a4) react with the chain extender (a3) to increase the molecular weight of the urethane prepolymer (a4) and obtain a urethane resin composition.
  • the temperature during the chain extension process is preferably 50°C or less.
  • the molar ratio of the isocyanate groups in the urethane prepolymer (a4) to the sum of the hydroxyl groups and amino groups in the chain extender (a3) [(hydroxyl groups and amino groups)/isocyanate groups] is preferably in the range of 0.8 to 1.1, and more preferably in the range of 0.9 to 1, in order to obtain even better film-forming properties and mechanical strength.
  • the chain extension process can be carried out using equipment similar to that used for the prepolymer process.
  • the urethane resin composition When producing the urethane resin composition, it is preferable to deactivate the isocyanate groups remaining in the urethane resin composition. When deactivating the isocyanate groups, it is preferable to use an alcohol having one hydroxyl group, such as methanol. The amount of the alcohol used is preferably in the range of 0.001 to 10 parts by mass per 100 parts by mass of the urethane resin composition.
  • an organic solvent may be used when producing the urethane resin composition.
  • the organic solvent that can be used include ketone compounds such as acetone and methyl ethyl ketone; ether compounds such as tetrahydrofuran and dioxane; acetate compounds such as ethyl acetate and butyl acetate; nitrile compounds such as acetonitrile; and amide compounds such as dimethylformamide and N-methylpyrrolidone.
  • These organic solvents may be used alone or in combination of two or more kinds. It is preferable that the organic solvent is finally removed by a method such as distillation.
  • the water used in the present invention may be ion-exchanged water, distilled water, ultrafiltered water, ultrapure water, etc. These waters may be used alone or in combination of two or more.
  • the urethane resin aqueous dispersion of the present invention preferably further contains a pigment.
  • the pigment By containing the pigment in the surface layer forming liquid 32, the surface layer itself can be given a color pattern, making it unnecessary to further form a decorative layer, and as a result, there are no problems such as ensuring adhesion between the decorative layer and the surface layer and sheet conformability of the decorative layer coating (whether the coating cracks when folded).
  • the pigment may be used alone or in combination with other components.
  • the pigment in the form of a pigment dispersion it is preferable to add the pigment in the form of a pigment dispersion to the urethane resin water dispersion and stir or mix it, from the viewpoints of ease of production and stability of the urethane resin water dispersion.
  • the pigment may be an inorganic pigment or an organic pigment.
  • any known inorganic or organic pigment that can be dispersed in water or a water-soluble organic solvent may be used.
  • the pigment may be either a non-acid-treated pigment or an acid-treated pigment, and may be in either a dry powder or wet cake form.
  • inorganic pigments include iron oxide, carbon black produced by known methods such as the contact method, furnace method, thermal method, etc.
  • oxides, hydroxides, sulfides, ferrocyanides, chromates, carbonates, silicates, phosphates, metal powders, etc. may also be used.
  • organic pigments examples include dye lakes, azo lakes, insoluble azos, monoazos, disazos, condensed azos, benzimidazolones, phthalocyanines, anthraquinones, perylenes, perinone pigments, quinacridones, dioxazines, isoindolines, azomethines, thioindigo pigments, quinophthalone pigments, pyrrolopyrroles, etc.
  • dye chelates e.g., basic dye chelates, acid dye chelates, etc.
  • nitro pigments nitroso pigments, aniline black, etc.
  • white pigments examples include alkaline earth metal sulfates, carbonates, finely powdered silicic acid, synthetic silicates, and other silicates, calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc, clay, and the like.
  • the inorganic white pigments may be surface-treated by various surface treatment methods. Among these, titanium oxide is preferred.
  • carbon black is preferred, for example, No. 2300, No. 2200B, No. 900, No. 960, No. 980, No. 33, No. 40, No. 45, No. 45L, and No. manufactured by Mitsubishi Chemical Corporation. 52, HCF88, MA7, MA8, MA100, etc. are manufactured by Columbia Corporation Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700, etc.
  • the pigment may be a color pigment.
  • yellow pigments include C.I. Pigment Yellow 1, 2, 12, 13, 14, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 120, 128, 129, 138, 150, 151, 154, 155, 174, 180, and 185.
  • magenta pigments include C.I. Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 57:1, 112, 122, 123, 146, 168, 176, 184, 185, 202, 209, 269, 282, and C.I. Pigment Violet 19.
  • Specific examples of cyan pigments include C.I. Pigment Blue 1, 2, 3, 15, 15:3, 15:4, 16, 22, 60, 63, 66, and the like.
  • red pigments that can be used include one or more selected from the group consisting of C.I. Pigment Red 17, 49:2, 112, 149, 150, 177, 178, 179, 188, 254, 255, and 264.
  • orange pigments include C.I. Pigment Orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, 63, 64, 71, 73, and 81.
  • green pigments include C.I. Pigment Green 7, 10, 36, 58, and 59.
  • violet pigments include C.I. Pigment Violet 19, 23, 32, 33, 36, 38, 43, and 50.
  • the volatile content of the carbon black is more preferably 1% or more.
  • the amount of functional groups (OH or COOH) on the carbon black surface is large, which is considered to facilitate maintaining compatibility with the urethane resin composition during film formation and to prevent particle aggregation, which is preferable.
  • the volatile content of carbon black refers to the amount of volatilization (weight loss) when heated at 950° C. for 7 minutes, for example, and this value can be found in the product catalog or the like.
  • a preferred method is to prepare an aqueous pigment dispersion by dispersing the pigment in a water-soluble solvent and/or water together with a general-purpose pigment dispersant such as a polymer dispersant, a surfactant, or a pigment derivative by a dispersion method described below, or to process the pigment into a self-dispersing pigment that disperses and/or dissolves in a water-soluble solvent and/or water without a general-purpose pigment dispersant by bonding a dispersibility-imparting group (hydrophilic functional group and/or a salt thereof) to the surface of the pigment directly or indirectly via an alkyl group, an alkyl ether group, an aryl group, or the like, and disperses and/or dissolves in a water-soluble solvent and/or water
  • the pigment dispersant is not particularly limited, and known polymer dispersants, surfactants, and pigment derivatives can be used.
  • aqueous resins are preferred, and preferred examples include polyvinyl alcohols, polyvinylpyrrolidones, acrylic resins such as acrylic acid-acrylic acid ester copolymers, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylic acid ester copolymers, styrene- ⁇ -methylstyrene-acrylic acid copolymers, styrene- ⁇ -methylstyrene-acrylic acid-acrylic acid ester copolymers, and other styrene-acrylic resins such as styrene-maleic acid copolymers, styrene-maleic anhydride copolymers, vinylnaphthalene-acrylic acid copo
  • commercially available products can also be used.
  • examples of commercially available products that can be used include the Ajisper PB series from Ajinomoto Fine-Techno Co., Ltd., the Disperbyk series from BYK Japan Co., Ltd., the EFKA series from BASF, the SOLSPERSE series from Lubrizol Japan Co., Ltd., and the TEGO series from Evonik.
  • the polymer-based dispersant for example, the polymer pigment dispersant described in JP-A-2022-75758 can be used. More specifically, for example, the polymer dispersants described below can be suitably used.
  • a comb-structured polymeric pigment dispersant having pigment affinity groups in the main chain and/or multiple side chains and multiple side chains that constitute solvation moieties (2) A polymeric pigment dispersant having multiple pigment affinity moieties consisting of pigment affinity groups in the main chain. (3) A linear polymeric pigment dispersant having a pigment affinity moiety consisting of a pigment affinity group at one end of the main chain.
  • the pigment dispersant is preferably a modified carboxyl group-containing polymer.
  • the pigment affinity group refers to a functional group that has a strong adsorption power to the surface of the pigment.
  • examples include tertiary amino groups, quaternary ammonium groups, heterocyclic groups with a basic nitrogen atom, hydroxyl groups, and carboxyl groups; and in hydrosols, examples include phenyl groups, lauryl groups, stearyl groups, dodecyl groups, and oleyl groups.
  • the anionic group is preferably neutralized.
  • the basic compound for neutralizing the anionic group any of the known and commonly used compounds can be used, for example, inorganic basic substances such as alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and organic basic compounds such as ammonia, triethylamine, and alkanolamines.
  • the neutralization rate of the anionic group does not have to be 100% relative to the acid value of the pigment dispersant. Specifically, the neutralization rate is preferably 20% to 200%, and more preferably 80% to 150%.
  • the pigment may be a self-dispersing pigment that can be dispersed in a water-soluble solvent or water without using the pigment dispersant.
  • the pigment is produced by subjecting the pigment to a physical or chemical treatment to bond (graft) a dispersibility-imparting group or an active species having a dispersibility-imparting group to the surface of the pigment.
  • Examples of the method include vacuum plasma treatment, oxidation treatment with hypohalous acid and/or a hypohalous acid salt, oxidation treatment with ozone, a wet oxidation method in which the pigment surface is oxidized with an oxidizing agent in water, and a method in which a carboxyl group is bonded via a phenyl group by bonding p-aminobenzoic acid to the pigment surface.
  • the aqueous ink containing the self-dispersing pigment does not need to contain the pigment dispersant, it is easy to prepare an ink with excellent ejection stability without foaming caused by the pigment dispersant.
  • a significant increase in viscosity caused by the pigment dispersant is suppressed, it is possible to contain a larger amount of pigment, which makes it possible to sufficiently increase the print density or makes the ink easier to handle.
  • the method for producing a pigment dispersion using a pigment dispersant is not particularly limited and may be a known method.
  • the pigment, the pigment dispersant, water, and various additives as necessary are mixed by stirring, and then dispersed and milled using various dispersing machines or milling machines, such as a bead mill, an ultrasonic homogenizer, a high-pressure homogenizer, a paint shaker, a ball mill, a roll mill, a sand mill, a sand grinder, a Dyno Mill, a Dispermat, an SC Mill, a Nanomizer, or the like, and the remaining materials are added and mixed to adjust the viscosity to an appropriate level.
  • various dispersing machines or milling machines such as a bead mill, an ultrasonic homogenizer, a high-pressure homogenizer, a paint shaker, a ball mill, a roll mill, a sand mill, a sand grinder, a Dyno Mill, a Disper
  • the dispersion liquid can be prepared by adding a water-soluble solvent and/or water and, if necessary, various additives to a high-concentration dispersion liquid (mill base) prepared in advance using the disperser, and diluting the mixture by mixing and stirring to the desired viscosity.
  • Self-dispersing pigments may be commercially available as water-based pigment dispersions, or a pigment dispersion can be obtained by adding the self-dispersing pigment to water or a water-soluble solvent and stirring.
  • the particle diameter of the pigment dispersion liquid is preferably such that the 95% particle diameter (D95) in the cumulative particle size distribution of the pigment is 1000 nm or less.
  • the 95% particle diameter (D95) in the cumulative particle size distribution of the pigment is in the above range, the pigment particle diameter can be prevented from becoming too large, the occurrence of aggregates can be suppressed, and the dispersion stability and inkjet dischargeability can be favorably maintained.
  • the particle size of the pigment dispersion can be obtained by diluting 0.2 g of the pigment dispersion by adding 50 g of water, pretreating the diluted solution with an ultrasonic homogenizer (ULTRA HOMOGENIZER US-300E manufactured by Nippon Seiki Seisakusho) at 2.5 A for 1 minute, and measuring the particle size distribution with a dynamic light scattering device, Nanotrac Wave II manufactured by Microtrac-Bell Corporation.
  • an ultrasonic homogenizer ULTRA HOMOGENIZER US-300E manufactured by Nippon Seiki Seisakusho
  • the urethane resin water dispersion of the present invention may further contain, in addition to the above-mentioned urethane resin composition, water, and pigment, a water-soluble solvent, a surfactant, and other additives, as necessary, in order to adjust the physical properties so as to enable inkjet ejection.
  • additives that can be used include, for example, emulsifiers, neutralizing agents, thickeners, urethane catalysts, fillers, flame retardants, leveling agents, antiblocking agents, film-forming aids, defoamers, foaming agents, preservatives, pH adjusters, chelating agents, antioxidants, UV absorbers, plasticizers, etc. These additives may be used alone or in combination of two or more.
  • the urethane resin aqueous dispersion may contain not only water but also a water-soluble solvent, and the viscosity and surface tension of the urethane resin aqueous dispersion can be adjusted to a range that allows inkjet ejection.
  • ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, and methyl isobutyl ketone
  • alcohols such as methanol, ethanol, 2-propanol, 2-methyl-1-propanol, 1-butanol, and 2-methoxyethanol
  • ethers such as tetrahydrofuran, 1,4-dioxane, and 1,2-dimethoxyethane
  • glycols such as dimethylformamide, N-methylpyrrolidone, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol
  • diols such as butanediol, pentanediol, hexanediol, and diols of the same group as these
  • glycosyl esters such as propylene glycol laurate.
  • water-soluble organic solvent examples include glycol ethers such as cellosolves including diethylene glycol monoethyl, diethylene glycol monobutyl, and diethylene glycol monohexyl ethers, propylene glycol ether, dipropylene glycol ether, and triethylene glycol ether; alcohols such as methanol, ethanol, isopropyl alcohol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, butyl alcohol, pentyl alcohol, and alcohols of the same family as these; or sulfolane; lactones such as ⁇ -butyrolactone; lactams such as N-(2-hydroxyethyl)pyrrolidone; and various other solvents known as water-soluble organic solvents, such as glycerin and its derivatives. These water-soluble organic solvents can be used alone or in combination of two or more.
  • glycol ethers such as cellosolves including diethylene glycol monoethyl
  • the water-soluble organic solvent used in this case is preferably a water-soluble organic solvent with a high boiling point, since there is no need for desolvation in a later step.
  • water-soluble organic solvents with a high boiling point include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; diols such as butanediol, pentanediol, hexanediol, and diols of the same group; glycol esters such as propylene glycol laurate; glycol ethers such as cellosolve containing diethylene glycol monoethyl, diethylene glycol monobutyl, and diethylene glycol monohexyl ethers, propylene glycol ether, dipropylene glycol ether, and triethylene glycol ether; sulfolane; lactones such as ⁇ -butyrolactone;
  • a water-soluble organic solvent as a wetting agent in the urethane resin aqueous dispersion so that the urethane resin aqueous dispersion is less likely to dry out in the nozzles of the ink-jet head.
  • wetting agents include glycerin, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycols having a molecular weight of 2000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propylene glycol, isopropylene glycol, isobutylene glycol, 1,2-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, It is more preferable to use diol compounds such as 1,2-hexanediol, 1,6-hexanediol, 2-methylpentane-2,4-diol, 1,2-heptanediol, 1,2-nonanediol, 1,2-octanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-nonanediol, and 1,2-o
  • the content of the wetting agent in the urethane resin aqueous dispersion is preferably 3 to 50% by mass.
  • a surfactant may be added to the urethane resin aqueous dispersion in order to adjust the surface tension or to control the wettability of the urethane resin aqueous dispersion to the fibrous substrate after extrusion.
  • the surfactant include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, etc., and among these, anionic surfactants or nonionic surfactants are preferred.
  • anionic surfactants include alkylbenzenesulfonates, alkylphenylsulfonates, alkylnaphthalenesulfonates, higher fatty acid salts, sulfates of higher fatty acid esters, sulfonates of higher fatty acid esters, sulfates and sulfonates of higher alcohol ethers, higher alkyl sulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, and polyoxyethylene alkyl ether phosphates.
  • dodecylbenzenesulfonates include dodecylbenzenesulfonates, isopropylnaphthalenesulfonates, monobutylphenylphenol monosulfonates, monobutylbiphenylsulfonates, and dibutylphenylphenol disulfonates.
  • nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, fatty acid alkylol amides, alkyl alkanol amides, acetylene glycol, oxyethylene adducts of acetylene glycol, polyethylene glycol polypropylene glycol block copolymers, and alkylphenol ethoxylates.
  • polyoxyethylene nonylphenyl ether polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid alkylol amides, acetylene glycol, oxyethylene adducts of acetylene glycol, polyethylene glycol polypropylene glycol block copolymers, and alkylphenol ethoxylates are preferred.
  • surfactants that can be used include silicon-based surfactants such as polysiloxane oxyethylene adducts; fluorine-based surfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers; and biosurfactants such as spiculisporic acid, rhamnolipids, and lysolecithin.
  • silicon-based surfactants such as polysiloxane oxyethylene adducts
  • fluorine-based surfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers
  • biosurfactants such as spiculisporic acid, rhamnolipids, and lysolecithin.
  • surfactants can be used alone or in combination of two or more. Taking into consideration the solubility stability of the surfactant, it is preferable that its HLB is in the range of 7 to 20.
  • fluorine-based surfactants include Novec FC-4430, FC-4432 (all manufactured by Sumitomo 3M), Zonyl FSO-100, FSN-100, FS-300, FSO (all manufactured by DuPont), EF-TOP EF-122A, EF-351, 352801, 802 (manufactured by Gemco), Megafac F-470, F-1405, F474, F-444 (manufactured by DIC), Surflon S-111, S-112, S-113, These include S121, S131, S132, S-141, S-145 (manufactured by Asahi Glass), Ftergent series (manufactured by Neos), Fluorad FC series (manufactured by Minnesota Mining and Manufacturing Company), Monflor (manufactured by Imperial Chemical Industries), and Licowet VPF series (manufactured by Parkwerke Hoechst).
  • Silicon-based surfactants include KF-351A, KF-642, Olfin PD-501, Olfin PD-502, Olfin PD-570 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK347, BYK348 (manufactured by BYK Japan), etc.
  • polyoxyethylene alkyl ether surfactants examples include the BT series (Nikko Chemicals), the Nonipol series (Sanyo Chemical Industry), the D-, P-series (Takemoto Oils & Fat), the EMALEXDAPE series (Nippon Emulsion), and the Pegnol series (Toho Chemical Industry).
  • polyethylene glycol alkyl ester surfactants examples include Pegnol (Toho Chemical Industry).
  • acetylene glycol surfactants include Olfine E1010, STG, and Y (all manufactured by Nissin Chemical Industry Co., Ltd.), and Surfynol 104, 82, 420, 440, 465, 485, and TG (manufactured by Air Products and Chemicals Inc.).
  • the viscosity of the urethane resin water dispersion is not particularly limited, but is preferably a viscosity that allows inkjet ejection, and the ejection viscosity (for example, when adjusted to 25°C using a temperature regulator, the viscosity at 25°C) is preferably 5 to 500 mPa ⁇ s, more preferably 8 to 200 mPa ⁇ s, and even more preferably 8 to 100 mPa ⁇ s.
  • the surface tension of the urethane resin water dispersion is not particularly limited, but is preferably such that it can be ejected by inkjet, and is preferably 15 to 50 mN/m at 25°C, and more preferably 20 to 40 mN/m.
  • the surface layer forming liquid 32 may be an active energy ray curable paint containing urethane acrylate.
  • the urethane acrylate is a (meth)acrylate having a urethane bond in the molecule.
  • a compound obtained by reacting a polyol, a polyisocyanate, and a (meth)acrylic compound having a hydroxyl group or an isocyanate group by a conventionally known method can be used.
  • (meth)acrylate refers to either or both of an acrylate and a methacrylate
  • (meth)acryloyl group refers to either or both of an acryloyl group and a methacryloyl group.
  • polyester polyol for example, polyester polyol, polycarbonate polyol, polyether polyol, acrylic polyol, caprolactone polyol, butadiene polyol, etc. can be used. These polyols can be used alone or in combination of two or more kinds.
  • polyisocyanate examples include aromatic diisocyanates such as phenylene diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate; and aromatic polyisocyanates such as xylylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, polyphenylene polymethylene polyisocyanate, formalin condensates of methylene diphenyl diiso
  • Examples of the (meth)acrylic compound having a hydroxyl group include (meth)acrylic acid alkyl esters having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; polyethylene glycol monoacrylate, and polypropylene glycol monoacrylate. These compounds may be used alone or in combination of two or more.
  • Examples of the (meth)acrylic compound having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate, 2-(2-(meth)acryloyloxyethyloxy)ethyl isocyanate, and 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate. These compounds may be used alone or in combination of two or more.
  • the active energy ray-curable coating material containing a urethane acrylate preferably contains a polymerizable compound other than the above-mentioned urethane acrylate.
  • the other polymerizable compound is not particularly limited as long as it can reproduce the texture of synthetic leather as a surface layer, but it is preferable to use a polymerizable compound with a low viscosity in order to adjust the viscosity to a level suitable for inkjet ejection.
  • the active energy ray curable paint containing urethane acrylate preferably further contains a pigment.
  • a pigment in the surface layer forming liquid 32, the surface layer itself can be given a color pattern, eliminating the need to further form a decorative layer.
  • the pigment may also be dispersed using a pigment dispersant.
  • the pigment dispersant may be the polymer dispersant described above or a surfactant.
  • additives may be added to the active energy ray curable paint containing urethane acrylate.
  • Such other additives may include photopolymerization initiators, photosensitizers, polymerization inhibitors, UV absorbers, antioxidants, surface tension adjusters, anti-fading agents, etc.
  • the viscosity of the active energy ray-curable coating material containing urethane acrylate is not particularly limited, but it is preferable that the viscosity is such that it can be ejected by inkjet, and the ejection viscosity (for example, when adjusted to 25°C using a temperature regulator, the viscosity at 25°C) is preferably 5 to 500 mPa ⁇ s, more preferably 8 to 200 mPa ⁇ s, and even more preferably 8 to 100 mPa ⁇ s.
  • the surface tension of the active energy ray curable coating containing urethane acrylate is not particularly limited, but is preferably a surface tension that allows inkjet ejection, and is preferably 15 to 50 mN/m at 25°C, and more preferably 20 to 40 mN/m.
  • the fibrous substrate 100 is also called a base fabric, and a skin layer 130 can be formed on the fibrous substrate 100 to obtain synthetic leather 150.
  • a primer layer 110 and/or an intermediate layer 120 can be formed on the fibrous substrate 100 as necessary to form a substrate, on which the skin layer 130 can be formed.
  • materials for the fibrous base material 100 include, but are not limited to, natural fibers (plant fibers/animal fibers) such as cotton, linen, and silk; and chemical fibers such as polyester, nylon, acrylic, and polyurethane.
  • Examples of the form of the fibrous base material 100 include, but are not limited to, knitted fabric, woven fabric, nonwoven fabric, and the like.
  • the fibrous substrate may be provided with an adhesive layer to improve the interlayer adhesion between layers (e.g., between the fibrous substrate and a surface layer, between the fibrous substrate and an intermediate layer, etc.) located above and below the adhesive layer.
  • the adhesive layer is preferably formed from a urethane resin composition containing water and a urethane resin made from an aromatic polyisocyanate, which has high intermolecular interactions.
  • the adhesive layer may also contain other additives, such as urethane catalysts, neutralizing agents, crosslinking agents, silane coupling agents, thickeners, fillers, thixotropic agents, tackifiers, waxes, heat stabilizers, light resistance stabilizers, fluorescent whitening agents, foaming agents, pigments, dyes, conductivity agents, antistatic agents, moisture permeability enhancers, water repellents, oil repellents, hollow foams, flame retardants, water absorbents, moisture absorbents, deodorizers, foam stabilizers, antiblocking agents, hydrolysis inhibitors, etc.
  • additives may be used alone or in combination of two or more.
  • the thickness of the adhesive layer is determined appropriately depending on the application for which the synthetic leather is to be used, but can be in the range of 5 to 100 ⁇ m, for example.
  • the method for producing a synthetic leather of the present invention may further include a step of forming a surface treatment layer on the surface of the above-mentioned skin layer using a surface treatment agent.
  • the surface treatment layer is added for the purpose of improving scratch resistance, light resistance, texture, etc.
  • the surface treatment layer may also be formed for the purpose of imparting antibacterial properties, flame retardancy, etc.
  • the step of forming the surface treatment layer may be a step of forming it by an inkjet method like the skin layer, or a step of forming it by gravure roll coating, comma roll coating or the like like a conventional method.
  • the surface treatment agent is not particularly limited, and known ones can be used.
  • it may be a solvent-based resin composition, may contain a polyurethane water dispersion and an ultraviolet absorbing polymer, may contain a urethane resin composition and a crosslinking agent, may contain a filler to impart a matte feel, may contain an antibacterial agent, a flame retardant, etc.
  • the materials used in conventional surface treatment agents were mainly solvent-based resin compositions containing organic solvents, but in response to the increasing environmental regulations in recent years, it is preferable to use an aqueous surface treatment agent that does not substantially contain organic solvents.
  • FIG. 2 is a schematic diagram of a preferred embodiment of the manufacturing method of the present invention.
  • the fibrous substrate 100 is transported from the substrate roll 70 in the same manner as in FIG. 1.
  • a primer liquid 12 is ejected from the primer layer inkjet head 11 installed at the destination of the fibrous substrate 100, and dried in the primer dryer 13.
  • an intermediate layer forming liquid 22 is ejected from the intermediate layer inkjet head 21, and dried in the intermediate layer dryer.
  • Such an intermediate layer forming process may be performed only once, or may be performed two or more times to obtain the required film thickness.
  • FIG. 2 shows an example in which it is performed twice.
  • the intermediate layer thickness meter 24 is used to confirm that the desired film thickness has been achieved. Furthermore, the skin layer forming process is performed in the same manner as in FIG. 1, and the synthetic leather 150 is wound up on the product winding roll 80 via the guide roll 50 as necessary.
  • the primer layer is added to improve the adhesion between the layers by sandwiching them between the layers.
  • the primer liquid for forming the primer layer is not particularly limited as long as it can achieve the purpose, and the adhesion between the layers may be improved by a liquid containing a highly adhesive resin or the like, or the adhesion between the layers may be improved by an anchor effect by improving the permeability of the liquid used in the upper layer of the primer layer by a liquid that enhances wettability, or the fixability may be improved by quickly coagulating the liquid used in the upper layer.
  • the primer liquid is not particularly limited, but may be, for example, a metal salt solution such as a cationic pretreatment agent such as calcium nitrate, calcium chloride, zinc nitrate, zinc chloride, magnesium acetate, aluminum sulfate, or sodium chloride, or a cationic polymer solution containing ammonium ions.
  • a metal salt solution such as a cationic pretreatment agent such as calcium nitrate, calcium chloride, zinc nitrate, zinc chloride, magnesium acetate, aluminum sulfate, or sodium chloride, or a cationic polymer solution containing ammonium ions.
  • the applied primer liquid is preferably dried using a dryer 13 before proceeding to the next step.
  • a dryer 13 There are no particular limitations on the type of dryer 13 used in the drying step, and drying can be carried out appropriately using equipment similar to that used for the surface layer.
  • the intermediate layer is added to impart a high-quality texture and a soft feel to the synthetic leather 150.
  • the intermediate layer is preferably formed by in-line inkjet coating of the intermediate layer forming liquid 22 on the fibrous substrate, but may be applied in-line using a roll coater, knife coater, comma coater, or the like, or a laminate in which the intermediate layer is separately formed on the fibrous substrate offline may be used as the fibrous substrate 100.
  • the intermediate layer is preferably formed of urethane foam.
  • the urethane foam may be produced by foaming an aqueous dispersion of urethane resin for the intermediate layer, which is prepared by dispersing urethane resin in water with a surfactant, in the same manner as in the urethane resin composition described above, to obtain a foamed liquid, applying this foamed liquid as the intermediate layer forming liquid 22 to the fibrous substrate 100 or a substrate having a primer layer, and drying as necessary to obtain a desired density.
  • an aqueous dispersion of urethane resin containing a foaming agent may be used as the intermediate layer forming liquid 22, or an aqueous dispersion of urethane resin containing a volatile solvent, liquefied gas, hollow spheres, etc. may be used as the intermediate layer forming liquid 22, and any publicly known foaming method may be used.
  • the method of foaming the aqueous urethane resin dispersion for the intermediate layer to obtain a foamed liquid includes, for example, stirring by hand or using a mixer such as a mechanical mixer.
  • a mixer for example, stirring at 500 to 3,000 rpm for 10 seconds to 3 minutes can be used.
  • the inkjet method is preferred as a method for applying the intermediate layer forming liquid 22 to the fibrous substrate 100 or a substrate having a primer layer 110.
  • a foaming liquid as the intermediate layer forming liquid 22, it may be applied by using, for example, a roll coater, knife coater, comma coater, applicator, etc.
  • Application to the substrate may also be performed in-line.
  • the intermediate layer forming liquid 22 After applying the intermediate layer forming liquid 22, it is preferable to have an intermediate layer drying process. There are no particular limitations on the drying process, and drying can be carried out under appropriate conditions using the same equipment as for the surface layer.
  • the density of the urethane foam is preferably 200 to 1,000 kg/m 3 , more preferably 300 to 900 kg/m 3, and even more preferably 400 to 800 kg/m 3 , in that more preferable texture and tensile strength can be obtained.
  • the density of the urethane foam is a value calculated by dividing the mass of the urethane foam by its volume.
  • the intermediate layer made of urethane foam may be formed by a conventional method. Specifically, a urethane resin composition containing an organic solvent is applied to a fibrous substrate or the like, and then the substrate is immersed in water, whereby the solvent in the urethane resin composition is replaced with water, and the solid matter in the urethane resin composition precipitates to form a film. Next, the remaining solvent is thoroughly washed away with water, and the substrate is squeezed with a mangle roll or the like, and then dried to obtain a laminate in which an intermediate layer made of urethane foam is laminated on a fibrous substrate or the like.
  • the laminate may be used as a substrate, and a surface layer may be formed on the intermediate layer by an inkjet method to obtain synthetic leather.
  • a wet film-forming aid may be appropriately blended into the urethane resin composition of the present invention in order to adjust the film-forming speed and to obtain good surface smoothness.
  • the wet film-forming aid include castor oil, glycerin tripalmitate, and silicone oil. These wet film-forming aids may be used alone or in combination of two or more.
  • the thickness of the intermediate layer 120 is preferably in the range of, for example, 0.1 to 500 ⁇ m.
  • Synthetic leather produced by the synthetic leather manufacturing method of the present invention does not require release paper, and CO2 emissions during the manufacturing process are significantly reduced compared to conventional manufacturing methods, making it possible to reduce the environmental impact. Also, unlike conventional manufacturing methods, each process can be carried out in-line, which leads to increased manufacturing efficiency through automation. Furthermore, by forming each layer using the inkjet method, the amount of waste liquid in all processes, including cleaning, can be reduced, a decoration process is unnecessary, small-scale production is facilitated, and on-demand demand can be met.
  • the synthetic leathers 201 and 202 obtained by the manufacturing method of the present invention include surface skin layers 221 and 222.
  • the synthetic leathers 201 and 202 are preferably formed by laminating the surface skin layers 221 and 222 on cushion materials 211 and 212 made of urethane foam or the like corresponding to the base material. Another layer may be included between the cushion materials 211 and 212 and the surface skin layers 221 and 222.
  • the synthetic leathers 201 and 202 may further include a surface treatment layer on the surface skin layers 221 and 222.
  • the skin layers typified by the skin layers 221 and 222 have a function of reproducing the texture of natural leather, similar to the above-mentioned skin layer 130.
  • the skin layer is formed by an inkjet method, and is similar to the above-mentioned skin layer 130, and the preferred aspects are also similar.
  • the method for producing the cushioning material made of urethane foam or the like is not particularly limited, and it can be produced by a publicly known method, for example, by injecting a foaming raw material such as urethane foam into a mold and allowing it to foam.
  • the cushion material serving as the base material may include a skeleton frame, a connecting shaft, an airbag, an air cell, an air supply tube, a fluid cell, a fluid supply tube, a seat heater, a lumbar support portion, a pressure sensor, a position adjustment mechanism, etc. Also, it may be a laminate of a pre-treatment layer, an intermediate layer, a seat cover pad layer, a wadding layer, a pleated pad layer, etc.
  • the cushion material may be, for example, a seating sheet and a backrest sheet integrated together, or a seating sheet and a lumbar support portion separated from each other, and the shape of the cushion material is not particularly limited, and may be a suitable shape depending on the application.
  • the synthetic leather 201 may be, for example, a seat for a seating portion of a vehicle, and the synthetic leather 202 may be, for example, a seat for a backrest of a vehicle.
  • the synthetic leather 203 may also be a synthetic leather having a skin layer, and may be, for example, a headrest.
  • the synthetic leathers 201, 202, and 203 may be assembled to produce the vehicle seat 200.
  • FIG. 5 is a schematic diagram of one embodiment of the manufacturing method of the present invention.
  • a cushion material 212 made of urethane foam or the like is placed under the inkjet head 31.
  • the cushion material 212 is a three-dimensional object, and the cushion material 212 and the inkjet head 31 do not need to be placed downward in the direction of gravity. As long as the cushion material 212 is positioned in the direction of the nozzle surface of the inkjet head 31, they may be arranged side by side or upside down. There are no particular limitations on the method of transporting the cushion material 212.
  • the inkjet head 31 may be sent under the inkjet head 31 fixed by a belt conveyer or the like, or the inkjet head 31 may be brought close to a place where the cushion material 212 is fixed by a support rod or the like by an arm 300 (only a part of which is shown) holding the inkjet head 31.
  • the arm 300 may be capable of moving in one dimension, two dimensions, or three dimensions.
  • the inkjet head 31 may be a single movable head, multiple inkjet heads 31 may be fixed to a carriage or arm 300, or multiple arms 300 with one inkjet head 31 fixed thereto may be used.
  • the skin layer forming liquid 32 is discharged from the inkjet head 31 and dried by a dryer or the like as necessary. Drying may be performed simultaneously with inkjet discharge as long as drying of the inkjet head 31 can be suppressed.
  • the skin layer forming liquid 32 is discharged while changing the position of the inkjet head 31 and the position of the cushion material 212 as necessary, and a uniform skin layer 222 is formed on the cushion material 212, thereby producing synthetic leather 202 to be used as a seat for the backrest of a vehicle.
  • a stage or support rod to which the cushion material 212 is fixed may be one that rotates, or a carriage or arm 300 to which the inkjet head 31 is fixed may be one that is movable.
  • another layer e.g., a primer layer, an intermediate layer, a seat cover pad layer, a wadding layer, a pleat pad layer, a surface treatment layer, etc.
  • the lamination method is not particularly limited, and may be spray painting, dip coating, or inkjet coating similar to that for the surface layer.
  • the process for forming the above-mentioned epidermal layer by the inkjet method is the same as the epidermal layer formation process in FIG. 1, and the preferred embodiment is also the same.
  • the inkjet head 31 and the epidermal layer formation liquid 32 can be the same as the inkjet head and the epidermal layer formation liquid described above.
  • the formation process and drying process of the other layers are also the same as the method described above, and the preferred embodiment is also the same.
  • the thickness meter is not particularly limited, and a known one can be used, for example, an electromagnetic thickness meter, an eddy current thickness meter, an ultrasonic thickness meter, a reflection spectroscopic thickness meter, a fluorescent X-ray thickness meter, etc. can be used. It is preferable to use a reflection spectroscopic thickness meter, a fluorescent X-ray thickness meter, etc., which are non-contact thickness meters advantageous for in-line measurement. However, if in-line measurement is not performed, the film thickness can also be determined from cross-sectional photographs of the synthetic leather taken with an electron microscope. Any method that can determine the film thickness can be applied, and there are no particular limitations.
  • the present invention further provides an apparatus for producing synthetic leather, which comprises a substrate transport means, an inkjet head, and a dryer, and forms a skin layer by an inkjet method, thereby achieving a significant reduction in the number of steps and in the amount of waste liquid and waste materials (such as release paper) including those produced during the cleaning process.
  • an apparatus for producing synthetic leather which comprises a substrate transport means, an inkjet head, and a dryer, and forms a skin layer by an inkjet method, thereby achieving a significant reduction in the number of steps and in the amount of waste liquid and waste materials (such as release paper) including those produced during the cleaning process.
  • the substrate transport means in the manufacturing apparatus may be realized by the substrate roll 70 and product winding roll 80 in FIG. 1, or may be realized by other means.
  • the inkjet head corresponds to the skin layer inkjet head 31 in FIG. 1 described above.
  • the dryer may be a dryer similar to the skin layer dryer 33 in FIG. 1 described above.
  • the manufacturing apparatus of the present invention may further include a film thickness measuring means, an intermediate layer foaming means, and other devices.
  • the present invention also provides a synthetic leather manufacturing device that is equipped with an inkjet head moving means, an inkjet head, and a dryer, and forms a skin layer using an inkjet method.
  • This manufacturing device can significantly reduce the number of processes and reduce waste liquid and waste materials (cut scraps, etc.) including the cleaning process.
  • the inkjet head moving means in the manufacturing apparatus may be a carriage or arm 300 to which the inkjet head is fixed, or may be other means.
  • the inkjet head corresponds to the epidermal layer inkjet head 31 in FIG. 5 described above.
  • the dryer may be a dryer similar to the epidermal layer dryer 33 described above.
  • a methyl ethyl ketone solution of a urethane prepolymer having an isocyanate group at the molecular end 51 parts by mass of triethylamine was added to the methyl ethyl ketone solution of the urethane prepolymer obtained above to neutralize the carboxyl groups in the urethane prepolymer, and then 1555 parts by mass of ion-exchanged water was added, followed by adding 128 parts by mass of isophorone diamine to cause a reaction. After completion of the reaction, methyl ethyl ketone was removed under reduced pressure at a temperature of 40° C. to 60° C., and water was added to adjust the concentration, thereby obtaining a urethane resin aqueous dispersion (A-1) having a nonvolatile content of 35% by mass.
  • A-1 urethane resin aqueous dispersion
  • a methyl ethyl ketone solution of a urethane prepolymer having an isocyanate group at the molecular terminal 14.3 parts by mass of 25% aqueous ammonia solution was added to the methyl ethyl ketone solution of the urethane prepolymer obtained above, and the carboxyl groups in the urethane prepolymer were neutralized, and then 1504 parts by mass of ion-exchanged water was added, and then 1.1 parts by mass of hydrazine was added to react. After the reaction was completed, methyl ethyl ketone was removed under reduced pressure at a temperature of 40° C. to 60° C., and water was added to adjust the concentration, thereby obtaining a urethane resin aqueous dispersion (A-2) with a non-volatile content of 23% by mass.
  • A-2 urethane resin aqueous dispersion
  • a leveling agent BYK-3455 (manufactured by BYK Japan Co., Ltd.) and 0.1 g of a defoaming agent BYK-093 (manufactured by BYK Japan Co., Ltd.) were then added, and a thickener ADEKA NOL UH-420 (manufactured by ADEKA Corporation) was added so that the viscosity became about 3,000 mPa ⁇ s. After that, the mixture was stirred for 10 minutes to prepare a black coating material (C-3) for forming a skin layer.
  • ADEKA NOL UH-420 manufactured by ADEKA Corporation
  • a leveling agent BYK-3455 (manufactured by BYK Japan Co., Ltd.) and 0.1 g of a defoaming agent BYK-093 (manufactured by BYK Japan Co., Ltd.) were then added, and a thickener ADEKA NOL UH-420 (manufactured by ADEKA Corporation) was added so that the viscosity became about 3,000 mPa ⁇ s. After that, the mixture was stirred for 10 minutes to prepare a white coating material (C-4) for forming a surface layer.
  • ADEKA NOL UH-420 manufactured by ADEKA Corporation
  • Example 1 Preparation of synthetic leather 1
  • the nonwoven fabric was immersed in a coagulant (aqueous solution of 5% by weight calcium nitrate) for 10 seconds, and then dried to prevent penetration.
  • the aqueous adhesive layer paint was applied to the nonwoven fabric using a knife coater to a thickness of 150 ⁇ m, and then dried using a hot air dryer (90-100°C x 3 minutes).
  • a printing device equipped with a Kyocera inkjet head KJ4B-YH was filled with the black skin layer forming liquid (C-1). After that, the gap between the inkjet head and the dried coating film of the adhesive layer paint was set to 3 mm, and the nozzle surface of the inkjet head was wiped.
  • Synthetic leather 1 was produced by repeating (1) to (3) until the film thickness after drying was about 30 ⁇ m.
  • Example 2 Preparation of synthetic leather 2
  • Synthetic leather 2 was produced through the same steps as in Example 1, except that the black skin layer forming liquid (C-1) was changed to a white skin layer forming liquid (C-2).
  • Synthetic leather 4 was produced by the same process as in Comparative Example 1, except that the black paint for forming the surface layer (C-3) was changed to the white paint for forming the surface layer (C-4).
  • a 2.5 cm wide hot melt tape (“BW-2” manufactured by Sun Chemical Industry Co., Ltd.) was placed on the synthetic leather obtained in the Examples and Comparative Examples, and heated at 150°C for 3 minutes to adhere. A sample was cut along the width of the hot melt tape. A portion of this sample was peeled off, and the substrate and hot melt tape were clamped with a chuck, and the peel strength was measured using an autograph ("AG-1” manufactured by Shimadzu Corporation) and converted to a 1 cm width. A peel strength of 1 kgf/cm or more was determined to be excellent. "T”: Excellent peel strength. "F”: The peel strength is insufficient.
  • the inkjet inks obtained in Production Examples 6 and 7 were filled into an inkjet head KJ4B-YH manufactured by Kyocera Corporation, and the supply pressure was adjusted by setting the head head head water head difference from the head nozzle plate surface to +35 cm and the negative pressure to -5.0 kPa.
  • the head driving conditions were the standard voltage and standard temperature of the inkjet head, the droplet size was set to 18 pL, and a lattice-shaped nozzle check pattern was printed at 20 kHz. After leaving it for 30 minutes, a nozzle check pattern was printed again, and the state of the printed matter was confirmed to determine the inkjet discharge reliability.
  • T The check pattern is printed without any missing parts.
  • "F” There is a gap in the check pattern or the pattern has not been printed.
  • Table 1 summarizes the evaluation results for the examples and comparative examples.
  • the synthetic leathers of Examples 1 and 2 which are produced by the synthetic leather production method of the present invention, were obtained without using release paper, which eliminated the waste of release paper. Furthermore, there were no problems with the texture and peel strength of the synthetic leather. It has been found that the method for producing synthetic leather of the present invention can reduce the amount of waste and greatly contribute to environmental friendliness.

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018127736A (ja) * 2017-02-08 2018-08-16 株式会社クラレ インクジェット印刷人工皮革及び加飾成形体
JP2019072914A (ja) * 2017-10-16 2019-05-16 株式会社ミマキエンジニアリング 立体模様印刷物の製造方法
JP2021046515A (ja) * 2019-09-20 2021-03-25 株式会社リコー インク、インクセット、印刷方法、及び印刷装置
JP2023065062A (ja) * 2021-10-27 2023-05-12 旭化成株式会社 人工皮革及びその製法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018127736A (ja) * 2017-02-08 2018-08-16 株式会社クラレ インクジェット印刷人工皮革及び加飾成形体
JP2019072914A (ja) * 2017-10-16 2019-05-16 株式会社ミマキエンジニアリング 立体模様印刷物の製造方法
JP2021046515A (ja) * 2019-09-20 2021-03-25 株式会社リコー インク、インクセット、印刷方法、及び印刷装置
JP2023065062A (ja) * 2021-10-27 2023-05-12 旭化成株式会社 人工皮革及びその製法

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