WO2018003222A1 - Polyurethane foam sheet, method for producing same, and method for producing laminate - Google Patents

Polyurethane foam sheet, method for producing same, and method for producing laminate 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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WO
WIPO (PCT)
Prior art keywords
polyurethane foam
foam sheet
urethane prepolymer
producing
main agent
Prior art date
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PCT/JP2017/014038
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French (fr)
Japanese (ja)
Inventor
大地 樋口
雅美 竹中
Original Assignee
Dic株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to CN201780035616.4A priority Critical patent/CN109312040B/en
Priority to JP2017531412A priority patent/JP6226109B1/en
Publication of WO2018003222A1 publication Critical patent/WO2018003222A1/en

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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.

Abstract

The problem the invention is intended to solve is to provide a polyurethane foam sheet having excellent foam retentivity after sheet formation, feel, and peel strength. The invention provides a polyurethane foam sheet formed from a polyurethane composition containing a main agent (i) including a urethane prepolymer (A) having isocyanate groups and a curing agent (ii) including a polyol (B), wherein the polyurethane foam sheet is characterized in that the urethane prepolymer (A) has polymerizable unsaturated groups introduced into 5-25 mol% of the remaining isocyanate groups relative to the urethane prepolymer (A-1) having an isocyanate group content of 2-20 mass%. The invention also provides a method for producing a polyurethane foam sheet characterized in that the above polyurethane composition is foamed by a gas loading method or a water foaming method.

Description

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Polyurethane foam sheet, method for producing the same, and method for producing a laminate
　本発明は、シート形成後の泡保持性、風合い、及び剥離強度に優れるポリウレタン発泡シートに関する。 The present invention relates to a polyurethane foam sheet excellent in foam retention, texture and peel strength after sheet formation.
　ポリウレタン発泡シートは、自動車内装材、靴底、複写機用ローラ、緩衝材、シール材、電子用パッキンなど様々な分野にて広く利用されている。ポリウレタン発泡シートの製造方法としては、例えば、基材上にウレタンアクリレートオリゴマーを塗布し、紫外線硬化した後に、巻き取って使用する方法が開示されている（例えば、特許文献１を参照。）。 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. As 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).
　前記ポリウレタン発泡シートとしては、それ単独ではなく、異素材との積層体として利用されることも多い。前記異素材としては、例えば、不織布、織布、編布などの繊維基材や、これらにポリウレタン等を含浸させた複合繊維基材等が挙げられる。これら異素材との積層体を製造する際には、離型紙上にポリウレタン発泡シートを塗布し、その塗布面上に繊維基材を接着した後、離型紙を除去して得られる積層体をロールに巻き取ることが一般的である。しかしながら、ロールに巻き取る段階で、ある程度以上のポリウレタン発泡シートの硬化が行われていないと、シート中の泡が潰れてしまい、硬いシートになってしまう問題や、積層体にシワ・よれ・剥がれ等が生じることがあった。 The polyurethane foam sheet is often used as a laminate with different materials, not alone. Examples of 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. When manufacturing a laminate with these different materials, 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. However, if 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.
特開２００８－１５６５４４号公報JP 2008-156544 A
　本発明が解決しようとする課題は、シート形成後の泡保持性、風合い、及び剥離強度に優れるポリウレタン発泡シートを提供することである。 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.
　本発明は、イソシアネート基を有するウレタンプレポリマー（Ａ）を含む主剤（ｉ）と、ポリオール（Ｂ）を含む硬化剤（ｉｉ）とを含有するポリウレタン組成物により形成されたポリウレタン発泡シートであって、前記ウレタンプレポリマー（Ａ）が、イソシアネート基含有率が２～２０質量％であるウレタンプレポリマー（Ａ－１）に対し、残存するイソシアネート基の５～２５モル％に重合性不飽和基を導入したものであることを特徴とするポリウレタン発泡シートを提供するものである。 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.
　また、本発明は、前記ポリウレタン組成物を、ガスローディング法、又は、水発泡法により発泡することを特徴とするポリウレタン発泡シートの製造方法を提供するものである。更に、本発明は、前記ポリウレタン組成物を、ガスローディング法、又は、水発泡法により発泡させた後に、基材上に塗布し、紫外線照射してポリウレタン発泡シートを得、次いで、繊維基材を貼り合せることを特徴とする積層体の製造方法を提供するものである。 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.
　本発明のポリウレタン発泡シートは、シート形成後の泡保持性、風合い、及び剥離強度に優れるものである。 The polyurethane foam sheet of the present invention is excellent in foam retention, texture and peel strength after sheet formation.
　本発明のポリウレタン発泡シートは、イソシアネート基含有率が２～２０質量％であるウレタンプレポリマー（Ａ－１）に対し、残存するイソシアネート基の５～２５モル％に重合性不飽和基を導入したウレタンプレポリマー（Ａ）を含む主剤（ｉ）と、ポリオール（Ｂ）を含む硬化剤（ｉｉ）とを含有するポリウレタン組成物により形成されたものである。 In the polyurethane foam sheet of the present invention, 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).
　前記ウレタンプレポリマー（Ａ）は、イソシアネート基含有率が２～２０質量％であるウレタンプレポリマー（Ａ－１）を原料とするものである。前記ウレタンプレポリマー（Ａ－１）のイソシアネート基含有率が前記範囲であることにより、泡の保持性、及び適度な塗工性が得られる。前記ウレタンプレポリマー（Ａ－１）のイソシアネート基含有率が２質量％を下回る場合には、粘度が高く、平滑で良好なシート自体を得ることができない場合や、所望の剥離強度が得られない場合があり、また、２０質量％を超える場合には、粘度が低く、実用上使用可能なレベルの厚さを有するシートを得ることができない場合や所望の剥離強度が得られない問題がある。前記ウレタンプレポリマー（Ａ－１）のイソシアネート基含有率としては、より一層優れた泡の保持性が得られる点から、４～１８質量％の範囲であることが好ましく、５～１５質量％の範囲がより好ましい。なお、前記ウレタンプレポリマー（Ａ－１）のイソシアネート基含有率は、ＪＩＳＫ１６０３－１：２００７に準拠し、電位差滴定法により測定した値を示す。以下、ウレタンプレポリマー（Ａ－１）のイソシアネート基含有率は、「ＮＣＯ％」と略記する。 The urethane prepolymer (A) is made from a urethane prepolymer (A-1) having an isocyanate group content of 2 to 20% by mass. When the isocyanate group content of the urethane prepolymer (A-1) is within the above range, foam retention and appropriate coating properties can be obtained. When 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. When the content exceeds 20% by mass, there is a problem that the viscosity is low and a sheet having a practically usable thickness cannot be obtained or a 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. Hereinafter, the isocyanate group content of the urethane prepolymer (A-1) is abbreviated as “NCO%”.
　前記ウレタンプレポリマー（Ａ）は、更に、前記ウレタンプレポリマー（Ａ－１）に対し、残存するイソシアネート基の５～２５モル％に重合性不飽和基を導入することが必須である。係る範囲で重合性不飽和基をウレタンプレポリマーに導入することで、ポリウレタン発泡シートを得る際に、紫外線硬化により初期粘度をコントロールすることができ、異素材への良好な接着を可能とする。特に、ポリウレタン発泡シートを貼り合せる被着体が繊維基材の場合には、繊維基材に対するポリウレタン発泡シートの浸み込み量をコントロールできるため、極めて優れた剥離強度を得ることができる。また、ポリウレタン発泡シートを有する積層体を巻き取った際に、泡が潰れることがなく、発泡セルの形状を良好に保持したポリウレタン発泡シートを有する積層体を得ることができ、該積層体は風合いに優れるものとなる。前記ウレタンプレポリマー（Ａ－１）に対する重合性不飽和基の導入率が５モル％を下回る場合には、所望の初期粘度が得られず、泡の保持性が不良となる問題があり、２５モル％を超える場合には、繊維基材への浸み込みが少なく、所望の剥離強度が得られない場合や、泡の保持性、及び風合いが不良となる場合がある。前記ウレタンプレポリマー（Ａ－１）に対する重合性不飽和基の導入率としては、より一層繊維基材への浸み込み量のコントロールが容易となり、一層優れた剥離強度、及び風合いが得られる点から、残存するイソシアネート基の７～２３モル％の範囲であることが好ましく、１０～２０モル％の範囲がより好ましい。 It is essential that 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). By introducing 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. In particular, when 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. In addition, 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. When 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. When 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. As 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.
　前記ウレタンプレポリマー（Ａ）としては、具体的には、例えば、ポリオール（ａ－１）とポリイソシアネート（ａ－２）と水酸基を有する（メタ）アクリル化合物（ａ－３）の反応物を用いることができる。 Specifically, as the 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.
　前記ポリオール（ａ－１）としては、例えば、ポリカーボネートポリオール、ポリエーテルポリオール、ポリエステルポリオール、ポリアクリルポリオール、ポリブタジエンポリオール等を用いることができる。これらのポリオールは単独で用いても２種以上を併用してもよい。 As the 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.
　前記ポリオール（ａ－１）の数平均分子量としては、良好な機械的物性が得られる点から、５００～１０，０００の範囲であることが好ましく、８００～６，０００の範囲であることがより好ましい。なお、前記ポリオール（ａ－１）の数平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により、下記の条件で測定した値を示す。 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.
測定装置：高速ＧＰＣ装置（東ソー株式会社製「ＨＬＣ－８２２０ＧＰＣ」）
カラム：東ソー株式会社製の下記のカラムを直列に接続して使用した。
　「ＴＳＫｇｅｌ　Ｇ５０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ４０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ３０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ２０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
検出器：ＲＩ（示差屈折計）
カラム温度：４０℃
溶離液：テトラヒドロフラン（ＴＨＦ）
流速：１．０ｍＬ／分
注入量：１００μＬ（試料濃度０．４質量％のテトラヒドロフラン溶液）
標準試料：下記の標準ポリスチレンを用いて検量線を作成した。 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 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%)
Standard sample: A calibration curve was prepared using the following standard polystyrene.
（標準ポリスチレン）
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－５００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－１０００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－２５００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－５０００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－４」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－４０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－８０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１２８」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２８８」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－５５０」 (Standard polystyrene)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation
　前記ポリオール（ａ－１）には、必要に応じて、数平均分子量が５０～４５０の範囲の鎖伸長剤を併用してもよい。 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.
　前記鎖伸長剤としては、例えば、エチレングリコール、プロピレングリコール、１，３－プロパンジオール、１，４－ブタンジオール、１，３－ブタンジオール、１，２－ブタンジオール、２－メチル－１，３－プロパンジオール、１，５－ペンタンジオール、ネオペンチルグリコール、１，６－ヘキサンジオール、１，５－ヘキサンジオール、３－メチル－１，５－ペンタンジオール、１，７－ヘプタンジオール、１，８－オクタンジオール、１，９－ノナンジオール、１，８－ノナンジオール、２－エチル－２－ブチル－１，３－プロパンジオール、１，１０－デカンジオール、１，１２－ドデカンジオール、１，４－シクロヘキサンジメタノール、１，３－シクロヘキサンジメタノール、トリメチロールプロパン、トリメチロールエタン、グリセリン等の水酸基を有する鎖伸長剤；エチレンジアミン、１，２－プロパンジアミン、１，６－ヘキサメチレンジアミン、ピペラジン、２，５－ジメチルピペラジン、イソホロンジアミン、１，２－シクロヘキサンジアミン、１，３－シクロヘキサンジアミン、１，４－シクロヘキサンジアミン、４，４’－ジシクロヘキシルメタンジアミン、３，３’－ジメチル－４，４’－ジシクロヘキシルメタンジアミン、１，４－シクロヘキサンジアミン、ヒドラジン等のアミノ基を有する鎖伸長剤などを用いることができる。これらの鎖伸長剤は単独で用いても２種以上を併用してもよい。 Examples of the chain extender include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2-methyl-1,3. -Propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,5-hexanediol, 3-methyl-1,5-pentanediol, 1,7-heptanediol, 1,8 -Octanediol, 1,9-nonanediol, 1,8-nonanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4 -Cyclohexanedimethanol, 1,3-cyclohexanedimethanol, trimethylolpropane, trimethylol ether Chain extenders having hydroxyl groups such as ethylene and glycerin; ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 1,2-cyclohexanediamine, 1, Amino groups such as 3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4′-dicyclohexylmethanediamine, 3,3′-dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, hydrazine, etc. The chain extender which has can be used. These chain extenders may be used alone or in combination of two or more.
　前記ポリイソシアネート（ａ－２）としては、例えば、ポリメチレンポリフェニルポリイソシアネート、ジフェニルメタンジイソシアネート、ポリメリックジフェニルメタンジイソシアネート、カルボジイミド変性ジフェニルメタンジイソシアネート、フェニレンジイソシアネート、トリレンジイソシアネート、ナフタレンジイソシアネート等の芳香族ポリイソシアネート；ヘキサメチレンジイソシアネート、リジンジイソシアネート、シクロヘキサンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート等の脂肪族又は脂環族ポリイソシアネートなどを用いることができる。これらのポリイソシアネートは単独で用いても２種以上を併用してもよい。これらの中でも、より一層優れた反応性及び機械的強度が得られる点から、芳香族ポリソシアネートを用いることが好ましく、ジフェニルメタンジイソシアネートがより好ましい。 Examples of the polyisocyanate (a-2) 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. These 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.
　前記水酸基を有する（メタ）アクリル化合物と（ａ－３）しては、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピルアクリレート、３－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、６－ヒドロキシヘキシルアクリレート、ヒドロキシエチルアクリルアミド等の水酸基を有する（メタ）アクリル酸アルキルエステル；トリメチロールプロパンジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート等の水酸基を有する多官能（メタ）アクリレート；ポリエチレングリコールモノアクリレート、ポリプロピレングリコールモノアクリレートなどを用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。 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.
　前記ウレタンプレポリマー（Ａ）の製造方法としては、例えば、無溶剤下で、前記ポリオール（ａ－１）と前記ポリイソシアネート（ａ－２）とを反応させることでウレタンプレポリマー（Ａ－１）を得、次いで、前記水酸基を有する（メタ）アクリル化合物（ａ－３）を反応させることによって製造する方法等を用いることができる。前記反応はいずれにおいても、例えば、２０～１２０℃の条件下で、例えば、３０分～２４時間程度行うことが好ましい。 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.
　前記ウレタンプレポリマー（Ａ－１）を製造する際の、前記ポリイソシアネート（ａ－２）が有するイソシアネート基と前記ポリオール（ａ－１）が有する水酸基の当量比（［ＮＣＯ／ＯＨ］）としては、機械的強度をより一層向上できる点から、１．５～２５の範囲であることが好ましく、３～１５の範囲であることがより好ましい。 When the urethane prepolymer (A-1) is produced, 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.
　前記硬化剤（ｉｉ）に用いる前記ポリオール（Ｂ）としては、例えば、前記ウレタンプレポリマー（Ａ）の原料である前記ポリオール（ａ－１）と同様のものを用いることができる。これらのポリオールは単独で用いても２種以上を併用してもよい。 As the polyol (B) used for the curing agent (ii), for example, 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.
　また、前記ポリオール（Ｂ）には、必要に応じて、前記鎖伸長剤と同様のものを併用してもよい。これらの鎖伸長剤は単独で用いても２種以上を併用してもよい。 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.
　本発明で用いるポリウレタン組成物は、前記ウレタンプレポリマー（Ａ）を含む主剤（ｉ）と、前記ポリオール（Ｂ）を含む硬化剤（ｉｉ）とを含有するが、必要に応じて、その他の添加剤を含有してもよい。 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.
　前記その他の添加剤としては、例えば、光重合開始剤、水、触媒、整泡剤、重合禁止剤、酸化防止剤、チキソ性付与剤、可塑剤、安定剤、無機充填剤、有機充填剤、染料、顔料等を用いることができる。これらの添加剤は単独で用いても２種以上を併用してもよく、前記主剤（ｉ）と前記硬化剤（ｉｉ）とのどちらに含有されていてもよいが、ウレタンプレポリマー（Ａ）の安定性を向上できる点から、前記硬化剤（ｉｉ）に含有されることが好ましい。 Examples of the other additives 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 | curing agent (ii) from the point which can improve stability.
　前記光重合開始剤は、光照射や加熱等によってラジカルを発生し、前記ウレタン（メタ）アクリレート（Ａ）のラジカル重合を開始させるため用いることが好ましく、例えば、４－フェノキシジクロロアセトフェノン、ジエトキシアセトフェノン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、１－（４－イソプロピルフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オン、１－ヒドロキシシクロヘキシルフェニルケトン、４－（２－ヒドロキシエトキシ）－フェニル（２－ヒドロキシ－２－プロピル）ケトン、２－メチル－［４－（メチルチオ）フェニル］－２－モルフォリノ－１－プロパノン、２，２－ジメトキシ－２－フェニルアセトフェノン等のアセトフェノン化合物；ベンゾイン、ベンゾインメチルエーテル、ベンゾインイソエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル等のベンゾイン化合物；ベンゾフェノン、ベンゾイル安息香酸、ベンゾイル安息香酸メチル、４－フェニルベンゾフェノン、ヒドロキシベンゾフェノン、４－ベンゾイル－４’－メチルジフェニルサルファイド、３，３’－ジメチル－４－メトキシベンゾフェノン等のベンゾフェノン化合物；チオキサントン、２－クロロチオキサントン、２，４－ジクロロチオキサントン、２－メチルチオキサントン、２，４－ジメチルチオキサントン、２，４－ジエチルチオキサントン、イソプロピルチオキサントン、２，４－ジイソプロピルチオキサントン等のチオキサントン化合物；４，４’－ジメチルアミノチオキサントン、４，４’－ジエチルアミノベンゾフェノン、α－アシロキシムエステル、ベンジル、メチルベンゾイルホルメート（「バイアキュア５５」）、２－エチルアンスラキノン等のアンスラキノン化合物；２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキサイド等のアシルフォスフィンオキサイド化合物；３，３’，４，４’－テトラ（ｔｅｒｔ－ブチルオパーオキシカルボニル）ベンゾフェノン、アクリル化ベンゾフェノン等を用いることができる。これらの光重合開始剤は単独で用いても２種以上を併用してもよい。 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). For example, 4-phenoxydichloroacetophenone, diethoxyacetophenone 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 4- ( 2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2,2-dimethoxy-2-phenylacetophenone, etc. 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′-dimethylaminothioxanthone, 4,4′- Anthraquinone compounds such as ethylaminobenzophenone, α-acyloxime ester, benzyl, methylbenzoylformate (“Biacure 55”), 2-ethylanthraquinone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2, Acylphosphine oxide compounds such as 4,6-trimethylbenzoyl) -phenylphosphine oxide; 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, acrylated benzophenone, and the like can be used. These photopolymerization initiators may be used alone or in combination of two or more.
　前記光重合開始剤を用いる場合の使用量としては、良好な紫外線硬化性が得られる点から、前記ウレタンプレポリマー（Ａ）１００質量部に対して、０．１～５質量部の範囲であることが好ましく、０．５～２質量部の範囲がより好ましい。 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.
　次に、本発明のポリウレタン発泡シートの製造方法について説明する。 Next, a method for producing the polyurethane foam sheet of the present invention will be described.
　本発明のポリウレタン発泡シートを製造する際のポリウレタン組成物の発泡方法としては、例えば、ガスローディング法、水発泡法、メカニカルフロス法等を使用する方法が挙げられる。これらの中でも、液成分の粘度許容範囲が広く、より一層優れた泡保持性が得られる点から、ガスローディング法、及び／又は、水発泡法を使用することが好ましく、不活性ガスがポリウレタン組成物に良く溶け込み、更に優れた泡保持性が得られる点から、ガスローディング法を使用することがより好ましい。 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. Among these, it is preferable to use the 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, and the inert gas is a polyurethane composition. It is more preferable to use a gas loading method from the viewpoint that it can be well dissolved in a product and an excellent foam retention can be obtained.
　前記ガスローディング法を使用してポリウレタン発泡シートを得る方法としては、例えば、前記主剤（ｉ）と前記硬化剤（ｉｉ）とを混合する前に、前記主剤（ｉ）及び／又は前記硬化剤（ｉｉ）に対し、不活性ガスを、好ましくは０．０５～０．２ＭＰａの範囲、より好ましくは０．０７～０．１８ＭＰａの範囲の圧力下で、ガスローディングする方法が挙げられる。 As a method of obtaining a polyurethane foam sheet using the gas loading method, for example, before mixing the main agent (i) and the curing agent (ii), the main agent (i) and / or the curing agent ( In contrast to ii), there is a method in which 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.
　前記ガスローディングとは、前記主剤（ｉ）及び／又は前記硬化剤（ｉｉ）に対して、圧力下で不活性ガスを外部から進入させ、強制的に抱き込ませる処理をいう。また、前記不活性ガスを進入させる際には、前記主剤（ｉ）及び／又は前記硬化剤（ｉｉ）を撹拌することが、不活性ガスの溶解性を向上できる点から好ましい。前記ガスローディングは、公知のローディング装置を使用して行うことができる。 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 | curing agent (ii). The gas loading can be performed using a known loading device.
　前記不活性ガスとしては、例えば、二酸化炭素、ヘリウムガス、窒素ガス、アルゴンガス、ネオンガス等を用いることができる。これらの中でも、原料入手の容易性、及び、主剤（ｉ）や硬化剤（ｉｉ）への溶解性が高いことから、二酸化炭素を用いることが好ましい。 As the inert gas, for example, carbon dioxide, helium gas, nitrogen gas, argon gas, neon gas or the like can be used. Among these, 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).
　前記ガスローディングを行う際の圧力としては、不活性ガスによる安定的な泡の保持を可能とするため、０．０５～０．２ＭＰａの範囲であることが好ましく、更に均一な泡を保持でき、一層優れた風合いが得られる点から、０．０７～０．１８ＭＰａの範囲であることがより好ましく、０．０８～０．１７ＭＰａの範囲が更に好ましい。 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.
　前記ガスローディングを行う時間としては、均一に不活性ガスをローディングでき、かつウレタンプレポリマーやポリオールの劣化を防ぐ点から、１０分～３時間の範囲であることが好ましく、１０～６０分の範囲であることが好ましい。 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
　前記ガスローディングとしては、前記主剤（ｉ）にのみ行うことが好ましい。この理由としては、同条件（圧力・時間）でガスローディングを行った場合に、前記硬化剤（ｉｉ）に比べ、前記主剤（ｉ）の方が不活性ガスの溶解性が高いことが挙げられ、これにより容易に安定的な泡を保持したポリウレタン発泡シートを得ることができるからである。なお、この際には、硬化剤（ｉｉ）に後述する水、好ましくは更に触媒及び製泡剤を含有させ、ガスローディングと共に、水発泡法を併用してもよい。 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. In this case, 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.
　また、前記ガスローディングを行う際の前記主剤（ｉ）の５０℃における粘度としては、前記圧力下でも不活性ガスを良好にローディングできる点から、２００～２０，０００ｍＰａ・ｓの範囲であることが好ましく、２５０～１５，０００ｍＰａ・ｓの範囲がより好ましい。なお、前記主剤（ｉ）の５０℃における粘度は、Ｂ型粘度計（ローターＮｏ．３、回転数：１２ｒｐｍ）により測定した値を示す。 Further, 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. In addition, 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).
　前記ガスローディングを前記主剤（ｉ）に行った場合において、前記ガスローディング後の主剤（ｉ）を常圧に開放した直後の主剤（ｉ）の比重としては、より一層優れた泡の保持、及び風合いが得られる点から、０．２～０．８の範囲であることが好ましく、０．３～０．７の範囲であることがより好ましい。 When the gas loading is performed on the main agent (i), 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.
　前記ガスローディングを行った後は、一旦常圧下に戻してから、前記主剤（ｉ）と前記硬化剤（ｉｉ）とを混合し、ウレタン化反応を進行させる方法；ガスローディングした前記主剤（ｉ）及び／又は硬化剤（ｉｉ）を、ローディング装置に連結させた混合機等に、圧力差を利用して移動させ、混合機等により混合してウレタン化反応を進行させる方法などが挙げられる。 After the gas loading is performed, 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.
　前記主剤（ｉ）と前記硬化剤（ｉｉ）との混合割合［（ｉ）：（ｉｉ）］としては、質量比で８０：２０～２０：８０の範囲であることが好ましく、７５：２５～２５：７５の範囲がより好ましい。 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.
　続いて、混合された前記主剤（ｉ）及び前記硬化剤（ｉｉ）は、例えば、離型紙、離型剤が塗布された基材等の基材上に、塗布され、紫外線照射することで、ポリウレタン発泡シートを得ることができる。 Subsequently, 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 polyurethane foam sheet can be obtained.
　前記混合された前記主剤（ｉ）及び前記硬化剤（ｉｉ）を塗布する方法としては、例えば、アプリケーター、ロールコーター、スプレーコーター、Ｔ－ダイコーター、ナイフコーター等を使用する方法が挙げられる。塗布する厚さとしては、例えば、１０～５００μｍの範囲である。 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 μm.
　前記紫外線照射を行う方法としては、例えば、蛍光ケミカルランプ、ブラックライト、ＬＥＤランプ等の低照度の紫外線光照射装置；キセノンランプ、キセノン－水銀ランプ、メタルハライドランプ、高圧水銀ランプ、低圧水銀ランプ、ＬＥＤランプ等の中・高照度の紫外線光照射装置を使用して所定の紫外線を照射する方法が挙げられる。 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.
　前記紫外線照射を行う際の積算光量としては、例えば、１００～１，５００ｍＪ／ｃｍ２の範囲であることが挙げられ、好ましくは、光重合反応を過不足なく進行させる点から、２００～１，０００ｍＪ／ｃｍ２の範囲である。なお、前記紫外線の積算光量は、ＧＳユアサ株式会社製ＵＶチェッカー「ＵＶＲ－Ｎ１」を用いて３００～３９０ｎｍの波長域において測定した値を基準とする。 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.
　前記紫外線照射後には、残存するウレタンプレポリマー（Ａ）のイソシアネートの硬化をすべく、例えば、４０～１３０℃の温度で３分～３日間の条件にてエージングを行うことが好ましい。その後更に、４０～８０℃の温度で１～３日間エージングを行ってもよい。 After the ultraviolet irradiation, 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.
　また、前記水発泡法を使用してポリウレタン発泡シートを得る方法としては、例えば、前記硬化剤（ｉｉ）に水、好ましくは更に触媒及び整泡剤を含有させ、前記主剤（ｉ）と前記硬化剤（ｉｉ）とを混合する方法が挙げられる。 Moreover, as a method of obtaining a polyurethane foam sheet using the water foaming method, for example, 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.
　前記水は発泡剤として機能するものであり、その使用量としては、前記硬化剤（ｉｉ）中０．０１～１０質量％の範囲であることが好ましく、０．０２～５質量％の範囲がより好ましい。 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.
　前記触媒としては、例えば、トリエチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルヘキサンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルプロパンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’’，Ｎ’’－ペンタメチルジエチレントリアミン、Ｎ，Ｎ’，Ｎ’－トリメチルアミノエチルピペラジン、Ｎ，Ｎ－ジメチルシクロヘキシルアミン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルエチレンジアミン、ビス（３－ジメチルアミノプロピル）－Ｎ，Ｎ－ジメチルプロパンジアミン、Ｎ，Ｎ－ジシクロヘキシルメチルアミン、ビス（ジメチルアミノエチル）エーテル、Ｎ，Ｎ’，Ｎ’’－トリス（３－ジメチルアミノプロピル）ヘキサヒドロ－Ｓ－トリアジン、Ｎ，Ｎ－ジメチルベンジルアミン、Ｎ，Ｎ－ジメチルアミノエトキシエトキシエタノール、Ｎ，Ｎ－ジメチルアミノヘキサノール、Ｎ，Ｎ－ジメチルアミノエトキシエタノール、Ｎ，Ｎ，Ｎ’－トリメチルアミノエチルエタノールアミン、Ｎ，Ｎ，Ｎ’－トリメチル－２－ヒドロキシエチルプロピレンジアミン、１－メチルイミダゾール、１－イソブチル－２－メチルイミダゾール、１，２－ジメチルイミダゾール、ジメチルエタノールアミン、トリエタノールアミン等のアミン化合物；ジブチルスズジウラウレート、ジオクチルチンジラウレート、オクチル酸スズ２－エチルヘキサン酸、オクチル酸カリウム、ジブチルスズラウリルメルカプタイド、ビスマストリス（２－エチルヘキサノエート）等の金属化合物などを用いることができる。これらの触媒は単独で用いても２種以上を併用してもよい。 Examples of the catalyst include triethylenediamine, N, N, N ′, N′-tetramethylhexanediamine, N, N, N ′, N′-tetramethylpropanediamine, N, N, N ′, N ″. , N ″ -pentamethyldiethylenetriamine, N, N ′, N′-trimethylaminoethylpiperazine, N, N-dimethylcyclohexylamine, N, N, N ′, N′-tetramethylethylenediamine, bis (3-dimethylamino Propyl) -N, N-dimethylpropanediamine, N, N-dicyclohexylmethylamine, bis (dimethylaminoethyl) ether, N, N ′, N ″ -tris (3-dimethylaminopropyl) hexahydro-S-triazine, N, N-dimethylbenzylamine, N, N-dimethylaminoethoxyethoxyethanol, N N-dimethylaminohexanol, N, N-dimethylaminoethoxyethanol, N, N, N′-trimethylaminoethylethanolamine, N, N, N′-trimethyl-2-hydroxyethylpropylenediamine, 1-methylimidazole, 1 -Amine compounds such as isobutyl-2-methylimidazole, 1,2-dimethylimidazole, dimethylethanolamine, triethanolamine; dibutyltin dilaurate, dioctyltin dilaurate, tin octylate 2-ethylhexanoic acid, potassium octylate, dibutyltin Metal compounds such as lauryl mercaptide and bismuth tris (2-ethylhexanoate) can be used. These catalysts may be used alone or in combination of two or more.
　前記触媒を用いる場合の使用量としては、前記硬化剤（ｉｉ）中０．０１～１質量％の範囲であることが好ましく、０．０５～０．５質量％の範囲がより好ましい。 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).
　前記整泡剤としては、シリコーン系界面活性剤を好ましく用いることができ、例えば、「ＳＺ－１９１９」、「ＳＨ－１９２」、「ＳＨ－１９０」、「ＳＺ－５８０」、「ＳＲＸ－２８０Ａ」、「ＳＺ－１９５９」、「ＳＺ－１３２８Ｅ」、「ＳＦ－２９３７Ｆ」、「ＳＦ－２９３８Ｆ」、「ＳＺ－１６７１」、「ＳＨ－１９３」、「ＳＺ－１９２３」、「シリコンＹ－７００６」（以上、東レ・ダウコーニング・シリコーン株式会社製）等を市販品として入手することができる。前記整泡剤を用いる場合の使用量としては、前記硬化剤（ｉｉ）中０．０１～５質量％の範囲であることが好ましく、０．０３～３質量％の範囲がより好ましい。 As the foam stabilizer, a silicone-based surfactant can be preferably used. For example, “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. When the foam stabilizer is used, 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).
　前記主剤（ｉ）と前記硬化剤（ｉｉ）とを混合する方法としては、例えば、混合注型機を使用する方法が挙げられる。 Examples of a method of mixing the main agent (i) and the curing agent (ii) include a method using a mixed casting machine.
　具体的には、例えば、前記主剤（ｉ）と前記硬化剤（ｉｉ）とを混合注型機のそれぞれのタンクへ入れて、前記主剤（ｉ）を好ましくは４０～８０℃の範囲で加温し、前記硬化剤（ｉｉ）を好ましくは４０～８０℃の範囲で加温し、それぞれを混合注型機で混合する方法が挙げられる。 Specifically, for example, 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.
　前記主剤（ｉ）と前記硬化剤（ｉｉ）との混合割合［（ｉ）：（ｉｉ）］としては、質量比で８０：２０～２０：８０の範囲であることが好ましく、７５：２５～２５：７５の範囲がより好ましい。 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.
　続いて、混合された前記主剤（ｉ）及び前記硬化剤（ｉｉ）は、例えば、離型紙、離型剤が塗布された基材等の基材上に、塗布され、紫外線照射することで、ポリウレタン発泡シートを得ることができる。この工程は、前記ガスローディング法を使用した場合と同様である。 Subsequently, 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 polyurethane foam sheet can be obtained. This step is the same as when the gas loading method is used.
　以上の方法により得られるポリウレタン発泡シートの密度としては、良好な風合いが得られる点から、０．５～０．９５ｇ／ｃｍ３の範囲であることが好ましく、０．６５～０．９ｇ／ｃｍ３の範囲であることがより好ましい。なお、前記ポリウレタン発泡シートの密度の測定方法は、縦１０ｃｍ、横１０ｃｍに裁断したポリウレタン発泡シートの、厚さと重量を測定して、下記式（１）に従って密度を算出する方法による。
　密度（ｇ／ｃｍ３）＝重量（ｇ）／１０（ｃｍ）×１０（ｃｍ）×厚さ（ｃｍ）（１） 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. In addition, 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)
　次に、本発明の積層体の製造方法について説明する。 Next, a method for manufacturing the laminate of the present invention will be described.
　前記積層体の製造方法としては、例えば、前記ガスローディング法を使用して得られるポリウレタン発泡シート、及び／又は、前記水発泡法を使用して得られるポリウレタン発泡シートを、繊維基材に貼り合せることにより製造する方法が好ましく挙げられる。なお、前記ポリウレタン発泡シートとしては、前記紫外線照射を行った後、エージングを行っていないものを使用してもよく、紫外線照射及びエージングを行った後のものを使用してもよい。これらの中でも、ポリウレタン発泡シートの繊維基材への浸み込み量をコントロールしやすく、一層優れた剥離強度が得られる点から、前者の方法を採用することが好ましい。 As the method for producing the laminate, for example, 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.
　前記繊維基材としては、例えば、不織布、織布、編み物等を使用することができる。前記繊維基材を構成するものとしては、例えば、ポリエステル繊維、ナイロン繊維、アクリル繊維、アセテート繊維、レーヨン繊維、ポリ乳酸繊維、綿、麻、絹、羊毛、それらの混紡繊維等を使用することができる。 For example, a nonwoven fabric, a woven fabric, a knitted fabric, or the like can be used as the fiber base material. For example, 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.
　以上、本発明のポリウレタン発泡シートは、シート形成後の泡保持性、風合い、及び剥離強度に優れるものである。 As described above, the polyurethane foam sheet of the present invention is excellent in foam retention, texture, and peel strength after sheet formation.
　以下、実施例を用いて本発明をより詳細に説明する。 Hereinafter, the present invention will be described in more detail using examples.
［調製例１］主剤（ｉ－１）の調製
　温度計、撹拌機、不活性ガス導入口、及び還流冷却器を備えた四口フラスコに、４，４’－ジフェニルメタンジイソシアネート（以下、「ＭＤＩ」と略記する。）を１００質量部、ポリテトラメチレングリコール（三菱化学株式会社製「ＰＴＭＧ２０００」、数平均分子量：２，０００）を１２０質量部入れ、８０℃で３時間反応させ、ＮＣＯ％：１２．９質量％のウレタンプレポリマー（Ａ－１－１）を得た。
　次いで、２－ヒドロキシエチルアクリレート（以下、「ＨＥＡ」と略記する。）を１１．８質量部入れ、６０℃で２時間反応させ、残存するイソシアネート基の１５モル％にアクリロイル基を導入したウレタンプレポリマー（Ａｉ）を得、これを主剤（ｉ－１）とした。前記主剤（ｉ－１）の５０℃における粘度は、１，５５０ｍＰａ・ｓであった。 [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.
Next, 11.8 parts by mass of 2-hydroxyethyl acrylate (hereinafter abbreviated as “HEA”) was added, reacted at 60 ° C. for 2 hours, and a urethane prepolymer having acryloyl groups introduced into 15 mol% of the remaining isocyanate groups. A polymer (Ai) 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.
［調製例２］主剤（ｉ－２）の調製
　温度計、撹拌機、不活性ガス導入口、及び還流冷却器を備えた四口フラスコに、ＭＤＩを１００質量部、ＰＴＭＧ２０００を１０７質量部入れ、８０℃で３時間反応させ、ＮＣＯ％：１４．２質量％のウレタンプレポリマー（Ａ－１－２）を得た。
　次いで、ＨＥＡを１６質量部入れ、６０℃で２時間反応させ、残存するイソシアネート基の２０モル％にアクリロイル基を導入したウレタンプレポリマー（Ａｉｉ）を得、これを主剤（ｉ－２）とした。前記主剤（ｉ－２）の５０℃における粘度は、１，８００ｍＰａ・ｓであった。 [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. for 2 hours to obtain a 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.
［調製例３］主剤（ｉ’－１）の調製
　温度計、撹拌機、不活性ガス導入口、及び還流冷却器を備えた四口フラスコに、ＭＤＩを１００質量部、ＰＴＭＧ２０００を１５０質量部入れ、８０℃で３時間反応させ、ＮＣＯ％：１１．２質量％のウレタンプレポリマー（Ａ’－１－１）を得た。
　次いで、ＨＥＡを２．３質量部入れ、６０℃で２時間反応させ、残存するイソシアネート基の３モル％にアクリロイル基を導入したウレタンプレポリマー（Ａ’ｉ）を得、これを主剤（ｉ’－１）とした。前記主剤（ｉ’－１）の５０℃における粘度は、１，３１０ｍＰａ・ｓであった。 [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.
［調製例４］主剤（ｉ’－２）の調製
　温度計、撹拌機、不活性ガス導入口、及び還流冷却器を備えた四口フラスコに、ＭＤＩを１００質量部、ＰＴＭＧ２０００を７５質量部入れ、８０℃で３時間反応させ、ＮＣＯ％：１７．４質量％のウレタンプレポリマー（Ａ’－１－２）を得た。
　次いで、ＨＥＡを２５．２質量部入れ、６０℃で２時間反応させ、残存するイソシアネート基の３０モル％にアクリロイル基を導入したウレタンプレポリマー（Ａ’ｉｉ）を得、これを主剤（ｉ’－２）とした。前記主剤（ｉ’－２）の５０℃における粘度は、３，６１０ｍＰａ・ｓであった。 [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.
［調製例５］主剤（ｉ’－３）の調製
　温度計、撹拌機、不活性ガス導入口、及び還流冷却器を備えた四口フラスコに、ＭＤＩを１００質量部、ＰＴＭＧ２０００を５２０質量部入れ、８０℃で３時間反応させ、ＮＣＯ％：１．９質量％のウレタンプレポリマー（Ａ’－１－３）を得た。
　次いで、ＨＥＡを４．９質量部入れ、６０℃で２時間反応させ、残存するイソシアネート基の１５モル％にアクリロイル基を導入したウレタンプレポリマー（Ａ’ｉｉｉ）を得、これを主剤（ｉ’－３）とした。前記主剤（ｉ’－３）の５０℃における粘度は、7，４００ｍＰａ・ｓであった。 [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.
［調製例６］主剤（ｉ’－４）の調製
　温度計、撹拌機、不活性ガス導入口、及び還流冷却器を備えた四口フラスコに、ＭＤＩを１００質量部、ＰＴＭＧ２０００を５０質量部入れ、８０℃で３時間反応させ、ＮＣＯ％：２１質量％のウレタンプレポリマー（Ａ’－１－４）を得た。
　次いで、ＨＥＡを１３.１質量部入れ、６０℃で２時間反応させ、残存するイソシアネート基の１５モル％にアクリロイル基を導入したウレタンプレポリマー（Ａ’ｉｖ）を得、これを主剤（ｉ’－４）とした。前記主剤（ｉ’－４）の５０℃における粘度は、８２０ｍＰａ・ｓであった。 [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.
［調製例７］硬化剤（ｉｉ－１）の調製
　ポリテトラメチレングリコール（数平均分子量：１，０００）を１００質量部、エチレングリコールを８質量部、光重合開始剤としてチバスペシャリティ株式会社製「Ｉｒｕｇａｃｕｒｅ１８４」を２質量部を混合、撹拌し、硬化剤（ｉｉ－１）を得た。 [Preparation Example 7] Preparation of curing agent (ii-1) 100 parts by mass of polytetramethylene glycol (number average molecular weight: 1,000), 8 parts by mass of ethylene glycol, manufactured by Ciba Specialty Co., Ltd. as a photopolymerization initiator 2 parts by mass of “Irugacure 184” was mixed and stirred to obtain a curing agent (ii-1).
［実施例１］
　前記主剤（ｉ－１）をローディング装置に入れた。その後、ローディング装置内を０．１ＭＰａに二酸化炭素で加圧し、原料を撹拌しながら３０分かけてローディングした。
　次いで、ポリマーエンジニアリング株式会社製低圧ウレタン注入発泡機「ＭＴ５」の主剤タンクへ、ローディング装置より圧力差を利用してガスローディングした主剤（ｉ－１）を仕込み、０．５ＭＰａの圧力下で循環した。
　硬化剤（ｉｉ－１）も硬化剤タンクに仕込み、０．５ＭＰａの圧力下で循環した。その後、（ｉ－１）と（ｉｉ－１）とを質量比１６７：１００となるように同時吐出して瞬間混合した後、離型剤を塗布したシートの上に厚み２５０μｍとなるよう混合液を塗布した。
　次いで、該塗布物に対し、日本電池株式会社製紫外線照射装置「ＣＳＯＴ－４０」（高圧水銀ランプ、照度：１２０ｍＷ／ｃｍ２、コンベアスピード：５ｍ／分）にて３００ｍＪ／ｃｍ２の紫外線を照射させ、その後、基布を貼り合せた。その後、１１０℃で５分間の加熱処理を行った。連続的に３０分間運転し、巻き取ることで、繊維積層体を得た。 [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. Thereafter, (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 μm on the sheet coated with the release agent. Was applied.
Next, 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. Then, the base fabric was bonded. Thereafter, heat treatment was performed at 110 ° C. for 5 minutes. The fiber laminate was obtained by continuously operating for 30 minutes and winding.
［実施例２、比較例１～４］
　用いる主剤（ｉ）の種類を表１～２に示す通りに変更した以外は、実施例１と同様にして繊維積層体を得た。 [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.
［ポリウレタン発泡シートの泡保持性の評価方法］
　実施例及び比較例で得られた繊維積層体を横から見た断面図を、日立ハイテクテクノロジー株式会社製走査型電子顕微鏡「ＳＵ３５００」（倍率：１００倍）にて観察した。更に、前記繊維積層体を、温度２３℃、湿度５０％の条件下で７日間放置したものを試験片とし、その断面図を、同様に走査型電子顕微鏡にて観察し、泡保持性を以下のように評価した。
　「Ｔ」：試験片の断面図において、繊維積層体作成直後に泡が確認され、７日後においてもほぼ変わらない状態で保持されている。
　「Ｆ」：試験片の断面図において、繊維積層体作成直後に泡が押しつぶされ泡が確認できない、又は、繊維積層体作成直後に泡が確認されるが、７日後、泡の形状が変わっている、若しくは泡が押しつぶされているのが確認される。 [Method for evaluating foam retention of polyurethane foam sheet]
Cross-sectional views of the fiber laminates obtained in Examples and Comparative Examples as viewed from the side were observed with a scanning electron microscope “SU3500” (magnification: 100 times) manufactured by Hitachi High-Technology Corporation. Further, the fiber laminate was left as it was for 7 days under the conditions of a temperature of 23 ° C. and a humidity of 50% as a test piece, and its cross-sectional view was similarly observed with a scanning electron microscope. It was evaluated as follows.
“T”: In the cross-sectional view of the test piece, bubbles were confirmed immediately after the fiber laminate was formed, and the foam was held in a state that remained almost unchanged after 7 days.
"F": In the cross-sectional view of the test piece, the foam is crushed immediately after the fiber laminate is created and the foam cannot be confirmed, or the foam is confirmed immediately after the fiber laminate is created, but after 7 days, the shape of the foam changes. Or bubbles are crushed.
［ポリウレタン発泡シートの風合いの評価］
　実施例及び比較例で得られた繊維積層体のポリウレタン発泡シート側を手で触り、以下のように評価した。
　「Ｔ」：柔らかい。
　「Ｆ」：硬い。 [Evaluation of the texture of polyurethane foam sheet]
The polyurethane foam sheet side of the fiber laminates obtained in Examples and Comparative Examples was touched by hand and evaluated as follows.
“T”: soft.
“F”: Hard.
［ポリウレタン発泡シートの繊維基材（基布）への染み込み量の評価方法］
　実施例及び比較例で得られた繊維積層体を１日放置し、その後巻きを解いた。巻きはじめより１０ｍの時点の繊維積層体を試験片とした。該試験片を横から見た断面図を、日立ハイテクテクノロジー株式会社製走査型電子顕微鏡「ＳＵ３５００」（倍率：２００倍）にて観察し、ポリウレタン発泡シートが基布へ浸み込んだ長さ（μｍ）を測定した。 [Evaluation method of amount of penetration of polyurethane foam sheet into fiber substrate (base fabric)]
The fiber laminates obtained in the examples and comparative examples were left for 1 day and then unwound. A fiber laminate at a point of 10 m from the beginning of winding was used as a test piece. A cross-sectional view of the test piece viewed from the side was observed with a scanning electron microscope “SU3500” (200 × magnification) manufactured by Hitachi High-Technology Corporation, and the length of the polyurethane foam sheet soaked into the base fabric ( μm).
［ポリウレタン発泡シートの剥離強度の評価方法］
　前記［ポリウレタン発泡シートの繊維基材（基布）への染み込み量の評価方法］にて使用した試験片を使用した。この試験片の表面に１インチ（２．５４ｃｍ）幅のホットメルト布テープを１３０℃で５秒間加熱融着し、温度２３℃、相対湿度６５％の条件下で、ＪＩＳＫ６８５４－２－１９９９に準拠して、株式会社島津製作所製オートグラフ「Ｇ－１」を使用して、ヘッドスピード：２００ｍｍ／分の条件にて剥離強度（Ｎ／ｃｍ）を測定した。なお、材料破壊を起こし、剥離強度が測定できなかったものは「－」と記載する。 [Method for evaluating peel strength of polyurethane foam sheet]
The test piece used in [Method for evaluating the amount of penetration of the polyurethane foam sheet into the fiber substrate (base fabric)] was used. A 1-inch (2.54 cm) wide hot-melt cloth tape was heat-sealed at 130 ° C. for 5 seconds on the surface of this test piece, in accordance with JIS K 6854-2-1999 under conditions of a temperature of 23 ° C. and a relative humidity of 65%. Then, using an autograph “G-1” manufactured by Shimadzu Corporation, the peel strength (N / cm) was measured at a head speed of 200 mm / min. Note that “−” indicates that the material was destroyed and the peel strength could not be measured.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　本発明の製造方法により得られたポリウレタン発泡シートは、シート形成後も良好に泡を保持し、更に風合い、及び剥離強度に優れることが分かった。 It was found that 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.
　一方、比較例１は、ウレタンプレポリマー（Ａ）として、残存するイソシアネート基に対する重合性不飽和基の導入量が、本発明で規定する範囲を下回るものを用いた態様であるが、泡の保持性が不良であり、基布への浸み込みが多すぎる為、材料破壊を起こした。 On the other hand, 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.
　比較例２は、ウレタンプレポリマー（Ａ）として、残存するイソシアネート基に対する重合性不飽和基の導入量が、本発明で規定する範囲を超えるものを用いた態様であるが、泡の保持性は良好であるものの、風合いが不良であった。また基布への浸み込みがなく、剥離強度も不良であった。 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.
　比較例３は、ウレタンプレポリマー（Ａ－１）のＮＣＯ％が、本発明で規定する範囲を下回る態様であるが、泡の保持性は良好であるものの、風合いが不良であった。また、基布への浸み込みがなく、剥離強度も不良であった。 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.
　比較例３は、ウレタンプレポリマー（Ａ－１）のＮＣＯ％が、本発明で規定する範囲を超える態様であるが、泡の保持性及び風合いが不良であり、基布への浸み込みが多すぎ、剥離強度も不良であった。 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.

Claims (9)

  1. イソシアネート基を有するウレタンプレポリマー（Ａ）を含む主剤（ｉ）と、ポリオール（Ｂ）を含む硬化剤（ｉｉ）とを含有するポリウレタン組成物により形成されたポリウレタン発泡シートであって、
    前記ウレタンプレポリマー（Ａ）が、
    イソシアネート基含有率が２～２０質量％であるウレタンプレポリマー（Ａ－１）に対し、残存するイソシアネート基の５～２５モル％に重合性不飽和基を導入したものであることを特徴とするポリウレタン発泡シート。     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) is
    It is characterized in that 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%. Polyurethane foam sheet.
  2. 請求項１記載のポリウレタン組成物を、ガスローディング法、及び／又は、水発泡法により発泡することを特徴とするポリウレタン発泡シートの製造方法。 A method for producing a polyurethane foam sheet, wherein the polyurethane composition according to claim 1 is foamed by a gas loading method and / or a water foaming method.
  3. 前記ガスローディング法が、前記主剤（ｉ）及び／又は前記硬化剤（ｉｉ）に対し、不活性ガスを、０．０５～０．２ＭＰａの範囲の圧力下で、ガスローディングするものである請求項２記載のポリウレタン発泡シートの製造方法。 The gas loading method is a method in which an inert gas is gas loaded at a pressure in a range of 0.05 to 0.2 MPa with respect to the main agent (i) and / or the curing agent (ii). 3. A method for producing a polyurethane foam sheet according to 2.
  4. 前記ガスローディングを、前記主剤（ｉ）にのみ行う請求項３記載のポリウレタン発泡シートの製造方法。 The method for producing a polyurethane foam sheet according to claim 3, wherein the gas loading is performed only on the main agent (i).
  5. 前記ガスローディングを行う際の前記主剤（ｉ）の５０℃における粘度が、２００～２０，０００ｍＰａ・ｓの範囲である請求項４記載のポリウレタン発泡シートの製造方法。 The method for producing a polyurethane foam sheet according to claim 4, wherein the viscosity of the main agent (i) at 50 ° C during the gas loading is in the range of 200 to 20,000 mPa · s.
  6. 請求項１記載のポリウレタン組成物を、ガスローディング法、及び／又は、水発泡法により発泡させた後に、基材上に塗布し、紫外線照射してポリウレタン発泡シートを得、次いで、繊維基材に貼り合せることを特徴とする積層体の製造方法。 After the polyurethane composition according to claim 1 is foamed by a gas loading method and / or a water foaming method, the polyurethane composition is applied on a base material and irradiated with ultraviolet rays to obtain a polyurethane foam sheet, and then applied to a fiber base material. A method for producing a laminate, wherein the laminate is bonded.
  7. 前記ガスローディング法が、前記主剤（ｉ）及び／又は前記硬化剤（ｉｉ）に対し、不活性ガスを、０．０５～０．２ＭＰａの範囲の圧力下で、ガスローディングするものである請求項６記載のポリウレタン発泡シートの製造方法。 The gas loading method is a method in which an inert gas is gas loaded at a pressure in a range of 0.05 to 0.2 MPa with respect to the main agent (i) and / or the curing agent (ii). 6. A process for producing a polyurethane foam sheet according to 6.
  8. 前記ガスローディングを、前記主剤（ｉ）にのみ行う請求項７記載のポリウレタン発泡シートの製造方法。 The method for producing a polyurethane foam sheet according to claim 7, wherein the gas loading is performed only on the main agent (i).
  9. 前記ガスローディングを行う際の前記主剤（ｉ）の５０℃における粘度が、２００～２０，０００ｍＰａ・ｓの範囲である請求項８記載のポリウレタン発泡シートの製造方法。 The method for producing a polyurethane foam sheet according to claim 8, wherein the viscosity of the main agent (i) at 50 ° C during the gas loading is in the range of 200 to 20,000 mPa · s.
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