TW201817758A - Polyurethane foam sheet, method for producing same, and method for producing laminate - Google Patents

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

   Polyurethane foamed sheet, manufacturing method thereof, and manufacturing method of laminated body   

The present invention relates to a polyurethane foamed sheet having excellent foam retention, hand feel, and peel strength after forming a sheet.

Polyurethane foamed sheets are widely used in various fields such as automotive interior materials, shoe soles, photocopier rolls, cushioning materials, sealing materials, and electronic packing. As a method for producing a polyurethane foamed sheet, for example, a method is disclosed in which a urethane acrylate oligomer is coated on a substrate, and is cured after being cured by ultraviolet rays (for example, refer to Patent Document 1).

In many cases, the polyurethane foamed sheet is used as a laminate of a different material than the polyurethane foamed sheet. Examples of the different materials include fibrous substrates such as nonwoven fabrics, woven fabrics, and knitted fabrics, and composite fiber substrates impregnated with polyurethane and the like. When manufacturing a laminated body of a material different from this, generally, a polyurethane foam sheet is coated on a release paper, and a fiber substrate is adhered to the coated surface, and then the release paper is removed. The obtained laminate was taken up on a roll. However, if the polyurethane foamed sheet is not cured to a certain degree or more at the stage of being wound on a roll, there is a problem that bubbles in the sheet may break, become a hard sheet, or Laminates produce wrinkles. distortion. Conditions such as spalling.

Advance technical literature Patent literature

Patent Document 1 Japanese Patent Application Publication No. 2008-156544

Summary of invention

The problem to be solved by the present invention is to provide a polyurethane foamed sheet having excellent foam retention, hand feel, and peel strength after forming a sheet.

The present invention provides a polyurethane foamed sheet, which is a polyurethane foam formed by a polyurethane composition containing a main agent (i) and a hardener (ii). A tablet, wherein the main agent (i) comprises an urethane prepolymer (A) having an isocyanate group, and the hardener (ii) comprises a polyol (B); The substance (A) is an urethane prepolymer (A-1) having an isocyanate group content of 2 to 20% by mass, and a polymerizable unsaturated group is introduced into 5 to 25 mol% of the remaining isocyanate group. Become.

The present invention also provides a method for producing a polyurethane foamed sheet, which is characterized in that the polyurethane composition is developed by a gas loading method or a water foaming method. bubble. Furthermore, the present invention provides a method for manufacturing a laminated body, characterized in that the polyurethane composition is foamed by a gas filling method or a water foaming method, and then coated on a substrate, Then, ultraviolet rays were irradiated to obtain a polyurethane foamed sheet, and then a fiber base material was bonded.

The polyurethane foamed sheet of the present invention has excellent foam retention, hand feel, and peel strength after forming a sheet.

Forms used to implement the invention

The polyurethane foamed sheet of the present invention is formed by a polyurethane composition containing a main agent (i) and a hardener (ii), wherein the main agent (i) contains The urethane prepolymer (A-1) having a base content of 2 to 20% by mass, and a carbamate formed by introducing a polymerizable unsaturated group into 5 to 25 mol% of the remaining isocyanate group An ester prepolymer (A), and the hardener (ii) contains a polyol (B).

The said urethane prepolymer (A) uses the urethane prepolymer (A-1) whose isocyanate group content rate is 2-20 mass% as a raw material. When the isocyanate group content ratio of the urethane prepolymer (A-1) is in the above-mentioned range, it is possible to obtain foam retention and moderate coating properties. When the content of the isocyanate group of the urethane prepolymer (A-1) is less than 2% by mass, the high-viscosity, smooth and good sheet itself may not be obtained, or the desired peeling may not be obtained. When the state of the strength exceeds 20% by mass, there is a problem that a sheet having a low viscosity and a practically usable thickness cannot be obtained, or a desired peeling 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 more excellent foam retention. 5 to 15% by mass. The isocyanate group content of the urethane prepolymer (A-1) is a value measured by a potentiometric titration method in accordance with JISK1603-1: 2007. Hereinafter, the content of the isocyanate group of the urethane prepolymer (A-1) is abbreviated as "NCO%".

The urethane prepolymer (A) needs to further introduce a polymerizable unsaturated group into the urethane prepolymer (A-1) at 5 to 25 mol% of the remaining isocyanate group. By introducing a polymerizable unsaturated group into the urethane prepolymer within such a range, when obtaining a polyurethane foamed sheet, the initial viscosity can be controlled by ultraviolet curing to make different Good connection of materials is possible. In particular, when the adherend of the polyurethane foamed sheet is a fibrous substrate, the amount of impregnation of the polyurethane foamed sheet to the fibrous substrate can be controlled, so that an extremely excellent Peel strength. Moreover, when winding up the laminated body which has a polyurethane foamed sheet, the laminated body which has the polyurethane foamed sheet which does not damage a bubble and maintains the shape of a foamed cell well is obtained. Moreover, the laminated body becomes a person with excellent hand feeling. When the introduction rate of the polymerizable unsaturated group with respect to the urethane prepolymer (A-1) is less than 5 mol%, the desired initial viscosity cannot be obtained, and the foam-holding property becomes poor. When it exceeds 25 mol%, there is a problem that the impregnation of the fibrous base material is insufficient, and the desired peeling strength cannot be obtained, or the foam retention and texture may become poor. From the point that it becomes easier to control the amount of infiltration into the fibrous substrate, and more excellent peel strength and feel can be obtained, it is not polymerizable for the aforementioned urethane prepolymer (A-1). The introduction rate of the saturated group is preferably in the range of 7 to 23 mol% of the remaining isocyanate group, and more preferably in the range of 10 to 20 mol%.

As said urethane prepolymer (A), the polyol (a-1) and the polyisocyanate (a-2), and the (meth) acrylic compound (a-3 which has a hydroxyl group) can be used specifically, for example. ) 'S reactants.

As the polyol (a-1), for example, polycarbonate polyol, polyether polyol, polyester polyol, polyacrylic 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 aforementioned polyol (a-1) is preferably in the range of 500 to 10,000, and more preferably in the range of 800 to 6,000, from the viewpoint of obtaining good mechanical properties. The number average molecular weight of the polyol (a-1) is a value measured by a gel permeation chromatography (GPC) method under the following conditions.

Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)

Columns: The following columns made by Tosoh Corporation are connected in series and used.

`` TSKgel G5000 '' (7.8mmI.D. × 30cm) × 1

`` TSKgel G4000 '' (7.8mmI.D. × 30cm) × 1

`` TSKgel G3000 '' (7.8mmI.D. × 30cm) × 1

`` TSKgel G2000 '' (7.8mmI.D. × 30cm) × 1

Detector: RI (differential refractometer)

Column temperature: 40 ℃

Eluent: Tetrahydrofuran (THF)

Flow rate: 1.0mL / min

Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)

Standard sample: A calibration curve was prepared using the following standard polystyrene.

    (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" made by Tosoh Corporation

"TSKgel Standard Polystyrene F-288" made by Tosoh Corporation

"TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

For the aforementioned polyol (a-1), a chain elongating agent having a number average molecular weight in the range of 50 to 450 may be used in combination as necessary.

Examples of the chain extender include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, and 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, trimethylolethane, glycerol, etc. Chain extender with hydroxyl group; ethylenediamine, 1,2-propanediamine, 1,6-hexanediamine, piperidine 2,5-dimethylpiperazine , Isophorone diamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-dicyclohexylmethanediamine, 3,3 A chain extender having an amine group such as'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, hydrazine, and the like. These chain elongating agents may be used alone or in combination of two or more.

As the polyisocyanate (a-2), for example, polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, polymerized diphenylmethane diisocyanate, and carbodiimide-modified diphenylmethane can be used. Aromatic polyisocyanates such as diisocyanate, benzene diisocyanate, toluene diisocyanate, naphthalene diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane Aliphatic or alicyclic polyisocyanates, such as diisocyanate, xylylene diisocyanate, and tetramethyl phenylene diisocyanate. These polyisocyanates may be used alone or in combination of two or more. Among these, in terms of obtaining more excellent reactivity and mechanical strength, an aromatic polyisocyanate is preferably used, and diphenylmethane diisocyanate is more preferable.

As the (meth) acrylic compound (a-3) having a hydroxyl group, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl acrylate, Alkyl (meth) acrylates having a hydroxyl group, such as 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl acrylate, and hydroxyethylpropenamide; trihydroxy Polyfunctional (meth) acrylates with hydroxyl groups, such as methylpropane di (meth) acrylate, neopentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate; polyethylene Glycol monoacrylate, polypropylene glycol monoacrylate, and the like. These compounds may be used alone or in combination of two or more.

As the method for producing the urethane prepolymer (A), for example, it can be obtained by reacting the polyol (a-1) with the polyisocyanate (a-2) in the absence of a solvent. A method for producing a urethane prepolymer (A-1) by reacting the (meth) acrylic compound (a-3) having a hydroxyl group as described above. In any of the above reactions, it is preferably carried out under conditions of 20 to 120 ° C, for example, for about 30 minutes to 24 hours.

The equivalent ratio of the isocyanate group of the polyisocyanate (a-2) to the hydroxyl group of the polyol (a-1) when producing the urethane prepolymer (A-1) ([ NCO / OH]), from the viewpoint of further improving the mechanical strength, the range of 1.5 to 25 is preferable, and the range of 3 to 15 is more preferable.

As the polyol (B) used in the hardener (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.

The polyol (B) may be used in combination with the same chain extender as necessary. These chain elongating agents may be used alone or in combination of two or more.

The polyurethane composition used in the present invention comprises: a main agent (i) containing the aforementioned urethane prepolymer (A); and a hardener (ii) containing the aforementioned polyol (B); However, other additives may be contained as required.

As the aforementioned other additives, for example, a photopolymerization initiator, water, a catalyst, a foam stabilizer, a polymerization inhibitor, an antioxidant, a thixotropy imparting agent, a plasticizer, a stabilizer, an inorganic filler, and an organic filler can be used. , Dyes, pigments, etc. These additives may be used singly or in combination of two or more kinds. These additives may be included in either of the aforementioned main agent (i) and the aforementioned hardening agent (ii), but may improve the urethane prepolymer (A). From the viewpoint of stability, it is preferably contained in the hardener (ii).

The aforementioned photopolymerization initiator generates radicals due to light irradiation or heating, etc., and is preferably used to initiate the radical polymerization of the aforementioned urethane (meth) acrylate (A). For example, 4 -Phenoxydichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- (4-isopropylphenyl) -2- Hydroxy-2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-methyl -[4- (methylthio) phenyl] -2- Acetophenone compounds such as phosphono-1-acetone, 2,2-dimethoxy-2-phenylacetophenone; benzoin, benzoin methyl ether, benzoin isoethyl ether, benzoin isopropyl Ethers, benzoin isobutyl ether and other benzoin compounds; benzophenone, benzophenobenzoate, methyl benzophenobenzoate, 4-phenylbenzophenone, hydroxybenzophenone, Benzophenone compounds such as 4-benzylidene-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone; oxygen sulfur (thioxanthone), 2-chlorooxysulfur 2,4-dichlorooxysulfur 2-methyloxysulfur 2,4-dimethyloxysulfur 2,4-diethyloxysulfur Isopropyloxysulfur 2,4-diisopropyloxysulfur Isosulfur Compound; 4,4'-dimethylaminooxysulfur , 4,4'-diethylaminobenzophenone, α-acyloxime ester, benzil, methyl benzylformate (`` Vicure55 '' ), Anthraquinone compounds such as 2-ethylanthraquinone; 2,4,6-trimethylbenzobenzoyl diphenylphosphine oxide, bis (2,4 , 6-trimethylbenzylidene) -phenylphosphine oxide and other phosphonium phosphine oxide compounds; 3,3 ', 4,4'-tetrakis (tertiary butylperoxycarbonyl) benzophenone, Acrylated benzophenone and the like. These photopolymerization initiators may be used alone or in combination of two or more.

The amount used when the photopolymerization initiator is used is preferably 0.1 to 5 based on 100 parts by mass of the urethane prepolymer (A) from the viewpoint of obtaining good ultraviolet curability. The range of parts by mass is more preferably in the range of 0.5 to 2 parts by mass.

Next, the manufacturing method of the polyurethane foam sheet of this invention is demonstrated.

Examples of the foaming method of the polyurethane composition in the production of the polyurethane foamed sheet of the present invention include a gas-filling method, a water-foaming method, and a mechanical foaming method. froth method). Among these, from the viewpoint of a wide allowable range of viscosity of the liquid component and obtaining more excellent bubble retention, it is preferable to use a gas filling method and / or a water foaming method to dissolve into the polymer from an inert gas well. The urethane composition is more preferably a gas-filled method in terms of obtaining better bubble retention.

As a method for obtaining a polyurethane foamed sheet using the gas filling method, for example, before mixing the main agent (i) and the hardener (ii), the main agent (i) and / Alternatively, the hardener (ii) is a method of gas-filling an inert gas at a pressure in the range of preferably 0.05 to 0.2 MPa, and more preferably 0.07 to 0.18 MPa.

The aforementioned gas filling refers to a process of forcibly incorporating an inert gas from the outside into the main agent (i) and / or the hardener (ii) under pressure. When the inert gas is introduced, it is preferable to stir the main agent (i) and / or the hardener (ii) from the viewpoint of improving the solubility of the inert gas. The gas filling can be performed using a known filling device.

Examples of the inert gas include carbon dioxide, helium, nitrogen, argon, and neon. Among these, carbon dioxide is preferably used because of ease of obtaining raw materials and high solubility in the main agent (i) and hardener (ii).

As the pressure during the above-mentioned gas filling, it is possible to maintain stable bubbles caused by an inert gas, and it is preferably in the range of 0.05 to 0.2 MPa. From this, a more uniform bubble can be maintained, and a better feel can be obtained. From the point of view, a range of 0.07 to 0.18 MPa is more preferable, and a range of 0.08 to 0.17 MPa is more preferable.

The time for performing the above-mentioned gas filling is preferably in the range of 10 minutes to 3 hours from the viewpoint that the inert gas can be uniformly filled and the deterioration of the urethane prepolymer and the polyol is prevented. 10 ~ 60 minutes range.

The gas filling is preferably performed only on the main agent (i). For this reason, when the gas filling is performed under the same conditions (pressure and time), the solubility of the inert gas is higher than that of the main agent (i) and the hardener (ii). This is because Thereby, a polyurethane foam sheet having a stable foam can be easily obtained. In addition, at this time, the hardening agent (ii) may contain water to be described later, and it is preferable to further contain a catalyst and a foam stabilizer, and to use a water foaming method together with gas filling.

The viscosity of the main agent (i) at 50 ° C when the gas is filled is preferably 200 to 20,000 mPa from the point that the inert gas can be filled well under the pressure. The range of s is more preferably 250 ~ 15,000mPa. The range of s. The viscosity of the main agent (i) at 50 ° C is a value measured by a B-type viscometer (rotor No. 3, rotation speed: 12 rpm).

When the main agent (i) is filled with the gas, from the viewpoint of obtaining better bubble retention and feel, the main agent (i) immediately after the gas is filled is opened to the main agent after normal pressure. The specific gravity of the agent (i) is preferably in the range of 0.2 to 0.8, and more preferably in the range of 0.3 to 0.7.

Examples include a method of filling the gas, then returning to normal pressure, mixing the main agent (i) and the hardener (ii), and performing a urethane reaction; filling the gas with a pressure difference The above-mentioned main agent (i) and / or hardener (ii) are moved to a mixer or the like that is connected to a filling device, and a method such as a urethane reaction is performed by mixing with a mixer or the like.

The mixing ratio [(i): (ii)] of the main agent (i) and the hardening agent (ii) is preferably in a range of 80:20 to 20:80, and more preferably 75:25 to The range of 25:75.

Next, the mixed main agent (i) and the hardening agent (ii) are coated on a substrate such as a release paper, a substrate coated with a release agent, and the like, and then irradiated with ultraviolet rays, thereby obtaining Polyurethane foam sheet.

Examples of a method for applying the mixed main agent (i) and the hardener (ii) include, for example, an applicator, a roll coater, a sprayer, a T-die coater, a knife coater, and the like. Methods. The applied thickness is, for example, in a range of 10 to 500 μm.

As a method for performing the aforementioned ultraviolet irradiation, for example, a low-illumination ultraviolet light irradiation device such as a fluorescent chemical lamp, a black light, and an LED lamp is used; a xenon lamp, a xenon-mercury lamp, a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, and an LED Lights and so on. A method for irradiating a predetermined ultraviolet ray with a high-illuminance ultraviolet light irradiation device.

Examples of the cumulative amount of light when the aforementioned ultraviolet irradiation is performed include a range of 100 to 1,500 mJ / cm ^2. From the viewpoint of allowing the photopolymerization reaction to proceed without any defects, it is preferably 200 to 1,000 mJ / cm. ² range. The cumulative light amount of the ultraviolet rays is based on a value measured in a wavelength region of 300 to 390 nm using a UV tester "UVR-N1" manufactured by GS-YUASA Corporation.

After the aforementioned ultraviolet irradiation, in order to harden the isocyanate of the remaining urethane prepolymer (A), it is preferable to perform aging at a temperature of 40 to 130 ° C. for 3 minutes to 3 days. Thereafter, it may be further aged at a temperature of 40 to 80 ° C for 1 to 3 days.

In addition, as a method for obtaining a polyurethane foamed sheet using the water foaming method, for example, the hardener (ii) is contained in water, and preferably a catalyst and a foam stabilizer are further contained, and A method of mixing the aforementioned main agent (i) and the aforementioned hardening agent (ii).

In the case where the above-mentioned water system functions as a foaming agent, the use amount thereof is preferably in the range of 0.01 to 10% by mass and more preferably in the range of 0.02 to 5% by mass in the hardener (ii).

For the aforementioned catalyst, for example, triethylenediamine, N, N, N ', N'-tetramethylhexamethylenediamine, 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-dimethylaminopropyl) -N, N-dimethylpropane Diamine, N, N-dicyclohexylmethylamine, bis (dimethylaminoethyl) ether, N, N ', N "-gins (3-dimethylaminopropyl) hexahydro-S- three , N, N-dimethylaniline, N, N-dimethylaminoethoxyethoxyethanol, N, N-dimethylaminohexanol, N, N-dimethylamino Ethoxyethanol, N, N, N'-trimethylaminoethylethanolamine, N, N, N'-trimethyl-2-hydroxyethylpropanediamine, 1-methylimidazole, 1-iso Butyl-2-methylimidazole, 1,2-dimethylimidazole, dimethylethanolamine, triethanolamine and other amine compounds; dibutyltin dilaurate, dioctyltin dilaurate, tin 2-ethylhexanoate Metal compounds such as acids, potassium octoate, dibutyltin lauryl mercaptide, and bismuth (2-ethylhexanoate) bismuth. These catalysts can be used alone or in combination of two or more.

The amount used when the catalyst is used is preferably in the range of 0.01 to 1% by mass, and more preferably in the range of 0.05 to 0.5% by mass in the hardener (ii).

As for the aforementioned foam stabilizer, a polysiloxane surfactant may be preferably used. For example, as a commercially available product, “SZ-1919”, “SH-192”, “SH-190”, and “SZ- 580 "," SRX-280A "," SZ-1959 "," SZ-1328E "," SF-2937F "," SF-2938F "," SZ-1671 "," SH-193 "," SZ-1923 " , "Silicon Y-7006" (above, manufactured by Dow Corning Toray Silicone Co., Ltd.), etc. The amount used when the foam stabilizer is used is preferably in the range of 0.01 to 5% by mass, and more preferably in the range of 0.03 to 3% by mass in the hardener (ii).

As a method of mixing the said main agent (i) and the said hardening | curing agent (ii), the method of using a hybrid injection molding machine is mentioned, for example.

Specifically, for example, the following method may be mentioned: the main agent (i) and the hardening agent (ii) are placed in each tank of a hybrid injection molding machine, and the main agent (i) is preferably 40 to 80 ° C. A method in which the temperature is increased within a range of 50 ° C., and the aforementioned hardener (ii) is preferably heated in a range of preferably 40 to 80 ° C., and each is mixed in a mixing injection molding machine.

The mixing ratio [(i): (ii)] of the main agent (i) and the hardener (ii) is preferably in a range of 80:20 to 20:80 in mass ratio, and more preferably 75:25. ~ 25: 75 range.

Next, the mixed main agent (i) and the hardening agent (ii) may be coated on a substrate such as a release paper, a substrate coated with a release agent, and the like, and then irradiated with ultraviolet rays, and A polyurethane foamed sheet was obtained. This step is the same as when using the aforementioned gas filling method.

The density of the polyurethane foamed sheet obtained by the above method is preferably in the range of 0.5 to 0.95 g / cm ³ , and more preferably in the range of 0.65 to 0.9 in terms of obtaining good hand feeling. g / cm ³ range. In addition, the method for measuring the density of the polyurethane foamed sheet is the following method: measuring the thickness and weight of the polyurethane foamed sheet cut to a length of 10 cm and a width of 10 cm, in accordance with the following Formula (1) is a method of calculating the density.

Density (g / cm ³ ) = weight (g) / 10 (cm) × 10 (cm) × thickness (cm) (1)

Next, the manufacturing method of the laminated body of this invention is demonstrated.

As the manufacturing method of the said laminated body, Preferably, the polyurethane foamed sheet obtained by using the said gas filling method, and / or the polyurethane foam obtained by using the said water foaming method are mentioned, for example. A method for producing a formic acid foamed sheet by bonding it to a fiber substrate. In addition, as for the said polyurethane foam sheet, the thing which did not perform the curing after performing the said ultraviolet irradiation, or the thing which performed the ultraviolet irradiation and the curing may be used. Among these, the former method is preferably used from the viewpoint that it is easy to control the amount of infiltration of the polyurethane foamed sheet into the fibrous substrate and to obtain more excellent peel strength.

As the fiber substrate, for example, a nonwoven fabric, a woven fabric, a knitted fabric, or the like can be used. As the fiber substrate, for example, polyester fiber, nylon fiber, acrylic fiber, acetate fiber, rayon fiber, polylactic acid fiber, cotton, hemp, silk, wool, etc. can be used. Blended fibers and so on.

As described above, the polyurethane foamed sheet of the present invention is one having excellent foam retention, hand feel, and peel strength after forming a sheet.

    [Example]    

Hereinafter, the present invention will be described in more detail using examples.

    [Preparation example 1] Preparation of main agent (i-1)    

100 parts by mass of 4,4'-diphenylmethane diisocyanate (hereinafter, abbreviated as "MDI") and 120 parts by mass of polytetramethylene glycol ("PTMG2000" manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 2,000) A four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser was allowed to react at 80 ° C for 3 hours to obtain NCO%: 12.9% by mass of a urethane prepolymer. (A-1-1).

Next, 11.8 parts by mass of 2-hydroxyethyl acrylate (hereinafter abbreviated as "HEA") was placed and allowed to react at 60 ° C for 2 hours to obtain 15 mol% of the remaining isocyanate group. The resulting urethane prepolymer (Ai) was used as the main agent (i-1). The viscosity of the aforementioned main agent (i-1) at 50 ° C was 1,550 mPa. s.

    [Preparation example 2] Preparation of main agent (i-2)    

100 parts by mass of MDI and 107 parts by mass of PTMG2000 were placed in a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, and allowed to react at 80 ° C for 3 hours to obtain NCO%: 14.2% by mass Urethane prepolymer (A-1-2).

Next, 16 parts by mass of HEA was placed and reacted at 60 ° C for 2 hours to obtain a urethane prepolymer (Aii) obtained by introducing an acrylic fluorenyl group at 20 mol% of the remaining isocyanate group. This was used as a main agent (i-2). The viscosity of the aforementioned 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, a stirrer, an inert gas inlet, and a reflux condenser, and allowed to react at 80 ° C for 3 hours to obtain NCO%: 11.2% by mass Urethane prepolymer (A'-1-1).

Next, 2.3 parts by mass of HEA was placed and allowed to react at 60 ° C for 2 hours to obtain a urethane prepolymer (A'i ) As the main agent (i'-1). The viscosity of the aforementioned 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, a stirrer, an inert gas inlet, and a reflux condenser, and allowed to react at 80 ° C for 3 hours to obtain NCO%: 17.4% by mass Urethane prepolymer (A'-1-2).

Next, 25.2 parts by mass of HEA was placed and reacted at 60 ° C for 2 hours to obtain a urethane prepolymer (A'ii) in which 30 mol% of the remaining isocyanate group was introduced with an acrylic fluorenyl group. ) As the main agent (i'-2). The viscosity of the aforementioned 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, a stirrer, an inert gas inlet, and a reflux condenser, and allowed to react at 80 ° C for 3 hours to obtain NCO%: 1.9% by mass. Urethane prepolymer (A'-1-3).

Next, 4.9 parts by mass of HEA was placed and reacted at 60 ° C for 2 hours to obtain a urethane prepolymer (A'iii) in which 15 mol% of the remaining isocyanate group was introduced with an acrylfluorene group. ) As the main agent (i'-3). The viscosity of the aforementioned 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, a stirrer, an inert gas inlet, and a reflux condenser, and allowed to react at 80 ° C for 3 hours to obtain NCO%: 21% by mass Urethane prepolymer (A'-1-4).

Next, 13.1 parts by mass of HEA was placed and reacted at 60 ° C for 2 hours to obtain an urethane prepolymer (A'iv) in which 15 mol% of the remaining isocyanate group was introduced with an acrylic fluorenyl group. ) As the main agent (i'-4). The viscosity of the aforementioned main agent (i'-4) at 50 ° C was 820 mPa. s.

    [Preparation example 7] Preparation of hardener (ii-1)    

100 parts by mass of polytetramethylene glycol (quantity average molecular weight: 1,000), 8 parts by mass of ethylene glycol, and 2 parts by mass of "Irugacure184" manufactured by Ciba Specialty Co., Ltd. as a photopolymerization initiator were mixed and stirred to obtain Hardener (ii-1).

    [Example 1]    

The aforementioned main agent (i-1) was placed in a filling device. Thereafter, the inside of the filling device was pressurized with carbon dioxide to 0.1 MPa, and it took 30 minutes to fill while stirring the raw materials.

Next, the gas-filled main agent (i-1) was fed from the filling device to the low-pressure urethane manufactured by Polymer Engineering Co., Ltd. using a pressure difference, and injected into the main agent tank of the foaming machine "MT5" at 0.5. Circulate at a pressure of MPa.

The hardener (ii-1) was also fed to the hardener tank and circulated under a pressure of 0.5 MPa. Thereafter, the mixture was simultaneously ejected so that (i-1) and (ii-1) had a mass ratio of 167: 100 and mixed instantaneously, and then the mixed solution was applied to a layer having a thickness of 250 μm so that it was coated with a release agent. On the sheet.

Next, an ultraviolet irradiation device "CSOT-40" (high-pressure mercury lamp, illuminance: 120 mW / cm ² , conveyor speed: 5 m / min) manufactured by Japan Battery Co., Ltd. was used to irradiate the coated object with 300 mJ / cm ² of ultraviolet light. After that, fit the base fabric. Thereafter, a heat treatment was performed at 110 ° C for 5 minutes. The continuous operation was performed for 30 minutes and the winding was performed to obtain a fiber laminate.

    [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.

    [Evaluation method of foam retention of polyurethane foam sheet]    

A scanning electron microscope "SU3500" (magnification: 100 times) manufactured by Hitachi High-Technologies Co., Ltd. was used to observe the cross-sectional views of the fiber laminates obtained in Examples and Comparative Examples as seen from the side. In addition, the fiber laminate was left as a test piece for 7 days under the conditions of a temperature of 23 ° C. and a humidity of 50%. The cross-sectional view was similarly observed with a scanning electron microscope, and the bubble retention was evaluated as follows.

"T": In the cross-sectional view of the test piece, a bubble was confirmed immediately after the fiber laminate was produced, and the state remained almost unchanged after 7 days.

"F": In the cross-sectional view of the test piece, the bubble was crushed immediately after the fiber laminate was prepared and the bubble could not be confirmed; or the bubble was confirmed immediately after the fiber laminate was prepared, but the shape of the bubble was changed after 7 days or The blister was crushed.

    [Evaluation of Hand Feel of Polyurethane Foam Sheet]    

The polyurethane foamed sheet side of the fiber laminate obtained in the examples and comparative examples was touched by hand, and evaluated as follows.

"T": Soft.

"F": Hard.

    [Evaluation method of the amount of impregnation of the polyurethane foam sheet with the fiber base material (base cloth)]    

The fiber laminates obtained in the examples and comparative examples were left for one day, and thereafter the rolls were unwound. A fiber laminate at a distance of 10 m from the start of winding was used as a test piece. A scanning electron microscope "SU3500" (magnification: 200 times) manufactured by Hitachi High-Technologies Co., Ltd. was used to observe the cross-sectional view of the test piece seen from the side, and to measure the penetration of the polyurethane foamed sheet into the base cloth. Length (μm).

    [Evaluation Method of Peel Strength of Polyurethane Foam Sheet]    

The test piece used in the said [Evaluation method of the penetration amount of a polyurethane foam sheet to a fiber base material (base cloth)] was used. A 1-inch (2.54cm) wide hot-melt cloth tape was heated and adhered to the surface of the test piece at 130 ° C for 5 seconds, and the temperature was 23 ° C and the relative humidity was 65%. According to JISK6854-2- In 1999, using the Autograph "G-1" manufactured by Shimadzu Corporation, the peel strength (N / cm) was measured under the conditions of head speed: 200 mm / minute. In addition, those who cause material failure and whose peel strength cannot be measured are described as "-".

It can be seen that the polyurethane foamed sheet obtained by the production method of the present invention maintains the foam well even after forming the sheet, and further has excellent feel and peel strength.

On the other hand, Comparative Example 1 uses the introduction amount of the polymerizable unsaturated group of the remaining isocyanate group below the range specified in the present invention as the urethane prepolymer (A). Poor retention and material damage due to excessive infiltration of the base cloth.

Comparative Example 2 is a state in which the introduction amount of the polymerizable unsaturated group for the remaining isocyanate group exceeds the range specified in the present invention as the urethane prepolymer (A). Although the foam retention is good, But it feels bad. In addition, there was no impregnation with the base fabric, and the peeling strength was also poor.

In Comparative Example 3, the NCO% of the urethane prepolymer (A-1) was lower than the range specified in the present invention. Although the foam retention was good, the texture was poor. In addition, there was no impregnation with the base fabric, and the peeling strength was also poor.

Comparative Example 3 In a state in which the NCO% of the urethane prepolymer (A-1) exceeds the range specified in the present invention, the foam retention and hand feeling are poor, and the base fabric is too much impregnated and the peel strength Also bad.

Claims (9)

    A polyurethane foamed sheet is a polyurethane foamed sheet formed by a polyurethane composition containing a main agent (i) and a hardener (ii), wherein The base agent (i) contains a urethane prepolymer (A) having an isocyanate group, and the hardener (ii) contains a polyol (B); it is characterized in that the urethane prepolymer (A ) Is based on an urethane prepolymer (A-1) having an isocyanate group content of 2 to 20% by mass, and a polymerizable unsaturated group is introduced into 5 to 25 mol% of the remaining isocyanate group. .         A method for producing a polyurethane foamed sheet, characterized in that the polyurethane composition as claimed in claim 1 is developed by a gas loading method and / or a water foaming method. bubble.         For example, the method for producing a polyurethane foamed sheet according to claim 2, wherein the gas filling method is a pressure in the range of 0.05 to 0.2 MPa for the main agent (i) and / or the hardener (ii). Next, the inert gas is gas-filled.         The method for producing a polyurethane foamed sheet according to claim 3, wherein the gas filling is performed only on the main agent (i).         For example, the method for manufacturing a polyurethane foamed sheet according to claim 4, wherein the viscosity of the main agent (i) at 50 ° C is 200 to 20,000 mPa when the gas is filled. The range of s.         A method for manufacturing a laminate, which is characterized in that the polyurethane composition according to claim 1 is foamed by a gas filling method and / or a water foaming method, and then coated on a substrate. Ultraviolet irradiation was performed to obtain a polyurethane foamed sheet, which was then bonded to a fiber substrate.         For example, the method for manufacturing a laminated body according to claim 6, wherein the gas filling method is to inert the main agent (i) and / or the hardener (ii) at a pressure in the range of 0.05 to 0.2 MPa. filling.         The method for manufacturing a laminated body according to claim 7, wherein the main agent (i) is filled with the gas only.         For example, the method for manufacturing a laminated body according to claim 8, wherein the viscosity of the main agent (i) at 50 ° C is 200 to 20,000 mPa when the gas is filled. The range of s.