WO2018003222A1 - Feuille de mousse de polyuréthane ainsi que procédé de fabrication de celle-ci, et procédé de fabrication de stratifié - Google Patents

Feuille de mousse de polyuréthane ainsi que procédé de fabrication de celle-ci, et procédé de fabrication de stratifié Download PDF

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Publication number
WO2018003222A1
WO2018003222A1 PCT/JP2017/014038 JP2017014038W WO2018003222A1 WO 2018003222 A1 WO2018003222 A1 WO 2018003222A1 JP 2017014038 W JP2017014038 W JP 2017014038W WO 2018003222 A1 WO2018003222 A1 WO 2018003222A1
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Prior art keywords
polyurethane foam
foam sheet
urethane prepolymer
producing
main agent
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PCT/JP2017/014038
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English (en)
Japanese (ja)
Inventor
大地 樋口
雅美 竹中
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Dic株式会社
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Priority to CN201780035616.4A priority Critical patent/CN109312040B/zh
Priority to JP2017531412A priority patent/JP6226109B1/ja
Publication of WO2018003222A1 publication Critical patent/WO2018003222A1/fr

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Classifications

    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen

Definitions

  • the present invention relates to a polyurethane foam sheet excellent in foam retention, texture and peel strength after sheet formation.
  • Polyurethane foam sheets are widely used in various fields such as automobile interior materials, shoe soles, copier rollers, cushioning materials, sealing materials, and electronic packing.
  • a method for producing a polyurethane foam sheet for example, a method is disclosed in which a urethane acrylate oligomer is applied on a substrate and cured by UV irradiation, and then wound up and used (see, for example, Patent Document 1).
  • the polyurethane foam sheet is often used as a laminate with different materials, not alone.
  • the different material include fiber base materials such as nonwoven fabrics, woven fabrics, and knitted fabrics, and composite fiber base materials impregnated with polyurethane or the like.
  • a polyurethane foam sheet is applied onto the release paper, the fiber base material is bonded onto the coated surface, and then the release paper is removed to roll the laminate. It is common to wind up.
  • the polyurethane foam sheet is not cured to a certain extent when it is wound on a roll, the foam in the sheet may be crushed and become a hard sheet, and the laminate may be wrinkled, twisted or peeled off. Etc. may occur.
  • the problem to be solved by the present invention is to provide a polyurethane foam sheet having excellent foam retention, texture and peel strength after sheet formation.
  • the present invention is a polyurethane foam sheet formed of a polyurethane composition containing a main agent (i) containing a urethane prepolymer (A) having an isocyanate group and a curing agent (ii) containing a polyol (B).
  • the urethane prepolymer (A) has a polymerizable unsaturated group in 5 to 25 mol% of the remaining isocyanate groups with respect to the urethane prepolymer (A-1) having an isocyanate group content of 2 to 20% by mass.
  • the present invention provides a polyurethane foam sheet characterized by being introduced.
  • the present invention also provides a method for producing a polyurethane foam sheet, wherein the polyurethane composition is foamed by a gas loading method or a water foaming method. Further, in the present invention, after the polyurethane composition is foamed by a gas loading method or a water foaming method, the polyurethane composition is applied onto a substrate and irradiated with ultraviolet rays to obtain a polyurethane foam sheet.
  • the present invention provides a method for producing a laminate, which is characterized by being bonded.
  • the polyurethane foam sheet of the present invention is excellent in foam retention, texture and peel strength after sheet formation.
  • polymerizable unsaturated groups are introduced into 5 to 25 mol% of the remaining isocyanate groups with respect to the urethane prepolymer (A-1) having an isocyanate group content of 2 to 20 mass%. It is formed of a polyurethane composition containing a main agent (i) containing a urethane prepolymer (A) and a curing agent (ii) containing a polyol (B).
  • the urethane prepolymer (A) is made from a urethane prepolymer (A-1) having an isocyanate group content of 2 to 20% by mass.
  • A-1 having an isocyanate group content of 2 to 20% by mass.
  • foam retention and appropriate coating properties can be obtained.
  • the isocyanate group content of the urethane prepolymer (A-1) is less than 2% by mass, the viscosity of the urethane prepolymer (A-1) is high, a smooth and good sheet itself cannot be obtained, or the desired peel strength cannot be obtained.
  • the isocyanate group content of the urethane prepolymer (A-1) is preferably in the range of 4 to 18% by mass from the viewpoint of obtaining even better foam retention. A range is more preferred.
  • the isocyanate group content of the urethane prepolymer (A-1) is a value measured by potentiometric titration in accordance with JIS K1603-1: 2007.
  • the isocyanate group content of the urethane prepolymer (A-1) is abbreviated as “NCO%”.
  • the urethane prepolymer (A) further introduces a polymerizable unsaturated group into 5 to 25 mol% of the remaining isocyanate groups with respect to the urethane prepolymer (A-1).
  • a polymerizable unsaturated group into the urethane prepolymer in such a range, when obtaining a polyurethane foam sheet, the initial viscosity can be controlled by ultraviolet curing, and good adhesion to different materials can be achieved.
  • the adherend to which the polyurethane foam sheet is bonded is a fiber base material, the amount of penetration of the polyurethane foam sheet into the fiber base material can be controlled, so that extremely excellent peel strength can be obtained.
  • the foam when the laminate having the polyurethane foam sheet is wound up, the foam is not crushed, and a laminate having a polyurethane foam sheet having a well-maintained foam cell shape can be obtained. It will be excellent.
  • the introduction ratio of the polymerizable unsaturated group with respect to the urethane prepolymer (A-1) is less than 5 mol%, there is a problem that a desired initial viscosity cannot be obtained and the foam retention is poor.
  • it exceeds mol% there is little penetration into the fiber substrate, and the desired peel strength may not be obtained, or the foam retention and texture may be poor.
  • the rate of introduction of polymerizable unsaturated groups into the urethane prepolymer (A-1) the amount of penetration into the fiber base material can be further easily controlled, and a further excellent peel strength and texture can be obtained. Accordingly, the range of 7 to 23 mol% of the remaining isocyanate groups is preferable, and the range of 10 to 20 mol% is more preferable.
  • urethane prepolymer (A) for example, a reaction product of a polyol (a-1), a polyisocyanate (a-2), and a (meth) acrylic compound (a-3) having a hydroxyl group is used. be able to.
  • polystyrene polyol (a-1) for example, polycarbonate polyol, polyether polyol, polyester polyol, polyacryl polyol, polybutadiene polyol and the like can be used. These polyols may be used alone or in combination of two or more.
  • the number average molecular weight of the polyol (a-1) is preferably in the range of 500 to 10,000, more preferably in the range of 800 to 6,000, from the viewpoint of obtaining good mechanical properties. preferable.
  • the number average molecular weight of the polyol (a-1) is a value measured under the following conditions by gel permeation chromatography (GPC) method.
  • Measuring device High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series. "TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000” (7.8 mm ID x 30 cm) x 1 "TSKgel G3000” (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID ⁇ 30 cm) ⁇ 1 detector: RI (differential refractometer) Column temperature: 40 ° C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection amount: 100 ⁇ L (tetrahydrofuran solution with a sample concentration of 0.4 mass%) Standard sample: A calibration curve was prepared using the following standard polystyrene.
  • the polyol (a-1) may be used in combination with a chain extender having a number average molecular weight in the range of 50 to 450, if necessary.
  • chain extender examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2-methyl-1,3.
  • polyisocyanate (a-2) examples include aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate; Aliphatic or alicyclic polyisocyanates such as diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate can be used.
  • aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, polymeric dipheny
  • polyisocyanates may be used alone or in combination of two or more. Among these, it is preferable to use an aromatic polysocyanate, and diphenylmethane diisocyanate is more preferable from the viewpoint that much more excellent reactivity and mechanical strength can be obtained.
  • Examples of the (meth) acrylic compound having a hydroxyl group and (a-3) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl acrylate, 3-hydroxybutyl ( (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl acrylate, hydroxyethyl (meth) acrylic acid alkyl ester such as hydroxyethylacrylamide; trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) Polyfunctional (meth) acrylates having hydroxyl groups such as acrylate and dipentaerythritol penta (meth) acrylate; polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, etc. It can be used. These compounds may be used alone or in combination of two or more.
  • the urethane prepolymer (A) can be produced, for example, by reacting the polyol (a-1) with the polyisocyanate (a-2) in the absence of a solvent, thereby producing the urethane prepolymer (A-1). Then, a method for producing the hydroxyl group-containing (meth) acrylic compound (a-3) by reaction can be used. In any of the above reactions, it is preferable to carry out, for example, under conditions of 20 to 120 ° C., for example, for about 30 minutes to 24 hours.
  • the equivalent ratio ([NCO / OH]) of the isocyanate group of the polyisocyanate (a-2) to the hydroxyl group of the polyol (a-1) is as follows: From the viewpoint of further improving the mechanical strength, it is preferably in the range of 1.5 to 25, more preferably in the range of 3 to 15.
  • the same polyol (a-1) as the raw material of the urethane prepolymer (A) can be used.
  • These polyols may be used alone or in combination of two or more.
  • the polyol (B) may be used in combination with the same chain extender as necessary. These chain extenders may be used alone or in combination of two or more.
  • the polyurethane composition used in the present invention contains a main agent (i) containing the urethane prepolymer (A) and a curing agent (ii) containing the polyol (B), but if necessary, other additions An agent may be contained.
  • additives examples include a photopolymerization initiator, water, a catalyst, a foam stabilizer, a polymerization inhibitor, an antioxidant, a thixotropic agent, a plasticizer, a stabilizer, an inorganic filler, an organic filler, Dyes, pigments and the like can be used.
  • These additives may be used alone or in combination of two or more, and may be contained in either the main agent (i) or the curing agent (ii), but the urethane prepolymer (A) It is preferable to contain in the said hardening
  • the photopolymerization initiator is preferably used for generating radicals by light irradiation, heating, or the like to initiate radical polymerization of the urethane (meth) acrylate (A).
  • A urethane (meth) acrylate
  • Acetophenone compounds benzoin, benzoin methyl Benzoin compounds such as ether, benzoin isoethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3 Benzophenone compounds such as 3,3'-dimethyl-4-methoxybenzophenone; thioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone Thioxanthone compounds such as 2,4-diisopropylthioxanthone; 4,4′-d
  • the amount used in the case of using the photopolymerization initiator is in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the urethane prepolymer (A) in terms of obtaining good ultraviolet curability.
  • the range of 0.5 to 2 parts by mass is more preferable.
  • Examples of the foaming method of the polyurethane composition when producing the polyurethane foam sheet of the present invention include a method using a gas loading method, a water foaming method, a mechanical flossing method and the like.
  • a gas loading method and / or the water foaming method from the viewpoint that the liquid component has a wide allowable viscosity range and can obtain more excellent foam retention
  • the inert gas is a polyurethane composition.
  • a gas loading method from the viewpoint that it can be well dissolved in a product and an excellent foam retention can be obtained.
  • an inert gas is gas loaded under a pressure of preferably 0.05 to 0.2 MPa, more preferably 0.07 to 0.18 MPa.
  • the gas loading refers to a process of forcibly embracing the main agent (i) and / or the curing agent (ii) by allowing an inert gas to enter from the outside under pressure. Moreover, when making the said inert gas approach, it is preferable from the point which can improve the solubility of an inert gas to stir the said main ingredient (i) and / or the said hardening
  • the gas loading can be performed using a known loading device.
  • the inert gas for example, carbon dioxide, helium gas, nitrogen gas, argon gas, neon gas or the like can be used.
  • carbon dioxide it is preferable to use carbon dioxide because of easy availability of raw materials and high solubility in the main agent (i) and the curing agent (ii).
  • the pressure at the time of gas loading is preferably in the range of 0.05 to 0.2 MPa in order to enable stable foam retention by an inert gas, and can maintain uniform foam. In view of obtaining a more excellent texture, the range is more preferably 0.07 to 0.18 MPa, and further preferably 0.08 to 0.17 MPa.
  • the time for performing the gas loading is preferably in the range of 10 minutes to 3 hours from the viewpoint of uniformly loading the inert gas and preventing deterioration of the urethane prepolymer or polyol. It is preferable that
  • the gas loading is preferably performed only on the main agent (i). This is because the main agent (i) has higher inert gas solubility than the curing agent (ii) when gas loading is performed under the same conditions (pressure and time). This is because it is possible to easily obtain a polyurethane foam sheet holding stable foam.
  • the curing agent (ii) may contain water described later, preferably a catalyst and a foaming agent, and may use a water foaming method together with gas loading.
  • the viscosity at 50 ° C. of the main agent (i) at the time of gas loading is in the range of 200 to 20,000 mPa ⁇ s from the viewpoint that an inert gas can be satisfactorily loaded even under the pressure.
  • the range of 250 to 15,000 mPa ⁇ s is more preferable.
  • the viscosity in 50 degreeC of the said main ingredient (i) shows the value measured with the B-type viscosity meter (rotor No. 3, rotation speed: 12rpm).
  • the specific gravity of the main agent (i) immediately after releasing the main agent (i) after the gas loading to normal pressure is more excellent in foam retention, and From the viewpoint of obtaining a texture, the range is preferably 0.2 to 0.8, and more preferably 0.3 to 0.7.
  • the pressure is once returned to normal pressure, and then the main agent (i) and the curing agent (ii) are mixed to proceed the urethanization reaction; the gas loaded main agent (i) And / or a method in which the curing agent (ii) is moved to a mixer or the like connected to a loading device using a pressure difference and mixed by a mixer or the like to advance the urethanization reaction.
  • the mixing ratio [(i) :( ii)] of the main agent (i) and the curing agent (ii) is preferably in the range of 80:20 to 20:80, and 75:25 to A range of 25:75 is more preferred.
  • the mixed main agent (i) and the curing agent (ii) are applied onto a substrate such as a release paper or a substrate coated with a release agent, and irradiated with ultraviolet rays.
  • a substrate such as a release paper or a substrate coated with a release agent, and irradiated with ultraviolet rays.
  • a polyurethane foam sheet can be obtained.
  • Examples of a method of applying the mixed main agent (i) and curing agent (ii) include a method using an applicator, a roll coater, a spray coater, a T-die coater, a knife coater, and the like.
  • the thickness to be applied is, for example, in the range of 10 to 500 ⁇ m.
  • Examples of the ultraviolet irradiation method include low-intensity ultraviolet light irradiation devices such as fluorescent chemical lamps, black lights, and LED lamps; xenon lamps, xenon-mercury lamps, metal halide lamps, high-pressure mercury lamps, low-pressure mercury lamps, and LEDs.
  • a method of irradiating a predetermined ultraviolet ray using a medium / high illuminance ultraviolet light irradiation device such as a lamp may be mentioned.
  • the integrated light amount when performing the ultraviolet irradiation is, for example, in the range of 100 to 1,500 mJ / cm 2 , and preferably 200 to 1, from the viewpoint of allowing the photopolymerization reaction to proceed without excess or deficiency.
  • the range is 000 mJ / cm 2 .
  • the accumulated light quantity of the ultraviolet rays is based on a value measured in a wavelength range of 300 to 390 nm using a UV checker “UVR-N1” manufactured by GS Yuasa Corporation.
  • aging is preferably performed at a temperature of 40 to 130 ° C. for 3 minutes to 3 days in order to cure the remaining isocyanate of the urethane prepolymer (A). Thereafter, aging may be performed at a temperature of 40 to 80 ° C. for 1 to 3 days.
  • the curing agent (ii) contains water, preferably further a catalyst and a foam stabilizer, and the main agent (i) and the curing
  • the method of mixing agent (ii) is mentioned.
  • the water functions as a foaming agent, and the amount used thereof is preferably in the range of 0.01 to 10% by mass, and in the range of 0.02 to 5% by mass in the curing agent (ii). More preferred.
  • Examples of the catalyst include triethylenediamine, N, N, N ′, N′-tetramethylhexanediamine, N, N, N ′, N′-tetramethylpropanediamine, N, N, N ′, N ′′.
  • the amount used in the case of using the catalyst is preferably in the range of 0.01 to 1% by mass, more preferably in the range of 0.05 to 0.5% by mass in the curing agent (ii).
  • a silicone-based surfactant can be preferably used.
  • silicone-based surfactant can be preferably used.
  • “SZ-1919”, “SH-192”, “SH-190”, “SZ-580”, “SRX-280A” , “SZ-1959”, “SZ-1328E”, “SF-2937F”, “SF-2938F”, “SZ-1671”, “SH-193”, “SZ-1923”, “Silicon Y-7006” As described above, Toray Dow Corning Silicone Co., Ltd.) and the like can be obtained as commercial products.
  • the amount used is preferably in the range of 0.01 to 5% by mass, more preferably in the range of 0.03 to 3% by mass in the curing agent (ii).
  • Examples of a method of mixing the main agent (i) and the curing agent (ii) include a method using a mixed casting machine.
  • the main agent (i) and the curing agent (ii) are put into respective tanks of a mixed casting machine, and the main agent (i) is preferably heated in the range of 40 to 80 ° C.
  • the curing agent (ii) is preferably heated in the range of 40 to 80 ° C., and each is mixed with a mixing caster.
  • the mixing ratio [(i) :( ii)] of the main agent (i) and the curing agent (ii) is preferably in the range of 80:20 to 20:80, and 75:25 to A range of 25:75 is more preferred.
  • the mixed main agent (i) and the curing agent (ii) are applied onto a substrate such as a release paper or a substrate coated with a release agent, and irradiated with ultraviolet rays.
  • a substrate such as a release paper or a substrate coated with a release agent, and irradiated with ultraviolet rays.
  • a polyurethane foam sheet can be obtained. This step is the same as when the gas loading method is used.
  • the density of the polyurethane foam sheet obtained by the above method is preferably in the range of 0.5 to 0.95 g / cm 3 from the viewpoint of obtaining a good texture, and 0.65 to 0.9 g / cm 3. A range of 3 is more preferable.
  • the measuring method of the density of the said polyurethane foam sheet is based on the method of measuring the thickness and weight of the polyurethane foam sheet cut
  • judged in length 10cm and width 10cm, and calculating a density according to following formula (1). Density (g / cm 3 ) Weight (g) / 10 (cm) ⁇ 10 (cm) ⁇ Thickness (cm) (1)
  • a polyurethane foam sheet obtained using the gas loading method and / or a polyurethane foam sheet obtained using the water foaming method are bonded to a fiber base material.
  • the method of manufacturing by this is mentioned preferably.
  • the polyurethane foam sheet may be one that has not been subjected to aging after the ultraviolet irradiation, or one that has been subjected to ultraviolet irradiation and aging. Among these, it is preferable to employ the former method from the viewpoint that it is easy to control the amount of penetration of the polyurethane foam sheet into the fiber substrate and that a more excellent peel strength can be obtained.
  • a nonwoven fabric, a woven fabric, a knitted fabric, or the like can be used as the fiber base material.
  • polyester fiber, nylon fiber, acrylic fiber, acetate fiber, rayon fiber, polylactic acid fiber, cotton, hemp, silk, wool, blended fiber thereof or the like can be used as the fiber substrate. it can.
  • the polyurethane foam sheet of the present invention is excellent in foam retention, texture, and peel strength after sheet formation.
  • Preparation Example 1 Preparation of main agent (i-1) 4,4′-diphenylmethane diisocyanate (hereinafter referred to as “MDI”) was placed in a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. 100 parts by mass and 120 parts by mass of polytetramethylene glycol ("PTMG2000" manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 2,000) are added and reacted at 80 ° C for 3 hours, NCO%: 12 9% by mass of urethane prepolymer (A-1-1) was obtained.
  • PTMG2000 polytetramethylene glycol
  • HSA 2-hydroxyethyl acrylate
  • a urethane prepolymer having acryloyl groups introduced into 15 mol% of the remaining isocyanate groups was obtained and used as a main agent (i-1).
  • the viscosity of the main agent (i-1) at 50 ° C. was 1,550 mPa ⁇ s.
  • Preparation Example 2 Preparation of main agent (i-2) In a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 100 parts by mass of MDI and 107 parts by mass of PTMG2000 were placed. The mixture was reacted at 80 ° C. for 3 hours to obtain a urethane prepolymer (A-1-2) having an NCO%: 14.2% by mass. Next, 16 parts by mass of HEA was added and reacted at 60 ° C.
  • urethane prepolymer (Aii) having acryloyl groups introduced into 20 mol% of the remaining isocyanate groups, which was used as the main agent (i-2).
  • the viscosity of the main agent (i-2) at 50 ° C. was 1,800 mPa ⁇ s.
  • Preparation Example 3 Preparation of main agent (i'-1) 100 parts by mass of MDI and 150 parts by mass of PTMG2000 were placed in a four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser. And a reaction at 80 ° C. for 3 hours to obtain a urethane prepolymer (A′-1-1) having an NCO% of 11.2% by mass. Next, 2.3 parts by mass of HEA was added and reacted at 60 ° C. for 2 hours to obtain a urethane prepolymer (A′i) in which acryloyl groups were introduced into 3 mol% of the remaining isocyanate groups. -1). The viscosity of the main agent (i′-1) at 50 ° C. was 1,310 mPa ⁇ s.
  • Preparation Example 4 Preparation of main agent (i'-2) 100 parts by mass of MDI and 75 parts by mass of PTMG2000 were placed in a four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser. And a reaction at 80 ° C. for 3 hours to obtain a urethane prepolymer (A′-1-2) having an NCO% of 17.4% by mass. Next, 25.2 parts by mass of HEA was added and reacted at 60 ° C. for 2 hours to obtain a urethane prepolymer (A′ii) in which acryloyl groups were introduced into 30 mol% of the remaining isocyanate groups. -2). The viscosity of the main agent (i′-2) at 50 ° C. was 3,610 mPa ⁇ s.
  • Preparation Example 5 Preparation of main agent (i'-3) 100 parts by mass of MDI and 520 parts by mass of PTMG2000 were placed in a four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser. And a reaction at 80 ° C. for 3 hours to obtain a urethane prepolymer (A′-1-3) having an NCO% of 1.9% by mass. Next, 4.9 parts by mass of HEA was added and reacted at 60 ° C. for 2 hours to obtain a urethane prepolymer (A′iii) in which acryloyl groups were introduced into 15 mol% of the remaining isocyanate groups. -3). The viscosity of the main agent (i′-3) at 50 ° C. was 7,400 mPa ⁇ s.
  • Preparation Example 6 Preparation of main agent (i′-4) 100 parts by mass of MDI and 50 parts by mass of PTMG2000 were placed in a four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser. And a reaction at 80 ° C. for 3 hours to obtain a urethane prepolymer (A′-1-4) having NCO%: 21% by mass. Next, 13.1 parts by mass of HEA was added and reacted at 60 ° C. for 2 hours to obtain a urethane prepolymer (A′iv) in which acryloyl groups were introduced into 15 mol% of the remaining isocyanate groups. -4). The viscosity of the main agent (i′-4) at 50 ° C. was 820 mPa ⁇ s.
  • Example 1 The main agent (i-1) was placed in a loading device. Thereafter, the inside of the loading apparatus was pressurized to 0.1 MPa with carbon dioxide, and the raw material was loaded with stirring for 30 minutes. Next, the main agent (i-1) loaded with gas using the pressure difference was charged from the loading device into the main agent tank of the low pressure urethane injection foaming machine “MT5” manufactured by Polymer Engineering Co., Ltd. and circulated under a pressure of 0.5 MPa. . Curing agent (ii-1) was also charged into the curing agent tank and circulated under a pressure of 0.5 MPa.
  • (i-1) and (ii-1) are simultaneously ejected so as to have a mass ratio of 167: 100 and instantaneously mixed, and then the mixed solution is formed to have a thickness of 250 ⁇ m on the sheet coated with the release agent.
  • the coated material was irradiated with 300 mJ / cm 2 of ultraviolet rays using an ultraviolet irradiation device “CSOT-40” (high pressure mercury lamp, illuminance: 120 mW / cm 2 , conveyor speed: 5 m / min) manufactured by Nippon Battery Co., Ltd.
  • CSOT-40 high pressure mercury lamp, illuminance: 120 mW / cm 2 , conveyor speed: 5 m / min
  • the base fabric was bonded.
  • heat treatment was performed at 110 ° C. for 5 minutes.
  • the fiber laminate was obtained by continuously operating for 30 minutes and winding.
  • Example 2 Comparative Examples 1 to 4
  • a fiber laminate was obtained in the same manner as in Example 1 except that the type of the main agent (i) used was changed as shown in Tables 1 and 2.
  • the polyurethane foam sheet obtained by the production method of the present invention retained the foam well even after the sheet was formed, and was excellent in texture and peel strength.
  • Comparative Example 1 is an embodiment using a urethane prepolymer (A) in which the amount of polymerizable unsaturated groups introduced to the remaining isocyanate groups is less than the range defined in the present invention, but the retention of foam. The material was damaged due to the poor quality and excessive penetration into the base fabric.
  • Comparative Example 2 is an embodiment using a urethane prepolymer (A) in which the amount of polymerizable unsaturated groups introduced to the remaining isocyanate groups exceeds the range specified in the present invention. Although it was good, the texture was poor. Moreover, there was no penetration into the base fabric and the peel strength was poor.
  • Comparative Example 3 is an embodiment in which the NCO% of the urethane prepolymer (A-1) is below the range defined in the present invention, but the foam retention is good but the texture is poor. Moreover, there was no penetration into the base fabric and the peel strength was poor.
  • Comparative Example 3 is an embodiment in which the NCO% of the urethane prepolymer (A-1) exceeds the range specified in the present invention, but the foam retention and texture are poor, and the penetration into the base fabric is poor. Too much and peel strength was poor.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention a pour objet de fournir une feuille de mousse de polyuréthane qui se révèle excellente en termes de caractéristique de maintien de mousse après formation de feuille, de texture et de résistance au pelage. Plus précisément, l'invention fournit une feuille de mousse de polyuréthane qui est formée à l'aide d'une composition de polyuréthane comprenant un agent principal (i) contenant un prépolymère d'uréthane (A) doté de groupes isocyanate, et un agent de durcissement (ii) contenant un polyol (B). Cette feuille de mousse de polyuréthane est caractéristique en ce que ledit prépolymère d'uréthane (A) est telle qu'un groupe insaturé polymérisable est induit dans 5 à 25% en moles des groupes isocyanates résiduels pour un prépolymère d'uréthane (A-1) de teneur en groupes isocyanate comprise entre 2 et 20% en masse. Enfin, la feuille de mousse de polyuréthane de l'invention est caractéristique en ce que ladite composition de polyuréthane est soumise à un moussage au moyen d'un procédé de chargement de gaz, ou d'un procédé de moussage à l'eau.
PCT/JP2017/014038 2016-06-28 2017-04-04 Feuille de mousse de polyuréthane ainsi que procédé de fabrication de celle-ci, et procédé de fabrication de stratifié WO2018003222A1 (fr)

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JP2017531412A JP6226109B1 (ja) 2016-06-28 2017-04-04 ポリウレタン発泡シート、その製造方法、及び積層体の製造方法

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JPH07102038A (ja) * 1993-10-01 1995-04-18 Nippon Polyurethane Ind Co Ltd 硬質ポリウレタンフォームの製造方法
JP2005506397A (ja) * 2001-04-01 2005-03-03 ダウ グローバル テクノロジーズ インコーポレイティド 硬質ポリウレタン発泡体
JP2008101149A (ja) * 2006-10-20 2008-05-01 Inoac Corp 紫外線硬化発泡体
JP2008156544A (ja) * 2006-12-26 2008-07-10 Inoac Corp 紫外線硬化発泡体
JP2014024880A (ja) * 2012-07-24 2014-02-06 Dic Corp 紫外線硬化型ウレタンアクリレート樹脂組成物、薄膜成形体、光学フィルム、及び薄膜成形体の製造方法
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JP5633768B2 (ja) * 2012-09-20 2014-12-03 Dic株式会社 紫外線硬化性ウレタンアクリレート組成物、薄膜成形体、光学フィルム、及び薄膜成形体の製造方法

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JPS5036559A (fr) * 1973-08-03 1975-04-05
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JPH07102038A (ja) * 1993-10-01 1995-04-18 Nippon Polyurethane Ind Co Ltd 硬質ポリウレタンフォームの製造方法
JP2005506397A (ja) * 2001-04-01 2005-03-03 ダウ グローバル テクノロジーズ インコーポレイティド 硬質ポリウレタン発泡体
JP2008101149A (ja) * 2006-10-20 2008-05-01 Inoac Corp 紫外線硬化発泡体
JP2008156544A (ja) * 2006-12-26 2008-07-10 Inoac Corp 紫外線硬化発泡体
JP2014024880A (ja) * 2012-07-24 2014-02-06 Dic Corp 紫外線硬化型ウレタンアクリレート樹脂組成物、薄膜成形体、光学フィルム、及び薄膜成形体の製造方法
JP2014084394A (ja) * 2012-10-23 2014-05-12 Inoac Gijutsu Kenkyusho:Kk 光硬化発泡体製造方法

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