WO2014192249A1 - Urethane foam sheet, cushion material, and method for producing urethane foam sheet - Google Patents

Urethane foam sheet, cushion material, and method for producing urethane foam sheet Download PDF

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WO2014192249A1
WO2014192249A1 PCT/JP2014/002643 JP2014002643W WO2014192249A1 WO 2014192249 A1 WO2014192249 A1 WO 2014192249A1 JP 2014002643 W JP2014002643 W JP 2014002643W WO 2014192249 A1 WO2014192249 A1 WO 2014192249A1
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film
sheet
water
urethane
foam sheet
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PCT/JP2014/002643
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French (fr)
Japanese (ja)
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前田　裕司
範幸 世羅
岳志 河上
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日本発條株式会社
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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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0278—Polyurethane
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/56—Damping, energy absorption
    • 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
    • B32B2439/00—Containers; Receptacles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes

Definitions

  • the present invention relates to a foamed urethane sheet, a cushioning material and a foamed urethane sheet having a thickness of 0.01 to 0.15 mm, which are useful for cushioning packing, waterproof packing, waterproof sheet, moisture permeable sheet, water absorbent sheet and the like. It relates to the manufacturing method.
  • urethane foams are used as cushioning materials for liquid crystals because of their flexibility and shock absorption, and thinner cushioning materials are required due to the recent thinning of products.
  • a silicone sheet having a thickness of about 0.1 mm as a thin sheet.
  • Silicone sheets are used as cushioning materials for liquid crystal televisions because of their low dust generation, mechanical strength, and slipperiness during processing, but the fact is that their shock absorption does not satisfy the requirements.
  • a foamed urethane sheet has been proposed in which a shrinkage is reduced by adding a large amount of a plasticizer, a filler, or a crosslinking agent to the foamed sheet.
  • the thickness can be easily controlled by foaming the raw material before coating.
  • the foamed urethane cannot be made as thin as 10 to 100 ⁇ m.
  • a urethane foam sheet of 0.1 to 3.0 mm is integrated with a polyethylene terephthalate film having a thickness of 0.01 to 0.1 mm for the purpose of facilitating handling such as shape retention and for the purpose of reinforcement.
  • a base material such as polyethylene terephthalate film
  • a polyethylene terephthalate film with a matte surface as the surface of the base material or electrostatic treatment or corona treatment to increase wettability
  • the conventional method of integrating the polyethylene terephthalate film and the foamed urethane sheet could not be applied due to peeling during drying or repelling after coating. Therefore, a polyester resin having a contact angle with water after 3 minutes of 55 ° or more is smoothly applied to a substrate that is a polyethylene terephthalate film by a method such as coating, transfer, spraying, and the like, and is handled by drying. It was confirmed that a urethane foam sheet integrated with a tape base material such as a polyethylene terephthalate film that can be reinforced and can be reinforced and does not shrink is obtained.
  • the present invention has been made in view of the above-mentioned circumstances, and the object thereof is as described above, being thin (thickness is 0.15 mm or less), rich in flexibility, having a fine uniform structure, and handling. It is an object to provide a foamed urethane sheet with a base material, a cushioning material, and a foamed urethane sheet that are easy to handle, have high strength, and do not shrink.
  • the characteristics of the urethane sheet targeted by the present invention are as follows. (1) The thickness is 0.15 mm or less. (2) Thickness accuracy is high (within 10% of soil) and surface flatness is high. (3) The foam is softer than the silicone sheet.
  • the foamed urethane sheet according to claim 1 of the present invention is a polyethylene terephthalate film, a polypropylene film or a methylpentene polymer film obtained by mixing a mixture of a urethane resin, an organic solvent, water and a fluorosurfactant.
  • the foamed urethane sheet is a sheet that is coated and integrated with a film of an organic synthetic polymer material such as polyethylene terephthalate, polypropylene, or methylpentene polymer. It becomes a urethane sheet.
  • the urethane foam sheet according to claim 2 of the present invention is characterized in that the thickness including the foam and the base material is 0.01 to 0.15 mm. With this configuration, it is more flexible than a silicone sheet, can satisfy the demand for shock absorption, and has satisfactory performance as a cushioning material for a liquid crystal television.
  • a surface treatment for adhering to the foam is applied to the other surface of the base material having the adhesive layer on one surface. It is a saturated polyester surface treatment agent having a contact angle with water later of 55 ° or more. By this structure, it becomes a foaming urethane sheet which has moderate 50% compression hardness and elongation, and also has the outstanding tensile strength.
  • fluorosurfactant examples include perfluoroalkylene ethylene oxide adducts, for example, trade name Surflon S-420 manufactured by AGC Seikagaku Co., Ltd., trade name Megafac F-444 manufactured by DIC Corporation, and perfluoroalkenyl polyethylene oxide. Additives such as Footage 250 and FTX-218 manufactured by Neos Co., Ltd. can be mentioned.
  • the cushion material according to claim 5 of the present invention is characterized by comprising the urethane foam sheet according to any one of claims 1 to 3. With this configuration, the cushion material has a low 50% compressive force, is flexible, and has excellent resilience.
  • the cushioning material according to claim 6 of the present invention is characterized in that the contact angle with water is 90 ° or more and is hydrophobic. With this configuration, the water repellency is high, and the water absorption and water swellability are low. Therefore, it is a sheet suitable for a polishing holding pad, a waterproof packing, a waterproof sheet or the like when polishing a hard disk substrate, a silicon wafer, a glass substrate for a liquid crystal display or the like as a buffer packing.
  • the cushion material according to claim 7 of the present invention is characterized in that the contact angle with water is less than 90 ° and is water-absorbing.
  • the urethane foam sheet constituting the cushion material is composed of fine cells having a continuous ventilation structure, and is excellent in moisture permeability and water permeability, so it is suitable for moisture permeable sheets, water absorbent sheets and the like. It becomes a sheet.
  • the method for producing a foamed urethane sheet according to claim 8 of the present invention includes a polyol, a polyisocyanate, a foaming agent, a fluorosurfactant, a catalyst, an organic solvent containing toluene and methyl ethyl ketone, and a crosslinking agent, if necessary.
  • a compound such as an additive selected from an agent, a flame retardant, an ultraviolet absorber, and a durability improver, and any one of a polyethylene terephthalate film, a polypropylene film, and a methylpentene film
  • the dispersion stability of the blended mixed raw material is high, so the production time can be lengthened, and thus the production cost can be reduced, and the flatness, cell uniformity, impact A foamed urethane sheet excellent in absorbency, mechanical strength, and abrasion resistance can be easily produced.
  • the adhesive strength is that obtained by attaching the urethane foam sheet to the substrate with an adhesive. In addition to being stronger, it is economical because it can save labor and equipment for bonding using another process.
  • a base material used for the foamed urethane sheet of the present invention various plastic films can be considered. From the viewpoint of strength, heat resistance, dimensional stability, a polyethylene terephthalate film, a polypropylene film, or a methylpentene polymer film is particularly preferable. preferable.
  • the method for producing a foamed urethane sheet according to claim 9 of the present invention is characterized in that the fluorosurfactant is a perfluoroalkylethylene oxide adduct or a perfluoroalkenyl polyethylene oxide adduct.
  • the perfluoroalkylene ethylene oxide adduct include, for example, trade name Surflon S-420 manufactured by AGC Sey Chemical Co., Ltd., trade name of Megafic F-444 manufactured by DIC Corporation, and examples of perfluoroalkenyl polyethylene oxide adduct include, for example, Examples include Neogent's Footage 250 and FTX-218.
  • the foamed urethane with a base material has high flexibility, a fine uniform structure, high shock absorption, and reduced shrinkage. Can provide a sheet.
  • the substrate 2 may be any one of a polyethylene terephthalate (hereinafter abbreviated as PET) film, a polypropylene (hereinafter abbreviated as PP) film, and a methylpentene polymer (hereinafter abbreviated as TPX) film obtained by polymerizing 4-methylpentene-1.
  • the film 3 has an adhesive layer 4 on one side.
  • PET100GS manufactured by Lintec Corporation is used as the film 3.
  • thermoplastic polyurethane solution Zoltex PX-550 manufactured by DIC Corporation
  • 2 parts of an isocyanate prepolymer CL-15 manufactured by DIC Corporation
  • an organotin catalyst manufactured by DIC Corporation
  • 2 parts of T.81E) and 1 part of a surfactant Surflon S-420 manufactured by AGC Seimi Chemical Co., Ltd.
  • a reaction is performed for 70 ° C. ⁇ 5 min, and then 120 ° C. ⁇ 20 min (10 to 30 min) to obtain a foamed urethane sheet in which the foam 1 is integrated on the substrate 2.
  • the addition amount of the surfactant is 0.68 parts or more, and a more preferable range is 0.68 to 4 parts.
  • Fluorosurfactants include perfluoroalkylethylene oxide adduct (Surflon S-420 manufactured by AGC Seimi Chemical Co., Ltd.), perfluoroalkylethylene oxide adduct (Megafac F-444 manufactured by DIC Corporation), and perfluoroalkenyl polyethylene oxide adduct. (Foogent 250, FTX-218 manufactured by Neos Co., Ltd.) is preferable.
  • the surfactant By adding the surfactant, the mixing and dispersibility (emulsification) of water and solvent is stabilized, and a foam stabilizing effect is obtained. Further, the contact angle can be adjusted by changing the addition amount of the crosslinking agent and the surfactant, and a foamed film from hydrophilic to hydrophobic can be produced.
  • paper and polypropylene laminate film can be used in addition to the PET film, PP film, TPX film obtained by polymerizing 4-methylpentene-1.
  • a foam (thermoplastic polyurethane resin or thermosetting polyurethane resin) 1 is provided on one surface of the film 3.
  • a separator (not shown) is detachably attached to the adhesive layer 4. When using this urethane foam sheet, the separator (not shown) bonded to the adhesive layer 4 is peeled off and then attached to a fixed plate or the like.
  • the foamed urethane sheet may be either thermoplastic or thermosetting resin as long as it is a polyurethane made by polyaddition of diisocyanate and polyol as long as it has the characteristics described in claim 1. .
  • a fluorosurfactant is particularly preferable from the viewpoints of the stability of the raw material of the obtained urethane foam sheet, surface flatness, cell uniformity, low air permeability, waterproofness / water absorption, and delamination force.
  • the foamed urethane sheet is selected from polyols, polyisocyanates, foaming agents, fluorosurfactants, if necessary, catalysts and crosslinking agents, colorants, resin modifiers, flame retardants, UV absorbers, and durability improvers.
  • the blended raw material obtained by mixing and stirring the blended additive, etc. is uniformly applied to the release surface of the release-processed paper, and then heated in an oven at 60 to 70 ° C. for methyl ethyl ketone. (MEK), an extremely thin foamed urethane with a thickness of 0.01 to 0.1 mm, by evaporating an organic solvent such as toluene and then heating in an oven at 90 to 120 ° C. to evaporate water. It was the first practical success in producing a sheet.
  • any material can be used without any limitation as long as it has been conventionally used as a raw material for polyurethane resin synthesis.
  • polyether urethane Zoltex PX-550 manufactured by DIC Corporation, HI-MURENATX series manufactured by Dainichi Seika Kogyo Co., Ltd.
  • Zoltex PX-550 manufactured by DIC Corporation
  • HI-MURENATX series manufactured by Dainichi Seika Kogyo Co., Ltd.
  • organic solvent for diluting the polyurethane resin examples include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, aromatic solvents such as toluene and xylene, ester solvents such as ethyl acetate and butyl acetate, isopropyl alcohol, and t-butyl.
  • Alcohol solvents such as alcohol and mixed solvents thereof can be used, but a mixed solution of toluene and methyl ethyl ketone is a particularly preferable dilution solvent from the viewpoint of storage stability of the raw material mixture solution.
  • foaming agent examples include microcapsules having an acrylonitrile skeleton that generates water, propane, butane, and the like. Further, instead of water, pressurized gas foaming may be performed using carbon dioxide gas or nitrogen gas after 70 ° drying.
  • a fluorosurfactant as described above in the method for producing a foamed urethane sheet, a fluorosurfactant is used. Thereby, the mixing dispersibility (emulsification) of water and a solvent is stabilized, and a preferable foam regulating effect is obtained. Furthermore, as described in the production method, the contact angle with water can be adjusted by changing the addition amount of the catalyst, the crosslinking agent and the surfactant.
  • the foamed urethane sheets according to the examples and comparative examples are prepared by first preparing a diluent solvent consisting of polyol, polyisocyanate, MEK and toluene, water, a fluorosurfactant, and if necessary a catalyst and a crosslinking agent. Mix.
  • reaction raw material obtained by mixing and stirring the blend is uniformly applied to the release surface of a process paper such as a PET film which has been subjected to a release treatment using an application bar.
  • the reaction raw material applied to the process paper is heated in an oven at 60 to 70 ° C. to evaporate the diluted solvent, and then foamed and cured while evaporating water in the oven at 90 to 120 ° C.
  • a foamed urethane sheet composed of fine cells can be obtained.
  • Example and comparative example of this foaming urethane sheet are given, and the various characteristics of each foaming urethane sheet are shown below. A method for evaluating these characteristics will be described later.
  • diltin dilaurate ethyl acetate / 2-butanone solution
  • the prepared liquid is further stirred for 5 minutes with a stirrer / defoamer, and then a 0.025 mm thick one side is coated with a polyester coating at a contact angle of 75 ° after 3 minutes, and the other side is a PET film base having an adhesive layer
  • a polyurethane foamed urethane sheet material having a thickness of 0.1 mm and a density of 510 kg / m3 was obtained.
  • the shrinkage ratio of this foamed urethane sheet material was 0%.
  • a polyester film base having a contact angle of 60 ° after 3 minutes on one side of 0.025 mm thickness and a pressure-sensitive adhesive layer on the other side was applied uniformly to obtain a polyurethane foamed urethane sheet material having a thickness of 0.04 mm and a density of 570 kg / m 3 .
  • the shrinkage ratio of this urethane foam sheet was 0%.
  • a polyester film base having a contact angle of 60 ° after 3 minutes on one side of 0.025 mm thickness and a pressure-sensitive adhesive layer on the other side was applied uniformly to obtain a polyurethane foamed urethane sheet material having a thickness of 0.1 mm and a density of 507 kg / m 3 .
  • the shrinkage ratio of this urethane foam sheet was 0%.
  • Various characteristics of the urethane foam sheets of Examples 1 to 5 are shown in Table 1.
  • Dry urethane raw material polyether urethane crosslinker; hexamethylene diisocyanate prepolymer, hexamethylene diisocyanate catalyst solution; organotin catalyst containing less than 1% (dibutyltin dilaurate) ethyl acetate / 2-butanone solution
  • surfactant A perfluoroalkyl Ethylene oxide copolymer (Surflon S-420 manufactured by AGC Seimi Chemical Co., Ltd.)
  • Surfactant B Perfluoroalkenyl polyethylene oxide adduct (Neos Corporation's Footgent 251)
  • Plasticizer dialkylene glycol dibenzoate (PB-3A manufactured by DIC Corporation) Coating Agent; Silicone; Silicone Release Coating, Polyester; Saturated Polyester Coating A comparative example is shown below.
  • a polyurethane foam urethane sheet material having a density of 500 kg / m 3 was obtained.
  • the shrinkage ratio of this foamed urethane sheet material was 5%, and a foamed urethane sheet with poor post-processability was obtained.
  • the prepared liquid is further stirred for 5 minutes with a stirrer / defoamer, and then uniformly applied to a base material subjected to a silicone release treatment on one side of a PET film having a thickness of 0.025 mm.
  • a polyurethane foamed urethane sheet material having a density of 580 kg / m 3 was obtained.
  • the shrinkage rate of this foamed urethane sheet material was 1.5%, a foamed urethane sheet having a 50% compression hardness of the foamed urethane sheet was obtained.
  • the prepared liquid is further stirred for 5 minutes with a stirrer / defoamer, and then uniformly applied to a base material subjected to a silicone release treatment on one side of a PET film having a thickness of 0.025 mm.
  • a polyurethane foam urethane sheet material having a density of 720 kg / m 3 was obtained. Although the shrinkage ratio of this foamed urethane sheet was 2.0%, a high-density foamed urethane sheet was obtained.
  • the prepared liquid is further stirred for 5 minutes with a stirrer / defoamer, and then a PET film having a contact angle of 25 ° after 3 minutes is applied to one side of a PET film having a thickness of 0.025 mm, and an adhesive layer is provided on the other side.
  • a nonuniform and uneven foamed urethane sheet was obtained.
  • Various characteristics of the urethane foam sheets of Comparative Examples 1 to 5 are shown in Table 2.
  • Dry urethane raw material polyether urethane (DIC Corporation Soltex PX-550) Hexamethylene diisocyanate prepolymer, hexamethylene diisocyanate catalyst solution; organotin catalyst containing less than 1% (dibutyltin dilaurate) ethyl acetate / 2-butanone solution surfactant A; perfluoroalkylethylene oxide copolymer (AGC Seimi) Chemical Corporation Surflon S-420) Plasticizer: dialkylene glycol dibenzoate (PB-3A manufactured by DIC Corporation) Coating agent; Silicone; Silicone release coating, Polyester; Saturated polyester coating
  • the value of the evaluation item (test item) of the various characteristics is measured as follows. Density: Physical property test of flexible polyurethane foam: Conforms to JIS K 6400. Contact angle: 15 ⁇ L of water was dropped onto the foam skin surface, and the contact angle after 3 minutes was measured with a contact angle meter. As the contact angle meter, a Kyowa contact angle meter (manufactured by CA-A Kyowa Scientific Co., Ltd.) was used. Tensile strength / elongation; Physical property test of flexible polyurethane foam: Conforms to JIS K 6400. The tensile strength was measured at 200 mm / min.
  • 50% compression hardness Compression stress value when two 30 ⁇ 30 mm samples are laminated and compressed by 50% at a speed of 1 mm / min.
  • the measuring instrument used was autograph AG-X manufactured by Shimadzu Corporation. Unit: MPa.
  • Bleed out The surface transition of the additive is visually confirmed by contacting the foamed urethane sheet.
  • the present invention has the effect that it is possible to provide a foamed urethane sheet with a base material that is thin, flexible, and has a fine uniform structure, such as a cushioning packing, a waterproof packing, a waterproof sheet, a moisture permeable sheet, and a water absorbent sheet. It is useful for an ultrathin sheet-like foamed urethane sheet having a shrinkage rate of 0 and a thickness of 0.01 to 0.15 mm, a method for producing the same, and the like.

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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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Abstract

The purpose of the present invention is to provide a urethane foam sheet with a substrate. The urethane foam sheet is thin, has excellent flexibility and a fine uniform structure, is easy to handle, has high strength, and does not contract. This urethane foam sheet is characterized by comprising a foam obtained by applying a mixture of a urethane resin, an organic solvent, water and a fluorine-based surfactant to one side of a substrate, which is a film of any one of a polyethylene terephthalate film, a polypropylene film or a methylpentene polymer film, and then applying heat. The urethane foam sheet is further characterized in that the organic solvent is a mixed solution of toluene and methyl ethyl ketone, and the foam is constituted by microcells having a continuous ventilation structure.

Description

発泡ウレタンシート、クッション材および発泡ウレタンシートの製造方法Urethane foam sheet, cushion material, and method for producing foamed urethane sheet
　本発明は、緩衝用パッキン、防水パッキン、防水シート、透湿性シート、吸水シートなどに有用な、厚さ０．０１～０．１５ｍｍの極薄シート状の発泡ウレタンシート、クッション材および発泡ウレタンシートの製造方法に関する。 The present invention relates to a foamed urethane sheet, a cushioning material and a foamed urethane sheet having a thickness of 0.01 to 0.15 mm, which are useful for cushioning packing, waterproof packing, waterproof sheet, moisture permeable sheet, water absorbent sheet and the like. It relates to the manufacturing method.
　現在本出願人は薄物緩衝用シートとして発泡ウレタンシートを市販しているが、その最低厚みは０．３ｍｍである。一方、メカニカルフロス方式で生産されたウレタン発泡シートも市場に見られるが、このシートは塗布前の原料泡立てにより厚み制御が容易に行えるため、厚み０．２ｍｍの製品が実用化されている。しかし、これより薄い製品は市販されておらず、現在の生産方式では厚み０．１ｍｍが技術的な生産限界であると考えられている（例えば、特許文献１参照）。 Currently, the present applicant sells a foamed urethane sheet as a thin material cushioning sheet, but its minimum thickness is 0.3 mm. On the other hand, a urethane foam sheet produced by the mechanical floss method is also found in the market. Since this sheet can be easily controlled in thickness by foaming the raw material before coating, a product having a thickness of 0.2 mm has been put into practical use. However, products thinner than this are not commercially available, and in the current production system, a thickness of 0.1 mm is considered to be the technical production limit (see, for example, Patent Document 1).
　これらウレタン発泡体は柔軟性・衝撃吸収性から液晶用の緩衝材として使用されており、近年の製品薄型化により更に薄いクッション材が求められている。これとは別に、薄物シートとして０．１ｍｍ厚み程度のシリコーンシートがある。しかしながら、柔軟性、衝撃吸収性に劣るため、携帯電話の液晶用途には使用出来ない。シリコーンシートは、加工時の低発塵性、機械的強度、滑り性から液晶テレビのクッション材として使用されているが、衝撃吸収性は要求を満足していないのが実状である。 These urethane foams are used as cushioning materials for liquid crystals because of their flexibility and shock absorption, and thinner cushioning materials are required due to the recent thinning of products. Apart from this, there is a silicone sheet having a thickness of about 0.1 mm as a thin sheet. However, since it is inferior in flexibility and shock absorption, it cannot be used for liquid crystal applications of mobile phones. Silicone sheets are used as cushioning materials for liquid crystal televisions because of their low dust generation, mechanical strength, and slipperiness during processing, but the fact is that their shock absorption does not satisfy the requirements.
　また、柔軟な薄物シート材は、肉薄で樹脂特有の収縮性を持つために抜き型を用いた打抜き加工や両面テープを貼り合わせるラミネート加工などの後加工工程時に発泡シートが収縮してカールや寸法変化を生じ、取り扱いが難しくなる。そこで、このような課題を解決するものとして従来から発泡シートに可塑剤やフィラー、または架橋剤を多量に添加して収縮性を低減させた発泡ウレタンシートが提案されている。 In addition, since flexible thin sheet materials are thin and have resin-specific shrinkage properties, the foamed sheet shrinks during post-processing such as punching using a punching die or laminating with double-sided tape, and curls and dimensions. Changes are made and handling becomes difficult. In order to solve such problems, conventionally, a foamed urethane sheet has been proposed in which a shrinkage is reduced by adding a large amount of a plasticizer, a filler, or a crosslinking agent to the foamed sheet.
　ところが、発泡シートに可塑剤、フィラ＋ーや架橋剤を多量に添加させた場合、発泡シートからのブリードアウトが生じたり、発泡シートが硬くなったりして、発泡シートのクッション性が低下してしまうとういう不都合があった。また、前述のメカニカルフロス方式は塗布前の原料泡立てにより厚み制御が容易に行えるものの、原料を希釈していないため１０～１００μｍと薄い発泡ウレタンにすることができない。 However, when a large amount of plasticizer, filler +-, or cross-linking agent is added to the foam sheet, bleeding out from the foam sheet occurs, or the foam sheet becomes hard, and the cushioning property of the foam sheet decreases. There was an inconvenience. In the mechanical floss method, the thickness can be easily controlled by foaming the raw material before coating. However, since the raw material is not diluted, the foamed urethane cannot be made as thin as 10 to 100 μm.
　また、０．１～３．０ｍｍのウレタン発泡シートは、形状保持性などの取扱いを容易にするためや補強の目的で０．０１～０．１ｍｍの厚みのポリエチレンテレフタレートフィルム等が一体化されている。一般的にポリエチレンテレフタレートフィルム等の基材と発泡ウレタンシートとを一体化するには、基材の表面をマット調の凹凸面としたポリエチレンテレフタレートフィルムや濡れ性を上げるために静電力処理、コロナ処理、超音波処理または温熱処理等によって、反応固化させ、密着性を高め、ウレタン樹脂と接着させることが一般的である（例えば、特許文献２参照）。 In addition, a urethane foam sheet of 0.1 to 3.0 mm is integrated with a polyethylene terephthalate film having a thickness of 0.01 to 0.1 mm for the purpose of facilitating handling such as shape retention and for the purpose of reinforcement. Yes. In general, in order to integrate a base material such as polyethylene terephthalate film with a foamed urethane sheet, a polyethylene terephthalate film with a matte surface as the surface of the base material or electrostatic treatment or corona treatment to increase wettability It is common to react and solidify by ultrasonic treatment or thermothermal treatment to improve adhesion and adhere to a urethane resin (see, for example, Patent Document 2).
特許第４６７７１３４号公報Japanese Patent No. 4677134 特許第３９０３２４４号公報Japanese Patent No. 3903244
　しかしながら、従来のポリエチレンテレフタレートフィルムと発泡ウレタンシートとの一体化の方法では、乾燥中の剥離や塗工後のハジキにより適用することができなかった。そこで、３分後の水との接触角が５５°以上のポリエステル系樹脂を、コーティング、転写、スプレー等の方法によってポリエチレンテレフタレートフィルムである基材に平滑に塗布し、乾燥させることによって、取扱いを容易化できるほか補強化でき、かつ収縮の生じないポリエチレンテレフタレートフィルム等のテープ基材一体化発泡ウレタンシートが得られることを確認した。 However, the conventional method of integrating the polyethylene terephthalate film and the foamed urethane sheet could not be applied due to peeling during drying or repelling after coating. Therefore, a polyester resin having a contact angle with water after 3 minutes of 55 ° or more is smoothly applied to a substrate that is a polyethylene terephthalate film by a method such as coating, transfer, spraying, and the like, and is handled by drying. It was confirmed that a urethane foam sheet integrated with a tape base material such as a polyethylene terephthalate film that can be reinforced and can be reinforced and does not shrink is obtained.
　本発明は、上述した諸事情に鑑みてなされたものであり、その目的は、上記したように、薄くて（厚みが０．１５ｍｍ以下）、柔軟性に富み、微細均一構造を有するとともに、取扱いが容易で、強度が高く、しかも収縮が生じない基材付きの発泡ウレタンシート、クッション材および発泡ウレタンシートの製造方法を提供することにある。
　換言すれば、本発明が目的とするウレタンシートの特性は以下の通りである。
（１）厚みが０．１５ｍｍ以下であること。
（２）厚み精度が高く（土１０％以内）、表面の平坦性が高いこと。
（３）発泡体であり、シリコーンシートよりも柔軟であること。
（４）フォーム内での上下構造に大きな差が無く均一性の高い構造であること。
（５）表面に開孔が均一にあり、フォーム全体が微細な連続通気構造であること。
（６）衝撃吸収性を有すること。
（７）引張・引裂・層間強度が高く、打抜き・テープ粘りなどの加工に支障がないこと。
（８）耐磨耗性があり、発塵性が低いこと。
（９）長期耐久性に優れること。
（１０）基材と一体化して長さ方向の収縮率が小さいこと。
（１１）（可能であれば）人工皮革のような耐候性を有すること。 The present invention has been made in view of the above-mentioned circumstances, and the object thereof is as described above, being thin (thickness is 0.15 mm or less), rich in flexibility, having a fine uniform structure, and handling. It is an object to provide a foamed urethane sheet with a base material, a cushioning material, and a foamed urethane sheet that are easy to handle, have high strength, and do not shrink.
In other words, the characteristics of the urethane sheet targeted by the present invention are as follows.
(1) The thickness is 0.15 mm or less.
(2) Thickness accuracy is high (within 10% of soil) and surface flatness is high.
(3) The foam is softer than the silicone sheet.
(4) A highly uniform structure with no significant difference in the upper and lower structures in the foam.
(5) The surface has uniform holes and the entire foam has a fine continuous ventilation structure.
(6) Having shock absorption.
(7) Tensile, tearing, and interlayer strength are high, and there is no hindrance to processing such as punching and sticking to tape.
(8) Wear resistance and low dust generation.
(9) Excellent long-term durability.
(10) The shrinkage rate in the length direction is small by integrating with the base material.
(11) Have weather resistance (if possible) like artificial leather.
　前記目的達成のために、本発明の請求項１にかかる発泡ウレタンシートは、ウレタン樹脂、有機溶剤、水およびフッ素系界面活性剤の混合物をポリエチレンテレフタレートフィルム、ポリプロピレンフィルムまたはメチルペンテンポリマーフィルムのいずれか一種のフィルムであって、片面に粘着剤を有する基材に塗布、加温することにより得られる発泡体を前記基材上に有する発泡ウレタンシートであって、前記有機溶剤がトルエンとメチルエチルケトンの混合溶液であり、前記発泡体が連続通気構造の微細セルで構成されることを特徴とする。 To achieve the above object, the foamed urethane sheet according to claim 1 of the present invention is a polyethylene terephthalate film, a polypropylene film or a methylpentene polymer film obtained by mixing a mixture of a urethane resin, an organic solvent, water and a fluorosurfactant. A foamed urethane sheet that is a kind of film and has a foam obtained by applying and heating to a base material having an adhesive on one side, and the organic solvent is a mixture of toluene and methyl ethyl ketone. It is a solution and the said foam is comprised by the fine cell of a continuous ventilation structure, It is characterized by the above-mentioned.
　この構成により、発泡ウレタンシートはポリエチレンテレフタレート、ポリプロピレン、メチルペンテンポリマーといった有機合成高分子物質のフィルムに塗工、一体化されたシートであるため、収縮性が低下し、寸法安定性に優れた発泡ウレタンシートとなる。 With this configuration, the foamed urethane sheet is a sheet that is coated and integrated with a film of an organic synthetic polymer material such as polyethylene terephthalate, polypropylene, or methylpentene polymer. It becomes a urethane sheet.
　また、本発明の請求項２にかかる発泡ウレタンシートは、前記発泡体および前記基材を含む厚みが０．０１～０．１５ｍｍであることを特徴とする。この構成により、シリコーンシートに比べて柔軟性を持ち、衝撃吸収性に対する要求を満たすことが可能になり、液晶テレビのクッション材として満足な性能を有するものとなる。 The urethane foam sheet according to claim 2 of the present invention is characterized in that the thickness including the foam and the base material is 0.01 to 0.15 mm. With this configuration, it is more flexible than a silicone sheet, can satisfy the demand for shock absorption, and has satisfactory performance as a cushioning material for a liquid crystal television.
　また、本発明の請求項３にかかる発泡ウレタンシートは、片面に粘着層を有する前記基材のもう一方の片面に、発泡体と接着する表面処理が施され、この表面処理剤は、３分後の水との接触角が５５°以上の飽和ポリエステル系表面処理剤であることを特徴とする。この構成により、適度の５０％圧縮硬さと伸びを有し、さらに優れた引張り強さを有する発泡ウレタンシートになる。 Further, in the foamed urethane sheet according to claim 3 of the present invention, a surface treatment for adhering to the foam is applied to the other surface of the base material having the adhesive layer on one surface. It is a saturated polyester surface treatment agent having a contact angle with water later of 55 ° or more. By this structure, it becomes a foaming urethane sheet which has moderate 50% compression hardness and elongation, and also has the outstanding tensile strength.
　上記のフッ素系界面活性剤としては、パーフルオロアルキレンエチレンオキシド付加物、例えばＡＧＣセイケミカル株式会社製の商品名サーフロンＳ－４２０、ＤＩＣ株式会社の商品名メガファックＦ－４４４や、パーフルオロアルケニルポリエチレンオキシド付加物、例えば、株式会社ネオス製のフタージェント２５０、ＦＴＸ－２１８が挙げられる。上記のフッ素系界面活性剤を添加することによって、水と溶剤との混合分散性（乳化）が安定し、整泡効果が得られるという利点がある。 Examples of the fluorosurfactant include perfluoroalkylene ethylene oxide adducts, for example, trade name Surflon S-420 manufactured by AGC Seikagaku Co., Ltd., trade name Megafac F-444 manufactured by DIC Corporation, and perfluoroalkenyl polyethylene oxide. Additives such as Footage 250 and FTX-218 manufactured by Neos Co., Ltd. can be mentioned. By adding the above-mentioned fluorosurfactant, there is an advantage that the mixing and dispersibility (emulsification) of water and a solvent is stabilized and a foam stabilizing effect is obtained.
　また、架橋剤および界面活性剤の添加量を変えることによって水と溶剤との混合分散性（乳化）の安定が得られるという利点が得られる。 Further, by changing the addition amount of the crosslinking agent and the surfactant, there is an advantage that the stability of mixing and dispersing (emulsification) of water and a solvent can be obtained.
　また、本発明の請求項５にかかるクッション材は、請求項１～３のいずれか１項に記載の発泡ウレタンシートからなることを特徴とする。この構成により、クッション材は５０％圧縮力が低く、柔軟で復元性に優れたものとなる。 Further, the cushion material according to claim 5 of the present invention is characterized by comprising the urethane foam sheet according to any one of claims 1 to 3. With this configuration, the cushion material has a low 50% compressive force, is flexible, and has excellent resilience.
　また、本発明の請求項６にかかるクッション材は、水との接触角が９０°以上で疎水性であることを特徴とする。この構成により、撥水性が高く、吸水率および水膨潤性が低くなる。従って、緩衝用パッキンとしてハードディスク基板、シリコンウエハ、液晶ディスプレイ用のガラス基板などを研磨する際の研磨保持用パッドや、防水パッキン、防水シートなどに好適なシートとなる。 The cushioning material according to claim 6 of the present invention is characterized in that the contact angle with water is 90 ° or more and is hydrophobic. With this configuration, the water repellency is high, and the water absorption and water swellability are low. Therefore, it is a sheet suitable for a polishing holding pad, a waterproof packing, a waterproof sheet or the like when polishing a hard disk substrate, a silicon wafer, a glass substrate for a liquid crystal display or the like as a buffer packing.
　また、本発明の請求項７にかかるクッション材は、水との接触角が９０°未満で吸水性であることを特徴とする。この構成により、クッション材を構成する発泡ウレタンシートが連続通気構造の微細セルで構成されていることと併せて、透湿性や通水性に優れているため、透湿性シート、吸水シート等に好適なシートとなる。 The cushion material according to claim 7 of the present invention is characterized in that the contact angle with water is less than 90 ° and is water-absorbing. With this configuration, the urethane foam sheet constituting the cushion material is composed of fine cells having a continuous ventilation structure, and is excellent in moisture permeability and water permeability, so it is suitable for moisture permeable sheets, water absorbent sheets and the like. It becomes a sheet.
　また、本発明の請求項８にかかる発泡ウレタンシートの製造方法は、ポリオール、ポリイソシアネート、発泡剤、フッ素系界面活性剤、触媒、トルエンとメチルエチルケトンを含む有機溶剤および必要に応じて架橋剤、着色剤、難燃剤、紫外線吸収剤、耐久性改良剤から選択される添加剤、等の配合物を混合撹拌して得られた反応原料を、ポリエチレンテレフタレートフィルム、ポリプロピレンフィルム、メチルペンテンフィルムのいずれか一種のフィルムであって片面に粘着層を有する基材のもう一方の片面に均一に塗布した後、２段階加熱発泡して連続気泡構造の微細セルからなる発泡体を形成することを特徴とする。 In addition, the method for producing a foamed urethane sheet according to claim 8 of the present invention includes a polyol, a polyisocyanate, a foaming agent, a fluorosurfactant, a catalyst, an organic solvent containing toluene and methyl ethyl ketone, and a crosslinking agent, if necessary. A reaction raw material obtained by mixing and stirring a compound such as an additive selected from an agent, a flame retardant, an ultraviolet absorber, and a durability improver, and any one of a polyethylene terephthalate film, a polypropylene film, and a methylpentene film After the film is uniformly coated on the other side of the substrate having an adhesive layer on one side, it is heated and foamed in two stages to form a foam composed of fine cells having an open-cell structure.
　前記いずれの製造方法にあっても、発泡ウレタンについては、配合した混合原料の分散安定性が高いので製造時間を長くでき、従って製造コストの低減が可能となり、平面平坦性、セル均一性、衝撃吸収性、機械的強度、耐摩耗性に優れた発泡ウレタンシートを、容易に製造することができる。 In any of the above production methods, for foamed urethane, the dispersion stability of the blended mixed raw material is high, so the production time can be lengthened, and thus the production cost can be reduced, and the flatness, cell uniformity, impact A foamed urethane sheet excellent in absorbency, mechanical strength, and abrasion resistance can be easily produced.
　また、製造時に、前記ウレタン発泡原料がフィルム状基材上で反応して硬化する際に、同時に接着も行われるので、その接着強度は発泡ウレタンシートを接着剤によって基材に貼り付けたものに比べて強くなるだけでなく、別の工程を使用して接着する手間や設備を省くことができ、経済的である。 In addition, when the urethane foam raw material reacts and cures on the film-like substrate at the time of manufacture, adhesion is also performed at the same time, so the adhesive strength is that obtained by attaching the urethane foam sheet to the substrate with an adhesive. In addition to being stronger, it is economical because it can save labor and equipment for bonding using another process.
　また、本発明の発泡ウレタンシートに用いる基材としては、各種のプラスチックフィルムが考えられるが、強度、耐熱性、寸法安定性などの点から、ポリエチレンテレフタレートフィルム、ポリプロピレンフィルムまたはメチルペンテンポリマーフィルムが特に好ましい。 Moreover, as a base material used for the foamed urethane sheet of the present invention, various plastic films can be considered. From the viewpoint of strength, heat resistance, dimensional stability, a polyethylene terephthalate film, a polypropylene film, or a methylpentene polymer film is particularly preferable. preferable.
　さらに、本発明の請求項９にかかる発泡ウレタンシートの製造方法は、前記フッ素系界面活性剤がパーフルオロアルキルエチレンオキシド付加物またはパーフルオロアルケニルポリエチレンオキシド付加物であることを特徴とする。
　パーフルオロアルキレンエチレンオキシド付加物としては、例えばＡＧＣセイケミカル株式会社製の商品名サーフロンＳ－４２０、ＤＩＣ株式会社の商品名メガファックＦ－４４４、パーフルオロアルケニルポリエチレンオキシド付加物としては、例えば、株式会社ネオス製のフタージェント２５０、ＦＴＸ－２１８が挙げられる。上記のフッ素系界面活性剤を添加することによって、水と溶剤との混合分散性（乳化）が安定し、整泡効果が得られるという利点がある。 Furthermore, the method for producing a foamed urethane sheet according to claim 9 of the present invention is characterized in that the fluorosurfactant is a perfluoroalkylethylene oxide adduct or a perfluoroalkenyl polyethylene oxide adduct.
Examples of the perfluoroalkylene ethylene oxide adduct include, for example, trade name Surflon S-420 manufactured by AGC Sey Chemical Co., Ltd., trade name of Megafic F-444 manufactured by DIC Corporation, and examples of perfluoroalkenyl polyethylene oxide adduct include, for example, Examples include Neogent's Footage 250 and FTX-218. By adding the above-mentioned fluorosurfactant, there is an advantage that the mixing and dispersibility (emulsification) of water and a solvent is stabilized and a foam stabilizing effect is obtained.
　本発明によれば、肉厚が厚み０．１５ｍｍ以下であるにも拘わらず、柔軟性に富み、微細均一構造を有して衝撃吸収性が高く、しかも収縮性を抑えた基材付き発泡ウレタンシートを提供できる。 According to the present invention, although the thickness is 0.15 mm or less, the foamed urethane with a base material has high flexibility, a fine uniform structure, high shock absorption, and reduced shrinkage. Can provide a sheet.
　以上、本発明について簡潔に説明した。更に、以下に本発明を実施するための最良の形態を添付の図面を参照して、詳細に説明する。 The present invention has been briefly described above. The best mode for carrying out the present invention will be described below in detail with reference to the accompanying drawings.
本発明にかかる発泡ウレタンシートの製造方法を示す断面説明図である。It is sectional explanatory drawing which shows the manufacturing method of the foaming urethane sheet concerning this invention.
　以下、本発明の実施形態に係る発泡ウレタンシートを、図面を参照して説明する。
　まず、基材２を用意する。該基材２は、ポリエチレンテレフタレート（以下、ＰＥＴと略す）フィルム、ポリプロピレン（以下、ＰＰと略す）フィルム、４－メチルペンテン－１を重合したメチルペンテンポリマー（以下、ＴＰＸと略す）フィルムのうちいずれかのフィルム３の片面に粘着層４を有する。フィルム３としては、例えば、リンテック株式会社製ＰＥＴ１００ＧＳを用いる。
　次に、熱可塑性ポリウレタン溶液（ＤＩＣ株式会社製ゾルテックスＰＸ－５５０）１００部に対し、架橋剤としてイソシアネートプレポリマー（ＤＩＣ株式会社製ＣＬ－１５）２部、触媒として有機錫触媒（ＤＩＣ株式会社製Ｔ・８１Ｅ）２部、界面活性剤（ＡＧＣセイミケミカル株式会社製サーフロンＳ－４２０）１部を混合して均一分散した後、これを前記粘着層４を有する基材２の他面にスキージ等を用いて塗工し、７０℃×５ｍｉｎ間、その後１２０℃×２０ｍｉｎ（１０～３０ｍｉｎ）間反応させ、前記基材２上に発泡体１を一体化した発泡ウレタンシートを得る。 Hereinafter, a urethane foam sheet according to an embodiment of the present invention will be described with reference to the drawings.
First, the base material 2 is prepared. The substrate 2 may be any one of a polyethylene terephthalate (hereinafter abbreviated as PET) film, a polypropylene (hereinafter abbreviated as PP) film, and a methylpentene polymer (hereinafter abbreviated as TPX) film obtained by polymerizing 4-methylpentene-1. The film 3 has an adhesive layer 4 on one side. As the film 3, for example, PET100GS manufactured by Lintec Corporation is used.
Next, 100 parts of a thermoplastic polyurethane solution (Zoltex PX-550 manufactured by DIC Corporation), 2 parts of an isocyanate prepolymer (CL-15 manufactured by DIC Corporation) as a crosslinking agent, and an organotin catalyst (manufactured by DIC Corporation) as a catalyst. 2 parts of T.81E) and 1 part of a surfactant (Surflon S-420 manufactured by AGC Seimi Chemical Co., Ltd.) were mixed and dispersed uniformly, and this was then squeegeeed on the other surface of the substrate 2 having the adhesive layer 4 And a reaction is performed for 70 ° C. × 5 min, and then 120 ° C. × 20 min (10 to 30 min) to obtain a foamed urethane sheet in which the foam 1 is integrated on the substrate 2.
　界面活性剤の添加量は０．６８部以上で、より好ましい範囲は０．６８～４部である。
　フッ素系界面活性剤はパーフルオロアルキルエチレンオキシド付加物（ＡＧＣセイミケミカル株式会社製サーフロンＳ－４２０）、パーフルオロアルキルエチレンオキシド付加物（ＤＩＣ株式会社製メガファックＦ－４４４）、パーフルオロアルケニルポリエチレンオキシド付加物（株式会社ネオス製フタージェント２５０、ＦＴＸ－２１８）が好ましい。
　上記界面活性剤を添加することによって、水と溶剤の混合分散性（乳化）が安定化し、整泡効果が得られる。
　また、架橋剤および界面活性剤の添加量を変えることで接触角を調整することができ、親水性から疎水性の発泡フィルムを作ることができる。 The addition amount of the surfactant is 0.68 parts or more, and a more preferable range is 0.68 to 4 parts.
Fluorosurfactants include perfluoroalkylethylene oxide adduct (Surflon S-420 manufactured by AGC Seimi Chemical Co., Ltd.), perfluoroalkylethylene oxide adduct (Megafac F-444 manufactured by DIC Corporation), and perfluoroalkenyl polyethylene oxide adduct. (Foogent 250, FTX-218 manufactured by Neos Co., Ltd.) is preferable.
By adding the surfactant, the mixing and dispersibility (emulsification) of water and solvent is stabilized, and a foam stabilizing effect is obtained.
Further, the contact angle can be adjusted by changing the addition amount of the crosslinking agent and the surfactant, and a foamed film from hydrophilic to hydrophobic can be produced.
　なお、図１中で基材２を構成するフィルム３としては、前記ＰＥＴフィルム、ＰＰフィルム、４－メチルペンテン－１を重合したＴＰＸフィルムのほか、紙とポリプロピレンラミネートフィルムなども使用できる。フィルム３の片面には発泡体（熱可塑性ポリウレタン樹脂又は熱硬化性ポリウレタン樹脂）１が設けられている。なお、前記粘着層４にはセパレータ（図示しない）が剥離可能に貼り付けられる。この発泡ウレタンシートを使用する際は、粘着層４に貼り合わせられたセパレータ（図示しない）を剥離してから固定板などに貼り付ける。 In addition, as the film 3 constituting the substrate 2 in FIG. 1, paper and polypropylene laminate film can be used in addition to the PET film, PP film, TPX film obtained by polymerizing 4-methylpentene-1. A foam (thermoplastic polyurethane resin or thermosetting polyurethane resin) 1 is provided on one surface of the film 3. A separator (not shown) is detachably attached to the adhesive layer 4. When using this urethane foam sheet, the separator (not shown) bonded to the adhesive layer 4 is peeled off and then attached to a fixed plate or the like.
　前記発泡ウレタンシートは、請求項１に記載の特徴を有するものであれば、ジイソシアナートとポリオールの重付加で作られるポリウレタンである限り熱可塑性、熱硬化性のどちらの樹脂であってもよい。ただし、フッ素系界面活性剤を用いると、得られる発泡ウレタンシートの原料の安定性、表面平坦性、セル均一性、低通気性、防水性／吸水性、層間剥離力の点から特に好ましい。 The foamed urethane sheet may be either thermoplastic or thermosetting resin as long as it is a polyurethane made by polyaddition of diisocyanate and polyol as long as it has the characteristics described in claim 1. . However, the use of a fluorosurfactant is particularly preferable from the viewpoints of the stability of the raw material of the obtained urethane foam sheet, surface flatness, cell uniformity, low air permeability, waterproofness / water absorption, and delamination force.
　前記発泡ウレタンシートは、ポリオール、ポリイソシアネート、発泡剤、フッ素系界面活性剤、必要に応じて触媒および架橋剤、着色剤、樹脂改質剤、難燃剤、紫外線吸収剤、耐久性改良材から選択される添加剤、等の配合物を混合撹拌して得られた配合原料を、剥離処理を施した工程紙の剥離面に均一に塗布した後、６０～７０℃のオーブン中で加熱してメチルエチルケトン（ＭＥＫ）、トルエン等の有機溶剤を蒸発させ、次いで９０～１２０℃のオーブン中で加熱し、水を蒸発させるという２段階加熱法により、厚さ０．０１～０．１ｍｍの極めて薄い発泡ウレタンシートを作製することに実用的に初めて成功した。 The foamed urethane sheet is selected from polyols, polyisocyanates, foaming agents, fluorosurfactants, if necessary, catalysts and crosslinking agents, colorants, resin modifiers, flame retardants, UV absorbers, and durability improvers. The blended raw material obtained by mixing and stirring the blended additive, etc., is uniformly applied to the release surface of the release-processed paper, and then heated in an oven at 60 to 70 ° C. for methyl ethyl ketone. (MEK), an extremely thin foamed urethane with a thickness of 0.01 to 0.1 mm, by evaporating an organic solvent such as toluene and then heating in an oven at 90 to 120 ° C. to evaporate water. It was the first practical success in producing a sheet.
　ポリウレタン樹脂の原料のポリオールおよびポリイソシアネートとしては、従来からポリウレタン樹脂の合成原料として使用されてきたものであれば、如何なるものでも何らの制限なく使用できる。例えば、ポリエーテル系ウレタン（ＤＩＣ株式会社製ゾルテックスＰＸ－５５０、大日精化工業株式会社製ＨＩ－ＭＵＲＥＮＡＴＸシリーズ）が挙げられる。
　また、ポリウレタン樹脂の希釈用有機溶剤としては、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤、トルエン、キシレン等の芳香族系溶剤、酢酸エチル、酢酸ブチル等のエステル系溶剤、イソプロピルアルコール、ｔ－ブチルアルコール等のアルコール系溶剤、およびこれらの混合溶剤などが使用できるが、トルエンとメチルエチルケトンとの混合液が原料混合物溶液の貯蔵安定性の点から特に好ましい希釈用溶剤である。 As the raw material polyol and polyisocyanate of the polyurethane resin, any material can be used without any limitation as long as it has been conventionally used as a raw material for polyurethane resin synthesis. For example, polyether urethane (Zoltex PX-550 manufactured by DIC Corporation, HI-MURENATX series manufactured by Dainichi Seika Kogyo Co., Ltd.) can be used.
Examples of the organic solvent for diluting the polyurethane resin include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, aromatic solvents such as toluene and xylene, ester solvents such as ethyl acetate and butyl acetate, isopropyl alcohol, and t-butyl. Alcohol solvents such as alcohol and mixed solvents thereof can be used, but a mixed solution of toluene and methyl ethyl ketone is a particularly preferable dilution solvent from the viewpoint of storage stability of the raw material mixture solution.
　前記発泡剤として、水、プロパン、ブタン等を発生するアクリロニトリル骨格を持つマイクロカプセルがあげられる。また、水の替わりに、７０°乾燥後に炭酸ガスや窒素ガスを用いて加圧ガス発泡を行っても良い。 Examples of the foaming agent include microcapsules having an acrylonitrile skeleton that generates water, propane, butane, and the like. Further, instead of water, pressurized gas foaming may be performed using carbon dioxide gas or nitrogen gas after 70 ° drying.
　また、特に好ましい界面活性剤として、先に発泡ウレタンシートの製造方法において記述した通りであり、フッ素系界面活性剤が用いられる。これにより水と溶剤との混合分散性（乳化）が安定し、好ましい整泡効果が得られる。
　さらに、触媒、架橋剤および界面活性剤の添加量を変えることにより水との接触角を調整することができることも製造方法において記述した通りである。 Further, as a particularly preferable surfactant, as described above in the method for producing a foamed urethane sheet, a fluorosurfactant is used. Thereby, the mixing dispersibility (emulsification) of water and a solvent is stabilized, and a preferable foam regulating effect is obtained.
Furthermore, as described in the production method, the contact angle with water can be adjusted by changing the addition amount of the catalyst, the crosslinking agent and the surfactant.
　次に、本発明を実施例および比較例により詳細に説明する。以下において、「部」および「％」は重量基準の単位とする。
　この実施例および比較例による発泡ウレタンシートの作製は、先ず、ポリオール、ポリイソシアネート、ＭＥＫおよびトルエンからなる希釈溶剤、水、フッ素系界面活性剤、必要に応じて触媒および架橋剤からなる配合物を混合する。 Next, the present invention will be described in detail with reference to examples and comparative examples. In the following, “parts” and “%” are units based on weight.
The foamed urethane sheets according to the examples and comparative examples are prepared by first preparing a diluent solvent consisting of polyol, polyisocyanate, MEK and toluene, water, a fluorosurfactant, and if necessary a catalyst and a crosslinking agent. Mix.
　次に、この配合物の混合撹拌によって得られた反応原料を、塗布バーを用いて剥離処理を施したＰＥＴフィルム等の工程紙の剥離面に均一に塗布する。そして、工程紙に塗布した反応原料を６０～７０℃のオーブン中で加熱し希釈溶剤を蒸発させ、次いで９０～１２０℃のオーブン中で水を蒸発させながら発泡硬化させることによって、連続気泡構造の微細セルからなる発泡ウレタンシートを得ることができる。そして、この発泡ウレタンシートの実施例および比較例を挙げ、その各発泡ウレタンシートの諸特性を、以下に示す。この諸特性の評価方法は、後述する。 Next, the reaction raw material obtained by mixing and stirring the blend is uniformly applied to the release surface of a process paper such as a PET film which has been subjected to a release treatment using an application bar. The reaction raw material applied to the process paper is heated in an oven at 60 to 70 ° C. to evaporate the diluted solvent, and then foamed and cured while evaporating water in the oven at 90 to 120 ° C. A foamed urethane sheet composed of fine cells can be obtained. And the Example and comparative example of this foaming urethane sheet are given, and the various characteristics of each foaming urethane sheet are shown below. A method for evaluating these characteristics will be described later.
　ポリウレタン樹脂溶液（ＤＩＣ株式会社製ゾルテックスＰＸ５５０）１００部と希釈溶剤（トルエン／２－ブタノン＝２／１で配合）５０部、発泡剤（水／２－ブタノン＝９／１）８０部、界面活性剤としてパーフルオロアルキルエチレンオキシド付加物（ＡＧＣセイミケミカル株式会社製サーフロンＳ－４２０）１部を良く攪拌しながら２５℃に調整した。調整した液を更に攪拌・脱泡機にて５分間攪拌後、０．０２５ｍｍ厚みの片面に３分後の接触角５５°ポリエステルコーティングを施し、もう一方の片面に粘着層を有するＰＥＴフィルムに均一に塗布することによって、厚み０．１ｍｍで密度５００ｋｇ／ｍ３のポリウレタン発泡ウレタアンシート材を得た。この発泡ウレタンシート材の収縮率は０％であった。 100 parts of polyurethane resin solution (DIC Corporation Soltex PX550), 50 parts of diluent solvent (formulated with toluene / 2-butanone = 2/1), 80 parts of blowing agent (water / 2-butanone = 9/1), surface active 1 part of a perfluoroalkylethylene oxide adduct (Surflon S-420 manufactured by AGC Seimi Chemical Co., Ltd.) as an agent was adjusted to 25 ° C. with good stirring. The prepared liquid is further stirred for 5 minutes with a stirrer / defoamer, then a polyester film with a contact angle of 55 ° after 3 minutes is applied on one side of a 0.025 mm thickness, and the PET film having an adhesive layer on the other side is uniform. Was applied to obtain a polyurethane foam urethane sheet material having a thickness of 0.1 mm and a density of 500 kg / m 3. The shrinkage ratio of this foamed urethane sheet material was 0%.
　ポリウレタン樹脂溶液（ＤＩＣ株式会社製ゾルテックスＰＸ５５０）１００部と希釈溶剤（トルエン／２－ブタノン＝２／１で配合）５０部、発泡剤（水／２－ブタノン＝９／１）８０部、界面活性剤としてパーフルオロアルキルエチレンオキシド付加物（ＡＧＣセイミケミカル株式会社製サーフロンＳ－４２０）１部、架橋剤および触媒（架橋剤；ヘキサメチレンジイソシアネートプレポリマー、ヘキサメチレンジイソシアネート、触媒溶液；１％未満含有有機錫触媒（ジブチルチンジラウレート）酢酸エチル／２－ブタノン溶液）をそれぞれ各１部添加し、良く攪拌しながら２５℃に調整した。調整した液を更に攪拌・脱泡機にて５分間攪拌後、０．０２５ｍｍ厚みの片面に３分後の接触角７５°でポリエステルコーティングを施し、もう一方の片面に粘着層を有するＰＥＴフィルム基材に均一に塗布することによって、厚み０．１ｍｍで密度が５１０ｋｇ／ｍ３のポリウレタン発泡ウレタンシート材を得た。この発泡ウレタンシート材の収縮率は０％であった。 100 parts of polyurethane resin solution (DIC Corporation Soltex PX550), 50 parts of diluent solvent (formulated with toluene / 2-butanone = 2/1), 80 parts of blowing agent (water / 2-butanone = 9/1), surface active Perfluoroalkylethylene oxide adduct (Surflon S-420, manufactured by AGC Seimi Chemical Co., Ltd.) as crosslinking agent, crosslinking agent and catalyst (crosslinking agent: hexamethylene diisocyanate prepolymer, hexamethylene diisocyanate, catalyst solution; organotin containing less than 1% 1 part each of catalyst (dibutyltin dilaurate) ethyl acetate / 2-butanone solution) was added, and the mixture was adjusted to 25 ° C. with good stirring. The prepared liquid is further stirred for 5 minutes with a stirrer / defoamer, and then a 0.025 mm thick one side is coated with a polyester coating at a contact angle of 75 ° after 3 minutes, and the other side is a PET film base having an adhesive layer By uniformly applying to the material, a polyurethane foamed urethane sheet material having a thickness of 0.1 mm and a density of 510 kg / m3 was obtained. The shrinkage ratio of this foamed urethane sheet material was 0%.
　ポリウレタン樹脂溶液（ＤＩＣ株式会社製ゾルテックスＰＸ５５０）１００部と希釈溶剤（トルエン／２－ブタノン＝２／１で配合）５０部、発泡材（水／２－ブタノン＝９／１）を５０部、界面活性剤としてパーフルオロアルキルエチレンオキシド付加物（ＡＧＣセイミケミカル株式会社製サーフロンＳ－４２０）１部を良く攪拌しながら２５℃に調整した。調整した液を更に攪拌・脱泡機にて５分間攪拌後、０．０２５ｍｍ厚みの片面に３分後の接触角５７°ポリエステルコーティングを施し、もう一方の片面に粘着層を有するＰＥＴフィルム基材に均一に塗布することによって、厚み０．０１ｍｍで密度６８０ｋｇ／ｍ３のポリウレタン発泡ウレタンシート材を得た。この発泡ウレタンシートの収縮率は０％であった。 100 parts of polyurethane resin solution (DIC Corporation Soltex PX550), 50 parts of diluent solvent (blended with toluene / 2-butanone = 2/1), 50 parts of foaming material (water / 2-butanone = 9/1), interface 1 part of a perfluoroalkylethylene oxide adduct (Surflon S-420 manufactured by AGC Seimi Chemical Co., Ltd.) as an activator was adjusted to 25 ° C. with good stirring. The prepared liquid is further stirred with a stirrer / degasser for 5 minutes, and then a polyester film base having a contact angle of 57 ° after 3 minutes on one side of 0.025 mm thickness and a pressure-sensitive adhesive layer on the other side. Was applied uniformly to obtain a polyurethane foamed urethane sheet having a thickness of 0.01 mm and a density of 680 kg / m 3 . The shrinkage ratio of this urethane foam sheet was 0%.
　ポリウレタン樹脂溶液（ＤＩＣ株式会社製ゾルテックスＰＸ５５０）１００部と希釈溶剤（トルエン／２－ブタノン＝２／１で配合）５０部、発泡材（水／２－ブタノン＝９／１）を８０部、界面活性剤としてパーフルオロアルキルエチレンオキシド付加物（ＡＧＣセイミケミカル株式会社製サーフロンＳ－４２０）１部、架橋剤および触媒（架橋剤；ヘキサメチレンジイソシアネート、触媒溶液；１％未満含有有機錫触媒（ジブチルチンジラウレート）酢酸エチル／２－ブタノン溶液）をそれぞれ各１部添加し、良く攪拌しながら２５℃に調整した。調整した液を更に攪拌・脱泡機にて５分間攪拌後、０．０２５ｍｍ厚みの片面に３分後の接触角６０°ポリエステルコーティングを施し、もう一方の片面に粘着層を有するＰＥＴフィルム基材に均一に塗布することによって、厚み０．０４ｍｍで密度５７０ｋｇ／ｍ３のポリウレタン発泡ウレタンシート材を得た。この発泡ウレタンシートの収縮率は０％であった。 100 parts of polyurethane resin solution (DIC Corporation Soltex PX550), 50 parts of diluting solvent (blended with toluene / 2-butanone = 2/1), 80 parts of foaming material (water / 2-butanone = 9/1), interface 1 part of perfluoroalkylethylene oxide adduct (Surflon S-420 manufactured by AGC Seimi Chemical Co., Ltd.) as activator, crosslinker and catalyst (crosslinker; hexamethylene diisocyanate, catalyst solution; organotin catalyst containing less than 1% (dibutyltin dilaurate) 1) each of ethyl acetate / 2-butanone solution) was added and adjusted to 25 ° C. with good stirring. After the prepared liquid is further stirred for 5 minutes with a stirrer / defoamer, a polyester film base having a contact angle of 60 ° after 3 minutes on one side of 0.025 mm thickness and a pressure-sensitive adhesive layer on the other side Was applied uniformly to obtain a polyurethane foamed urethane sheet material having a thickness of 0.04 mm and a density of 570 kg / m 3 . The shrinkage ratio of this urethane foam sheet was 0%.
　ポリウレタン樹脂溶液（ＤＩＣ株式会社製ゾルテックスＰＸ５５０）１００部と希釈溶剤（トルエン／２－ブタノン＝２／１で配合）５０部、発泡材（水／２－ブタノン＝９／１）を８０部、界面活性剤としてパーフルオロアルケニルポリエチレンオキシド付加物（株式会社ネオス製フタージェント２５１）１部、架橋剤および触媒（架橋剤；ヘキサメチレンジイソシアネート、触媒溶液；１％未満含有有機錫触媒（ジブチルチンジラウレート）酢酸エチル／２－ブタノン溶液）をそれぞれ各１部添加し、良く攪拌しながら２５℃に調整した。調整した液を更に攪拌・脱泡機にて５分間攪拌後、０．０２５ｍｍ厚みの片面に３分後の接触角６０°ポリエステルコーティングを施し、もう一方の片面に粘着層を有するＰＥＴフィルム基材に均一に塗布することによって、厚み０．１ｍｍで密度５０７ｋｇ／ｍ３のポリウレタン発泡ウレタンシート材を得た。この発泡ウレタンシートの収縮率は０％であった。
　この実施例１乃至実施例５の発泡ウレタンシートの諸特性は、表１の通りである。 100 parts of polyurethane resin solution (DIC Corporation Soltex PX550), 50 parts of diluting solvent (blended with toluene / 2-butanone = 2/1), 80 parts of foaming material (water / 2-butanone = 9/1), interface 1 part of perfluoroalkenyl polyethylene oxide adduct (Fuentgent 251 manufactured by Neos Co., Ltd.) as an activator, crosslinker and catalyst (crosslinker; hexamethylene diisocyanate, catalyst solution; less than 1% organic tin catalyst (dibutyltin dilaurate) acetic acid 1 part each of ethyl / 2-butanone solution) was added, and the mixture was adjusted to 25 ° C. with good stirring. After the prepared liquid is further stirred for 5 minutes with a stirrer / defoamer, a polyester film base having a contact angle of 60 ° after 3 minutes on one side of 0.025 mm thickness and a pressure-sensitive adhesive layer on the other side Was applied uniformly to obtain a polyurethane foamed urethane sheet material having a thickness of 0.1 mm and a density of 507 kg / m 3 . The shrinkage ratio of this urethane foam sheet was 0%.
Various characteristics of the urethane foam sheets of Examples 1 to 5 are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
 　　　　　　　　　　　　　　　　　　
乾式ウレタン原料；ポリエーテル系ウレタン
架橋剤；ヘキサメチレンジイソシアネートプレポリマー、ヘキサメチレンジイソシアネート
触媒溶液；１％未満含有有機錫触媒（ジブチルチンジラウレート）酢酸エチル／２－ブタノン溶液
界面活性剤Ａ；パーフルオロアルキルエチレンオキサイド共重合体（ＡＧＣセイミケミカル株式会社製サーフロンＳ－４２０）
界面活性剤Ｂ；パーフルオロアルケニルポリエチレンオキシド付加物（株式会社ネオス製フタージェント２５１）
可塑剤；ジアルキレングリコールジベンゾエート（ＤＩＣ株式会社製ＰＢ－３Ａ）
コーティング剤；シリコーン；シリコーン系離型コーティング、ポリエステル；飽和ポリエステル系コーティング
　次に比較例を示す。
Figure JPOXMLDOC01-appb-T000001
Dry urethane raw material; polyether urethane crosslinker; hexamethylene diisocyanate prepolymer, hexamethylene diisocyanate catalyst solution; organotin catalyst containing less than 1% (dibutyltin dilaurate) ethyl acetate / 2-butanone solution surfactant A; perfluoroalkyl Ethylene oxide copolymer (Surflon S-420 manufactured by AGC Seimi Chemical Co., Ltd.)
Surfactant B: Perfluoroalkenyl polyethylene oxide adduct (Neos Corporation's Footgent 251)
Plasticizer: dialkylene glycol dibenzoate (PB-3A manufactured by DIC Corporation)
Coating Agent; Silicone; Silicone Release Coating, Polyester; Saturated Polyester Coating A comparative example is shown below.
比較例１Comparative Example 1
　ポリウレタン樹脂溶液（ＤＩＣ株式会社製ゾルテックスＰＸ５５０）１００部と希釈溶剤（トルエン／２－ブタノン＝２／１で配合）５０部、発泡剤（水／２－ブタノン＝９／１）８０部、界面活性剤としてパーフルオロアルキルエチレンオキシド付加物（ＡＧＣセイミケミカル株式会社製サーフロンＳ－４２０）１部を良く攪拌しながら２５℃に調整した。調整した液を更に攪拌・脱泡機にて５分間攪拌後、０．０２５ｍｍ厚みのＰＥＴフィルムの片面にシリコーン系離型処理を施した基材に均一に塗布することによって、厚み０．１ｍｍで密度５００ｋｇ／ｍ３のポリウレタン発泡ウレタンシート材を得た。この発泡ウレタンシート材の収縮率は５％であり、後加工性の悪い発泡ウレタンシートが得られた。 100 parts of polyurethane resin solution (DIC Corporation Soltex PX550), 50 parts of diluent solvent (formulated with toluene / 2-butanone = 2/1), 80 parts of blowing agent (water / 2-butanone = 9/1), surface active 1 part of a perfluoroalkylethylene oxide adduct (Surflon S-420 manufactured by AGC Seimi Chemical Co., Ltd.) as an agent was adjusted to 25 ° C. with good stirring. The prepared liquid is further stirred for 5 minutes with a stirrer / defoamer, and then uniformly applied to a base material subjected to a silicone release treatment on one side of a PET film having a thickness of 0.025 mm. A polyurethane foam urethane sheet material having a density of 500 kg / m 3 was obtained. The shrinkage ratio of this foamed urethane sheet material was 5%, and a foamed urethane sheet with poor post-processability was obtained.
比較例２Comparative Example 2
　ポリウレタン樹脂溶液（ＤＩＣ株式会社製ゾルテックスＰＸ５５０）１００部と希釈溶剤（トルエン／２－ブタノン＝２／１）５０部、発泡剤（水／２－ブタノン＝９／１）８０部、界面活性剤としてパーフルオロアルキルエチレンオキシド付加物（ＡＧＣセイミケミカル株式会社製サーフロンＳ－４２０）１部、架橋剤および触媒（架橋剤；ヘキサメチレンジイソシアネートプレポリマー、ヘキサメチレンジイソシアネート、触媒溶液；１％未満含有有機錫触媒（ジブチルチンジラウレート）酢酸エチル／２－ブタノン溶液）をそれぞれ各７部添加し、良く攪拌しながら２５℃に調整した。調整した液を更に攪拌・脱泡機にて５分間攪拌後、０．０２５ｍｍ厚みのＰＥＴフィルムの片面にシリコーン系離型処理を施した基材に均一に塗布することによって、厚み０．１ｍｍで密度が５８０ｋｇ／ｍ３のポリウレタン発泡ウレタンシート材を得た。この発泡ウレタンシート材の収縮率は１．５％であったが、発泡ウレタンシートの５０％圧縮硬さが硬い発泡ウレタンシートが得られた。 100 parts of polyurethane resin solution (DIC Corporation Soltex PX550), 50 parts of diluent solvent (toluene / 2-butanone = 2/1), 80 parts of foaming agent (water / 2-butanone = 9/1), surfactant 1 part of perfluoroalkylethylene oxide adduct (Surflon S-420 manufactured by AGC Seimi Chemical Co., Ltd.), crosslinking agent and catalyst (crosslinking agent; hexamethylene diisocyanate prepolymer, hexamethylene diisocyanate, catalyst solution; organotin catalyst containing less than 1% ( 7 parts of each of dibutyltin dilaurate) ethyl acetate / 2-butanone solution) were added and adjusted to 25 ° C. with good stirring. The prepared liquid is further stirred for 5 minutes with a stirrer / defoamer, and then uniformly applied to a base material subjected to a silicone release treatment on one side of a PET film having a thickness of 0.025 mm. A polyurethane foamed urethane sheet material having a density of 580 kg / m 3 was obtained. Although the shrinkage rate of this foamed urethane sheet material was 1.5%, a foamed urethane sheet having a 50% compression hardness of the foamed urethane sheet was obtained.
比較例３Comparative Example 3
　ポリウレタン樹脂溶液（ＤＩＣ株式会社製ゾルテックスＰＸ５５０）１００部と希釈溶剤（トルエン／２－ブタノン＝２／１）５０部、発泡剤（水／２－ブタノン＝９／１）８０部、界面活性剤としてパーフルオロアルキルエチレンオキシド付加物（ＡＧＣセイミケミカル株式会社製サーフロンＳ－４２０）１部、可塑剤（ジアルキレングリコールジベンゾエート（ＤＩＣ株式会社製ＰＢ－３Ａ））１０部を配合し、良く攪拌しながら２５℃に調整した。調整した液を更に攪拌・脱泡機にて５分間攪拌後、０．０２５ｍｍ厚みのＰＥＴフィルムの片面にシリコーン系離型処理を施した基材に均一に塗布することによって、厚み０．１ｍｍで密度７２０ｋｇ／ｍ３のポリウレタン発泡ウレタンシート材を得た。この発泡ウレタンシートの収縮率は２．０％であったが、密度の高い発泡ウレタンシートが得られた。 100 parts of polyurethane resin solution (DIC Corporation Soltex PX550), 50 parts of diluent solvent (toluene / 2-butanone = 2/1), 80 parts of foaming agent (water / 2-butanone = 9/1), surfactant 1 part of a perfluoroalkylethylene oxide adduct (Surflon S-420 manufactured by AGC Seimi Chemical Co., Ltd.) and 10 parts of a plasticizer (dialkylene glycol dibenzoate (PB-3A manufactured by DIC Co., Ltd.)) were mixed and mixed with stirring. Adjusted to ° C. The prepared liquid is further stirred for 5 minutes with a stirrer / defoamer, and then uniformly applied to a base material subjected to a silicone release treatment on one side of a PET film having a thickness of 0.025 mm. A polyurethane foam urethane sheet material having a density of 720 kg / m 3 was obtained. Although the shrinkage ratio of this foamed urethane sheet was 2.0%, a high-density foamed urethane sheet was obtained.
比較例４Comparative Example 4
　ポリウレタン樹脂溶液（ＤＩＣ株式会社製ゾルテックスＰＸ５５０）１００部と希釈溶剤（トルエン／２－ブタノン＝２／１）５０部、発泡剤（水／２－ブタノン＝９／１）８０部、界面活性剤としてパーフルオロアルキルエチレンオキシド付加物（ＡＧＣセイミケミカル株式会社製サーフロンＳ－４２０）１部を良く攪拌しながら２５℃に調整した。調整した液を更に攪拌・脱泡機にて５分間攪拌後、０．０２５ｍｍ厚みのＰＥＴフィルムの片面に３分後の接触角５０°ポリエステルコーティングを施し、もう一方の片面に粘着層を有するＰＥＴフィルム基材に均一に塗布すると不均一で斑な発泡ウレタンシートが得られた。 100 parts of polyurethane resin solution (DIC Corporation Soltex PX550), 50 parts of diluent solvent (toluene / 2-butanone = 2/1), 80 parts of foaming agent (water / 2-butanone = 9/1), surfactant 1 part of perfluoroalkylethylene oxide adduct (Surflon S-420 manufactured by AGC Seimi Chemical Co., Ltd.) was adjusted to 25 ° C. with good stirring. The prepared liquid is further stirred for 5 minutes with a stirrer / defoamer, and then a PET film having a contact angle of 50 ° after 3 minutes is applied to one side of a PET film having a thickness of 0.025 mm and an adhesive layer is provided on the other side. When uniformly applied to the film substrate, a nonuniform and uneven foamed urethane sheet was obtained.
比較例５Comparative Example 5
　ポリウレタン樹脂溶液（ＤＩＣ株式会社製ゾルテックスＰＸ５５０）１００部と希釈溶剤（トルエン／２－ブタノン＝２／１）５０部、発泡剤（水／２－ブタノン＝９／１）８０部、界面活性剤としてパーフルオロアルキルエチレンオキシド付加物（ＡＧＣセイミケミカル株式会社製サーフロンＳ－４２０）１部、架橋剤および触媒（架橋剤；ヘキサメチレンジイソシアネートプレポリマー、ヘキサメチレンジイソシアネート。触媒溶液；１％未満含有有機錫触媒（ジブチルチンジラウレート）酢酸エチル／２ブタノン溶液）をそれぞれ各２部添加し、良く攪拌しながら２５℃に調整した。調整した液を更に攪拌・脱泡機にて５分間攪拌後、０．０２５ｍｍ厚みのＰＥＴフィルムの片面に３分後の接触角２５°ポリエステルコーティングを施し、もう一方の片面に粘着層を有するＰＥＴフィルム基材に均一に塗布すると不均一で斑な発泡ウレタンシートが得られた。
　上記比較例１乃至５の発泡ウレタンシートの諸特性は、表２の通りである。 100 parts of polyurethane resin solution (DIC Corporation Soltex PX550), 50 parts of diluent solvent (toluene / 2-butanone = 2/1), 80 parts of foaming agent (water / 2-butanone = 9/1), surfactant 1 part of perfluoroalkylethylene oxide adduct (Surflon S-420 manufactured by AGC Seimi Chemical Co., Ltd.), crosslinking agent and catalyst (crosslinking agent: hexamethylene diisocyanate prepolymer, hexamethylene diisocyanate, catalyst solution; organotin catalyst containing less than 1% ( 2 parts each of dibutyltin dilaurate) ethyl acetate / 2 butanone solution) were added and adjusted to 25 ° C. with good stirring. The prepared liquid is further stirred for 5 minutes with a stirrer / defoamer, and then a PET film having a contact angle of 25 ° after 3 minutes is applied to one side of a PET film having a thickness of 0.025 mm, and an adhesive layer is provided on the other side. When uniformly applied to the film substrate, a nonuniform and uneven foamed urethane sheet was obtained.
Various characteristics of the urethane foam sheets of Comparative Examples 1 to 5 are shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
乾式ウレタン原料；ポリエーテル系ウレタン（ＤＩＣ株式会社製ゾルテックスＰＸ－５５０）
架橋剤；ヘキサメチレンジイソシアネートプレポリマー、ヘキサメチレンジイソシアネート
触媒溶液；１％未満含有有機錫触媒（ジブチルチンジラウレート）酢酸エチル／２－ブタノン溶液
界面活性剤Ａ；パーフルオロアルキルエチレンオキサイド共重合体（ＡＧＣセイミケミカル株式会社製サーフロンＳ－４２０）
可塑剤；ジアルキレングリコールジベンゾエート（ＤＩＣ株式会社製ＰＢ－３Ａ）
コーティング剤；シリコーン；シリコーン系離型コーティング、ポリエステル；飽和ポリエステル系コーティング
Figure JPOXMLDOC01-appb-T000002
Dry urethane raw material; polyether urethane (DIC Corporation Soltex PX-550)
Hexamethylene diisocyanate prepolymer, hexamethylene diisocyanate catalyst solution; organotin catalyst containing less than 1% (dibutyltin dilaurate) ethyl acetate / 2-butanone solution surfactant A; perfluoroalkylethylene oxide copolymer (AGC Seimi) Chemical Corporation Surflon S-420)
Plasticizer: dialkylene glycol dibenzoate (PB-3A manufactured by DIC Corporation)
Coating agent; Silicone; Silicone release coating, Polyester; Saturated polyester coating
　なお、前記諸特性の評価項目（試験項目）の値は、次のようにして測定したものである。
　密度；軟質ポリウレタンフォームの物性試験：ＪＩＳ　Ｋ　６４００に準ずる。
　接触角；発泡体スキン面状に水を１５μＬ滴下した後、３分後の接触角を接触角計で測定した値である。接触角計としては、協和接触角計（ＣＡ－Ａ協和科学社製）を使用した。
　引張り強さ・伸び；軟質ポリウレタンフォームの物性試験：ＪＩＳ　Ｋ　６４００に準ずる。引張強度は２００ｍｍ／ｍｉｎで測定した。
　５０％圧縮硬さ；３０×３０ｍｍのサンプルを２枚積層し、１ｍｍ／ｍｉｎの速度で５０％圧縮したときの圧縮応力値。測定器は株式会社島津製作所製ａｕｔｏｇｒａｐｈＡＧ－Ｘを使用した。単位；ＭＰａ。
　収縮率；１００×１００のサンプルを打ち抜き、離型ＰＥＴフィルムから剥がし、横方向（ＴＤ＝Ｔｒａｖｅｒｓｅ　Ｄｉｒｅｃｔｉоｎ）と縦方向（ＭＤ＝Ｍａｃｈｉｎｅ　Ｄｉｒｅｃｔｉоｎ）の収縮率を測定し、それらの平均値を記載した。
　ブリードアウト；添加剤の表面移行を発泡ウレタンシートを接触させて目視で確認する。 In addition, the value of the evaluation item (test item) of the various characteristics is measured as follows.
Density: Physical property test of flexible polyurethane foam: Conforms to JIS K 6400.
Contact angle: 15 μL of water was dropped onto the foam skin surface, and the contact angle after 3 minutes was measured with a contact angle meter. As the contact angle meter, a Kyowa contact angle meter (manufactured by CA-A Kyowa Scientific Co., Ltd.) was used.
Tensile strength / elongation; Physical property test of flexible polyurethane foam: Conforms to JIS K 6400. The tensile strength was measured at 200 mm / min.
50% compression hardness: Compression stress value when two 30 × 30 mm samples are laminated and compressed by 50% at a speed of 1 mm / min. The measuring instrument used was autograph AG-X manufactured by Shimadzu Corporation. Unit: MPa.
Shrinkage rate: A 100 × 100 sample was punched and peeled from the release PET film, and the shrinkage rate in the transverse direction (TD = Traverse Direction) and the longitudinal direction (MD = Machine Direction) was measured, and the average value thereof was described.
Bleed out: The surface transition of the additive is visually confirmed by contacting the foamed urethane sheet.
　本発明は、薄くて柔軟性に富み、微細均一構造を有する基材付き発泡ウレタンシートを提供実施できるという効果を有し、緩衝用パッキン、防水パッキン、防水シート、透湿性シート、吸水シートなどに有用な、収縮率が０、厚さが０．０１～０．１５ｍｍの極薄シート状発泡ウレタンシートおよびその製造方法等に有用である。 The present invention has the effect that it is possible to provide a foamed urethane sheet with a base material that is thin, flexible, and has a fine uniform structure, such as a cushioning packing, a waterproof packing, a waterproof sheet, a moisture permeable sheet, and a water absorbent sheet. It is useful for an ultrathin sheet-like foamed urethane sheet having a shrinkage rate of 0 and a thickness of 0.01 to 0.15 mm, a method for producing the same, and the like.
　１　発泡体
　２　基材
　３　フィルム（ＰＥＴフィルム等）
　４　粘着層 DESCRIPTION OF SYMBOLS 1 Foam 2 Base material 3 Film (PET film etc.)
4 Adhesive layer

Claims (9)

  1. 　ウレタン樹脂、有機溶剤、水およびフッ素系界面活性剤の混合物をポリエチレンテレフタレートフィルム、ポリプロピレンフィルムまたはメチルペンテンポリマーフィルムのいずれか一種のフィルムであって、片面に粘着剤を有する基材に塗布、加温することにより得られる発泡体を前記基材上に有する発泡ウレタンシートであって、前記有機溶剤がトルエンとメチルエチルケトンの混合溶液であり、前記発泡体が連続通気構造の微細セルで構成されることを特徴とする発泡ウレタンシート。 Apply and heat a mixture of urethane resin, organic solvent, water and fluorosurfactant to a base material that is a polyethylene terephthalate film, polypropylene film or methylpentene polymer film and has an adhesive on one side A foamed urethane sheet having a foam on the substrate, wherein the organic solvent is a mixed solution of toluene and methyl ethyl ketone, and the foam is composed of fine cells having a continuous ventilation structure. A featured urethane foam sheet.
  2. 　前記混合物および前記基材を含む厚みが０．０１～０．１５ｍｍであることを特徴とする請求項１記載の発泡ウレタンシート。 The urethane foam sheet according to claim 1, wherein the thickness including the mixture and the substrate is 0.01 to 0.15 mm.
  3. 　片面に粘着層を有する前記基材のもう一方の片面には、発泡ウレタンシートと接着する表面処理が施され、この表面処理剤は、３分後の水との接触角が５５°以上の飽和ポリエステル系表面処理剤であることを特徴とする請求項１または２記載の発泡ウレタンシート。 The other surface of the base material having an adhesive layer on one surface is subjected to a surface treatment that adheres to the urethane foam sheet, and the surface treatment agent is saturated with a contact angle with water of 55 ° or more after 3 minutes. The foamed urethane sheet according to claim 1 or 2, which is a polyester-based surface treatment agent.
  4. 　前記フッ素系界面活性剤はパーフルオロアルキルエチレンオキシド付加物またはパーフルオロアルケニルポリエチレンオキシド付加物であることを特徴とする請求項１乃至３のいずれか１項に記載の発泡ウレタンシート。 The foamed urethane sheet according to any one of claims 1 to 3, wherein the fluorosurfactant is a perfluoroalkylethylene oxide adduct or a perfluoroalkenyl polyethylene oxide adduct.
  5. 　請求項１～４のいずれか１項に記載の発泡ウレタンシートからなることを特徴とするクッション材。 A cushioning material comprising the foamed urethane sheet according to any one of claims 1 to 4.
  6. 　水との接触角が９０°以上で疎水性であることを特徴とする請求項５記載のクッション材。 The cushioning material according to claim 5, wherein the contact angle with water is 90 ° or more and is hydrophobic.
  7. 　水との接触角が９０°未満で吸水性であることを特徴とする請求項５記載のクッション材。 6. The cushioning material according to claim 5, wherein the cushioning material has a water contact angle of less than 90 ° with water.
  8. 　ポリオール、ポリイソシアネート、発泡剤、フッ素系界面活性剤、触媒、トルエンとメチルエチルケトンを含む有機溶剤および必要に応じて架橋剤、着色剤、難燃剤、紫外線吸収剤、耐久性改良剤から選択される添加剤、等の配合物を混合撹拌して得られた反応原料を、ポリエチレンテレフタレートフィルム、ポリプロピレンフィルム、メチルペンテンフィルムのいずれか一種のフィルムであって、片面に粘着層を有する基材のもう一方の片面に均一に塗布した後、２段階加熱発泡して連続気泡構造の微細セルからなる発泡体を形成することを特徴とする発泡ウレタンシートの製造方法。 Additions selected from polyols, polyisocyanates, foaming agents, fluorosurfactants, catalysts, organic solvents containing toluene and methyl ethyl ketone, and optionally crosslinking agents, colorants, flame retardants, UV absorbers, and durability improvers The reaction raw material obtained by mixing and stirring a compound such as an agent is a film of any one of a polyethylene terephthalate film, a polypropylene film, and a methylpentene film, and the other of the base material having an adhesive layer on one side A method for producing a foamed urethane sheet, comprising uniformly applying to one side and then foaming by two-stage heating and foaming to form fine cells having an open-cell structure.
  9. 　前記フッ素系界面活性剤はパーフルオロアルキルエチレンオキシド付加物またはパーフルオロアルケニルポリエチレンオキシド付加物であることを特徴とする請求項８に記載の発泡ウレタンシートの製造方法。 The method for producing a urethane foam sheet according to claim 8, wherein the fluorosurfactant is a perfluoroalkylethylene oxide adduct or a perfluoroalkenyl polyethylene oxide adduct.
PCT/JP2014/002643 2013-05-29 2014-05-20 Urethane foam sheet, cushion material, and method for producing urethane foam sheet WO2014192249A1 (en)

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