Moisture curable hot melt urethane composition, method for producing cured foam of same, synthetic leather and method for producing synthetic leather

CROSS REFERENCE

This application is the U.S. National Phase under 35 U.S.C. § 371 of International Application No. PCT/JP2016/067218, filed on Jun. 9, 2016, which claims the benefit of Japanese Application No. 2015-172935, filed on Sep. 2, 2015, Japanese Application No. 2015-221298, filed on Nov. 11, 2015, and Japanese Application No. 2015-221299, filed on Nov. 11, 2015, the entire contents of each are hereby incorporated by reference.

TECHNICAL FIELD

The present invention provides a moisture-curable hot melt urethane composition, a method for producing a foamed and cured product of the same, a synthetic leather, and a method for producing the same.

BACKGROUND ART

With the regulations on the use of dimethylformamide (DMF) gaining momentum in Europe, it is highly desirable to provide a solvent-free, energy-saving, environmentally responsible resin. In this situation, a moisture-curable hot melt urethane composition, which is solvent-free, is attracting much attention and has been widely used in the production of synthetic leathers, building materials, automotive interior materials, refrigerators, smartphones, personal computers, and car navigation systems, and like electrical and electric devices, for example. In particular, in recent years, for the purposes of improving the impact resistance and texture through the buffering effect, reducing the usage of moisture-curable hot melt urethane compositions, and the like, moisture-curable hot melt urethane compositions are increasingly foamed and used as foamed and cured products.

As a method for foaming and curing the moisture-curable hot melt urethane composition, a water foaming method, which uses water or steam, has been widely studied (see, e.g., PTLs 1 and 2). In the water foaming method, water or steam reacts with the isocyanate groups in a moisture-curable hot melt urethane to produce carbon dioxide, and such carbon dioxide is allowed to remain as bubbles in the cured product. In addition, in the water foaming method, generally, the moisture-curable hot melt urethane is vigorously stirred with moisture or the like to increase the bubble generation rate, and the bubbles involved during vigorous stirring are positively allowed to remain.

However, in the water foaming method described above, the foaming degree varies depending on the mixed state in the system upon vigorous stirring. Accordingly, when the production is scaled up from experiment facilities to production facilities, it is extremely difficult to produce a foamed and cured product having a uniform foamed state stably with high reproducibility. In particular, in the water foaming method, particularly in the case where the foamed and cured product is in the form of a thin film having a thickness of less than 100 μm, it often happens that carbon dioxide escapes from the film, and there remain only bubbles involved during vigorous stirring. Thus, it has been extremely difficult to make a design such that an excellent foamed state can be formed stably with high reproducibility.

As a foaming method other than the water foaming method, for example, a method in which a composition containing a ketoxime-blocked urethane prepolymer, an aliphatic diamine, thermally expandable fine particles, and DMF is heated and foamed has been disclosed (see, e.g., PTL 3). However, this method uses DMF, and also the heating temperature is as extremely high as 180° C., which possibly adversely affects the substrate or base fabric. In addition, there also is a problem in that because the thermally expandable fine particles are solid and hard even after heating and foaming, the texture of the resulting foamed and cured product is poor.

Meanwhile, a synthetic leather, which is actively studied in recent years as an application example of polyurethane, generally includes a base fabric, an intermediate layer, and a surface skin layer, and such synthetic leathers have been widely utilized for the production of car interior materials, furnishings, moisture-permeable waterproof clothes, and the like. As the intermediate layer, generally, a foamed layer or porous layer formed from an N,N-dimethylformamide (DMF) solution of polyurethane by wet processing or the like is used. However, as described above, the regulations on the use of DMF are gaining momentum in Europe and China. Accordingly, also in synthetic leather applications, there is an urgent need for reduction in use or shift toward a solvent-free system.

As a method for DMF reduction in the formation of an intermediate layer, for example, the method as described in the PTL 3 has been disclosed. However, in the above method, the amount of DMF used is still large, and also the heating temperature is as extremely high as 180° C., which possibly adversely affects the base fabric or release paper, for example. In addition, there also is a problem in that because the thermally expandable fine particles are solid and hard even after heating and foaming, the texture of the resulting synthetic leather is poor.

Meanwhile, as a method in which no DMF is used for the formation of an intermediate layer, for example, the water foaming method as described in the PTL 1 or 2, which uses water or steam, has been widely studied. However, in the water foaming method described above, the foaming degree varies depending on the mixed state in the system upon vigorous stirring. Accordingly, when the production is scaled up from experiment facilities to production facilities, it is extremely difficult to produce an intermediate layer having a uniform foamed state stably with high reproducibility. In addition, in the water foaming method, particularly in the case where the intermediate layer is in the form of a thin film having a thickness of less than 100 μm, it often happens that carbon dioxide escapes from the film, and there remain only bubbles involved during vigorous stirring. Thus, it has been extremely difficult to make a design such that an excellent foamed state can be formed stably with high reproducibility.

CITATION LIST
Patent Literature

PTL 1: JP-A-2004-115705

PTL 2: JP-A-2003-306526

PTL 3: WO 2014/192283

SUMMARY OF INVENTION
Technical Problem

An object of the present invention is to provide a solvent-free foaming system, according to which a foamed and cured product with excellent texture can be obtained, and an excellent foamed state can be maintained even in a thin film.

Solution to Problem

The present invention provides a moisture-curable hot melt urethane composition, including a hot melt urethane prepolymer (A) having an isocyanate group and a foaming agent composition (B) containing N,N′-dinitrosopentamethylenetetramine (b1), urea (b2) and a polyol (b3).

The present invention also provides a method for producing a foamed and cured product of a moisture-curable hot melt urethane composition, which includes heat-melting a hot melt urethane prepolymer (A) having an isocyanate group, then mixing a foaming agent composition (B) containing N,N′-dinitrosopentamethylenetetramine (b1), urea (b2), and a polyol (b3) therewith, applying the resultant mixture to a substrate, and performing a heating treatment at a temperature equal to or higher than the heat-melting temperature of the hot melt urethane prepolymer (A) to thereby cause foaming and curing.

The present invention also provides a synthetic leather including a base fabric (i), an intermediate layer (ii), and a surface skin layer (iii), in which the intermediate layer (ii) is a foamed and cured product of the above moisture-curable hot melt urethane composition.

The present invention further provides a method for producing a synthetic leather, which includes heat-melting a hot melt urethane prepolymer (A) having an isocyanate group, then mixing a foaming agent composition (B) containing N,N′-dinitrosopentamethylenetetramine (b1), urea (b2), and a polyol (b3) therewith to give a moisture-curable hot melt urethane composition, applying the moisture-curable hot melt composition onto a surface skin layer (iii) formed on a release paper, performing a heating treatment at a temperature equal to or higher than the heat-melting temperature of the hot melt urethane prepolymer (A) to form an intermediate layer (ii), and subsequently attaching a base fabric (i) onto the intermediate layer (ii).

Advantageous Effects of Invention

In the moisture-curable hot melt urethane composition of the present invention, a specific heat-decomposable foaming agent is used. As a result, an excellent foamed state can be maintained even in a thin film, and a foamed and cured product with excellent texture can be obtained. In addition, even after foaming, no deterioration is caused in the mechanical properties of the foamed and cured product. In addition, foaming can be caused without the influence of water. Thus, even in the case where the moisture-curable hot melt urethane composition is once cooled and solidified from a melted state, or even during moisture curing, by performing a heating treatment again, the foaming of the heat-decomposable foaming agent can be promoted.

In addition, in the synthetic leather of the present invention, an organic solvent, such as DMF, is not used in the formation of an intermediate layer. As a result, the synthetic leather has less adverse effects on human health. In addition, because a specific heat-decomposable foaming agent is used in the formation of an intermediate layer, an excellent foamed state can be maintained even in the case where the intermediate layer is a thin film, and an intermediate layer and a synthetic leather with excellent texture can be obtained.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 shows an electron micrograph of a cross-sectional view of a foamed and cured product obtained in Example 1 (magnification: 200).

FIG. 2 shows an electron micrograph of a cross-sectional view of a foamed and cured product obtained in Example 15 (magnification: 200).

FIG. 3 shows an electron micrograph of a cross-sectional view of a foamed and cured product obtained in Comparative Example 1 (magnification: 200).

FIG. 4 shows an electron micrograph of a cross-sectional view of a foamed and cured product obtained in Comparative Example 2 (magnification: 200).

FIG. 5 shows an electron micrograph of a cross-sectional view of a foamed and cured product obtained in Comparative Example 4 (magnification: 200).

DESCRIPTION OF EMBODIMENTS

The moisture-curable hot melt urethane composition of the present invention includes, as essential components, a hot melt urethane prepolymer (A) having an isocyanate group and a foaming agent composition (B) containing N,N′-dinitrosopentamethylenetetramine (b1), urea (b2), and a polyol (b3).

In the present invention, the foaming agent composition (B) essentially contains N,N′-dinitrosopentamethylenetetramine (b1), urea (b2), and a polyol (b3). When this specific foaming agent composition is used, a foamed and cured product with excellent texture can be obtained without causing deterioration in the mechanical properties of the foamed and cured product, and an excellent foamed state can be maintained even in a thin film. In addition, foaming can be caused without the influence of water. Thus, even in the case where the moisture-curable hot melt urethane composition is once cooled and solidified from a melted state, or even during moisture curing, by performing a heating treatment again, foaming can be caused.

The N,N′-dinitrosopentamethylenetetramine (b1) functions as a heat-decomposable foaming agent. The (b1) has been mainly used as a foaming agent for natural rubber and synthetic rubber, and is known to generate an extremely large amount of gas or an extremely large amount of heat upon decomposition. Thus, such an agent has been believed to be unsuitable for use in a moisture-curable hot melt urethane composition, which is applied in a heat-melted state to a substrate or the like and used, because the agent is expected to undergo thermal decomposition immediately after mixing. However, it has been found that whereas the hot melt urethane prepolymer (A) used in the moisture-curable hot melt urethane composition is usually heat-melted at a temperature of 80 to 120° C., the (b1) foams when subjected to a heating treatment at a temperature equal to or higher than this temperature range (hereinafter abbreviated to “post-heating”), and an excellent foamed state can be formed and maintained even in a thin film. In this case, it is presumed that the component after the thermal decomposition of the (b1) has reacted with the isocyanate groups in the hot melt urethane prepolymer (A) and thus immobilized the bubbles. Although there are a large number of heat-decomposable foaming agents that generate an increased amount of gas in a temperature region equal to or higher than the heat-melting temperature of the hot melt urethane prepolymer (A), in the case of heat-decomposable foaming agents other than the (b1), the component after thermal decomposition does not react with the isocyanate groups in the hot melt urethane prepolymer (A). Accordingly, it is difficult to immobilize bubbles, and the obtained bubbles may deform or collapse after curing, leading to a problem in that the texture of the resulting foamed and cured product is impaired, or the surface appearance is impaired due to asperities.

The amount of the N,N′-dinitrosopentamethylenetetramine (b1) used is preferably in the range of 3 to 50 mass % in the foaming agent composition (B), and more preferably in the range of 5 to 40 mass %, since an excellent foamed state can be formed by post-heating, and less adverse effects are caused on the mechanical properties of the foamed and cured product.

The urea (b2) functions as a foaming aid for the (b1). In the case where the urea (b2) is not used, although foaming takes place, the bubbles may deform or collapse after curing, or the foaming of the (b1) may be uncontrollable, whereby the texture or surface appearance of the resulting foamed and cured product is impaired. The amount of the urea (b2) used is preferably in the range of 3 to 50 mass % in the foaming agent composition (B), and more preferably in the range of 8 to 40 mass %, since an excellent foamed state can be formed by post-heating even in a thin film.

The mass ratio [(b1)/(b2)] between the N,N′-dinitrosopentamethylenetetramine (b1) and urea (b2) is preferably in the range of 10/90 to 90/10, and more preferably in the range of 30/70 to 70/30, since an excellent foamed state can be formed by post-heating even in a thin film.

The polyol (b3) functions as a vehicle and is used in order to uniformly mix the (b1) and (b2) in the hot melt urethane prepolymer (A).

As the polyol (b3), for example, it is possible to use a polyester polyol, a polyether polyol, a polycarbonate polyol, a polyacrylic polyol, a polyolefin polyol, a castor oil polyol, a polyhydric alcohol, or the like; a copolymer thereof; etc. These polyols may be suitably determined according to the intended use of the foamed and cured product. They may be used alone, and it is also possible to use two or more kinds together.

As the polyether polyol, for example, it is possible to use a polymerization product of a polyhydric alcohol and an alkylene oxide.

As the polyhydric alcohol, for example, it is possible to use a glycol such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane-1,4-diol, or cyclohexane-1,4-dimethanol; a polyester polyol; etc. These compounds may be used alone, and it is also possible to use two or more kinds together.

As the alkylene oxide, for example, it is possible to use ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc. These compounds may be used alone, and it is also possible to use two or more kinds together.

As the polyester polyol, for example, it is possible to use a polymerization product of a polyhydric alcohol and a polybasic acid; a polymerization product of the polyether polyol and a lactone compound; etc.

As the polyhydric alcohol, for example, it is possible to use ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, an ethylene oxide or propylene oxide adduct of bisphenol A, etc. These polyhydric alcohols may be used alone, and it is also possible to use two or more kinds together.

As the polybasic acid, for example, it is possible to use succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, hexahydroisophthalic acid, etc. These polybasic acids may be used alone, and it is also possible to use two or more kinds together.

As the lactone compound, for example, it is also possible to use a polymerization product obtained by the ring-opening addition of γ-butyrolactone or ε-caprolactone.

As the polycarbonate polyol, for example, it is possible to use one obtained by allowing a carbonate and/or a phosgene to react with a compound having two or more hydroxyl groups.

As the carbonate, for example, it is possible to use dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, etc. These compounds may be used alone, and it is also possible to use two or more kinds together.

As the compound having two or more hydroxyl groups, for example, it is possible to use 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-dihydroxyhexane, 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, glycerin, etc. These compounds may be used alone, and it is also possible to use two or more kinds together.

As the polyol (b3), among those described above, in terms of reaction with the hot melt urethane prepolymer (A), and since a foamed and cured product or a synthetic leather with excellent texture can be obtained, it is preferable to use a polyether polyol, it is preferable to use a polyoxypropylene polyol, and it is more preferable to use a polymerization product of polyoxypropylene triol and/or glycerin and propylene oxide.

In terms of ease of mixing with the hot melt urethane prepolymer (A), the number average molecular weight of the polyol (b3) is preferably in the range of 500 to 10,000, and more preferably in the range of 700 to 5,000. Incidentally, the number average molecular weight of the polyol (b3) refers to a value measured by gel permeation chromatography (GPC) under the following conditions.

Measuring device: High-performance GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)

Column: The following columns manufactured by Tosoh Corporation were connected in series and used.

“TSKgel G5000” (7.8 mm I.D.×30 cm)×1

“TSKgel G4000” (7.8 mm I.D.×30 cm)×1

“TSKgel G3000” (7.8 mm I.D.×30 cm)×1

“TSKgel G2000” (7.8 mm I.D.×30 cm)×1

Detector: RI (differential refractometer)

Column temperature: 40° C.

Eluent: Tetrahydrofuran (THF)

Flow rate: 1.0 mL/min

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

Standard: Calibration curves were prepared using the following standard polystyrenes.

(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

In terms of ease of mixing with the hot melt urethane prepolymer (A) and the mechanical properties of the foamed and cured product, the amount of the polyol (b3) used is preferably in the range of 30 to 90 mass % in the foaming agent composition (B), and more preferably in the range of 40 to 80 mass %.

In addition, the mass ratio [(b1)+(b2)/(b3)] between the total mass of the N,N′-dinitrosopentamethylenetetramine (b1) and urea (b2) and the polyol (b3) is preferably in the range of 10/90 to 70/30, and more preferably in the range of 30/70 to 60/40, since the mixture does not become pasty, whereby fluidity can be ensured to give excellent workability, and also in terms of excellent miscibility with the hot melt urethane prepolymer (A).

The foaming agent composition (B) contains the (b1) to (b3) as essential components, and may also contain other additives as necessary.

As the other additives, for example, it is possible to use heat-decomposable foaming agents other than the (b1), such as azodicarbonamide, 4,4′-oxybis(benzenesulfonyl hydrazide), and sodium hydrogen carbonate; boric acid (b4); etc. These additives may be used alone, and it is also possible to use two or more kinds together. Among them, it is preferable to use boric acid (b4), since the foaming aid function of the urea (b2) is further enhanced, whereby larger bubbles can be formed, and a foamed and cured product or a synthetic leather with even superior texture can be obtained.

In the case where the boric acid (b4) is used, the amount used is preferably in the range of 5 to 150 parts by mass, more preferably in the range of 10 to 120 parts by mass, per 100 parts by mass of the urea (b2).

The amount of the foaming agent composition (B) used is preferably in the range of 1 to 30 parts by mass, more preferably in the range of 5 to 25 parts by mass, per 100 parts by mass of the hot melt urethane prepolymer (A), since a foamed and cured product or a synthetic leather with excellent texture can be obtained without causing deterioration in the mechanical properties of the foamed and cured product, and an excellent foamed state can be maintained even in a thin film.

The hot melt urethane prepolymer (A) having an isocyanate group is solid at room temperature and preferably melts at a temperature of 80 to 120° C. The melt viscosity at 100° C. of the hot melt urethane prepolymer (A) measured with a cone-plate viscometer is preferably in the range of 100 to 100,000 mPa·s, and more preferably in the range of 500 to 70,000 mPa·s. Incidentally, the melt viscosity of the hot melt urethane prepolymer (A) refers to a value measured as follows. The hot melt urethane prepolymer (A) is melted at 100° C. for 1 hour and then subjected to measurement using a cone-plate viscometer (Digital Cone Viscometer “CV-1S, RT Type” manufactured by MST Engineering Co., Ltd.).

The hot melt urethane prepolymer (A) may be a known prepolymer. For example, it is possible to use a reaction product between a polyol (a1) and a polyisocyanate (a2).

As the polyol (a1), those same as the examples of the polyol (b3) are usable. These polyols may be suitably determined according to the intended use. They may be used alone, and it is also possible to use two or more kinds together. Among them, in the case where the synthetic leather of the present invention is used in applications where excellent bending resistance and hydrolysis resistance are required, it is preferable to use polyoxytetramethylene glycol in an amount of 50 mass % or more in the polyol (a1), and more preferably in the range of 60 to 90 mass %. In addition, in the case where the synthetic leather of the present invention is used in applications where excellent durability is required, it is preferable to use a polycarbonate polyol in an amount of 50 mass % or more in the polyol (a1), and more preferably in the range of 60 to 90 mass %.

In addition, in the case where polyoxytetramethylene glycol is used as the polyol (a1), it is preferable to use a polyester polyol together, and it is more preferable to use an aromatic polyester polyol together, since the cohesive strength is improved, whereby even more excellent bending resistance, hydrolysis resistance, and heat resistance can be obtained, and an excellent foamed state can be formed even in a thin film. In addition, in the case where a polycarbonate polyol is used as the polyol (a1), it is preferable to use a polyester polyol together, since the cohesive strength is improved, whereby even more excellent flexibility, hydrolysis resistance, and heat resistance can be obtained, and an excellent foamed state can be formed even in a thin film.

The number average molecular weight of the polyol (a1) is preferably in the range of 500 to 7,000, and more preferably in the range of 700 to 4,000, in terms of mechanical properties. Incidentally, the number average molecular weight of the polyol (a1) refers to a value measured in the same manner as for the number average molecular weight of the polyol (b3).

As the polyisocyanate (a2), for example, it is possible to use an aromatic polyisocyanate such as polymethylenepolyphenyl polyisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, or naphthalene diisocyanate; an aliphatic or alicyclic polyisocyanate such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, or tetramethylxylylene diisocyanate; etc. These polyisocyanates may be used alone, and it is also possible to use two or more kinds together. Among them, it is preferable to use an aromatic polyisocyanate, and it is more preferable to use diphenylmethane diisocyanate and/or xylylene diisocyanate, since excellent reactivity and mechanical properties can be obtained.

A method for producing the hot melt urethane prepolymer (A) may be as follows, for example. The polyol (a1) is added dropwise to a reaction vessel containing the polyisocyanate (a2) and then heated, and they are allowed to react under conditions where the isocyanate groups in the polyisocyanate (a2) are in excess of the hydroxyl groups in the polyol (a1).

In terms of mechanical strength, the equivalence ratio ([NCO/OH]) between the isocyanate groups in the polyisocyanate (a2) and the hydroxyl groups in the polyol (a1) in the production of the hot melt urethane prepolymer (A) is preferably in the range of 1.1 to 5, and more preferably in the range of 1.5 to 3.5.

In terms of mechanical strength, the isocyanate group content of the hot melt urethane prepolymer (A) (hereinafter abbreviated to “NCO %”) is preferably in the range of 1.1 to 5 mass %, and more preferably in the range of 1.5 to 4 mass %. Incidentally, the isocyanate group content of the hot melt urethane prepolymer (A) refers to a value measured by potentiometric titration in accordance with JISK1603-1:2007.

The moisture-curable hot melt urethane composition of the present invention contains the hot melt urethane prepolymer (A) and the foaming agent composition (B) as essential components, and may also contain other additives as necessary.

As the other additives, for example, it is possible to use urethanization catalysts, silane coupling agents, thixotropy-imparting agents, antioxidants, plasticizers, fillers, dyes, pigments, waxes, etc. These additives may be used alone, and it is also possible to use two or more kinds together.

Next, the method for producing a foamed and cured product of the moisture-curable hot melt urethane composition will be described.

In the method for producing a foamed and cured product of the moisture-curable hot melt urethane composition of the present invention, it is essential that the hot melt urethane prepolymer (A) having an isocyanate group is heat-melted, then a foaming agent composition (B) containing N,N′-dinitrosopentamethylenetetramine (b1), urea (b2), and a polyol (b3) is mixed with the heat-melted hot melt urethane prepolymer (A), and the mixture is applied to a substrate, followed by a heating treatment at a temperature equal to or higher than the heat-melting temperature of the hot melt urethane prepolymer (A), thereby causing foaming and curing.

The heat-melting temperature of the hot melt urethane prepolymer (A) is in the range of 80 to 120° C., for example.

In the foaming agent composition (B), it is preferable that the (b1) to (b3), preferably as well as the (b4), are stirred and mixed, and the (b1) and (b2), preferably as well as the (b4), are uniformly dispersed in the polyol (b3). In addition, before being mixed with the hot melt urethane prepolymer (A), the foaming agent composition (B) may be warmed at a temperature of 25 to 100° C., for example.

As a method for mixing the foaming agent composition (B) with the heat-melted hot melt urethane prepolymer (A), a method that uses a mixer or the like, such as a batch stirrer, a static mixer, a rotor stator, or a two-component mixer, can be mentioned, for example.

Incidentally, when the hot melt urethane prepolymer (A) and the foaming agent composition (B) are mixed, bubbles may be involved during mixing, or isocyanate groups in the hot melt urethane prepolymer (A) may react with part of the urea (b2) to produce carbon dioxide.

As a method for applying the mixture of (A) and (B) to a substrate, a method that uses an applicator, a roll coater, a spray coater, a T-die coater, a knife coater, a comma coater, or the like can be mentioned, for example.

Incidentally, the applied mixture of (A) and (B) foams upon the post-heating described below and increases in thickness. Accordingly, the thickness at the time of application is preferably determined considering the foaming degree described below and the like.

As the substrate, for example, it is possible to use a nonwoven fabric, a woven fabric, or a knitted fabric made of polyester fibers, nylon fibers, acrylic fibers, polyurethane fibers, acetate fibers, rayon fibers, polylactic acid fibers, cotton, hemp, silk, wool, mixed fibers thereof, or the like; a release paper; etc. Further, as the substrate, it is possible to use a wood substrate such as a plate, MDF (medium density fiberboard), or a particle board; a metal substrate such as aluminum or iron; a plastic substrate such as a polycarbonate substrate, a cycloolefin resin substrate, an acrylic resin substrate, a silicon resin substrate, an epoxy resin substrate, a fluororesin substrate, a polystyrene resin substrate, a polyester resin substrate, a polysulfone resin substrate, a polyarylate resin substrate, a polyvinyl chloride resin substrate, a polyvinylidene chloride substrate, an amorphous polyolefin resin substrate, a polyimide resin substrate, an alicyclic polyimide resin substrate, a cellulose resin substrate, a TAC (triacetylcellulose) substrate, a COP (cycloolefin polymer) substrate, a PC (polycarbonate) substrate, a PBT (polybutylene terephthalate) substrate, a modified PPE (polyphenylene ether) substrate, a PEN (polyethylene naphthalate) substrate, a PET (polyethylene terephthalate) substrate, or a polylactic acid polymer substrate; a glass plate; etc. In addition, the substrate may have a complex-shape part, such as a groove part, an R-shaped part, or an inverted R-shaped part.

After the mixture of (A) and (B) is applied onto the substrate, the above substrate may be further attached onto the applied surface.

Next, the laminate having the substrate and the mixture of (A) and (B) is subjected to a heating treatment at a temperature equal to or higher than the heat-melting temperature of the hot melt urethane prepolymer (A), thereby promoting the foaming and curing of the foaming agent composition (B) (particularly the (b1)). The heating treatment at this time is performed in the range of 100 to 150° C., for example. In terms of ease of suppressing adverse effects on the substrate or deterioration in the properties of the foamed and cured product, the temperature is more preferably in the range of 110 to 140° C. The time of the heating treatment is preferably 1 to 10 minutes, for example.

After the heating treatment, as necessary, post-curing may be performed at a temperature of 20 to 80° C. for 1 to 7 days, for example.

The thickness of the foamed and cured product layer of the moisture-curable hot melt composition obtained by the above method is in the range of 10 to 500 μm, for example. Within this range, an excellent foamed state can be formed. The thickness may be suitably determined according to the intended use of the foamed and cured product. In addition, in the present invention, an excellent foamed state can be maintained even in a thin film, whose thickness is less than 100 μm, for example, preferably in the range of 20 to 90 μm, more preferably in the range of 30 to 80 μm, and particularly preferably in the range of 40 to 70 μm.

The bubbles remaining in the foamed and cured product are mainly formed by foaming upon the post-heating of the (b1). The foaming degree of the foamed and cured product is preferably 1.2 or more, more preferably in the range of 1.5 to 3, and still more preferably in the range of 1.7 to 2.8. Incidentally, the foaming degree of the foamed and cured product refers to a value calculated from the ratio (V₂/V₁) between the volume of the mixture of (A) and (B) before foaming (V₁) and the volume after foaming (V₂).

As described above, in the moisture-curable hot melt urethane composition of the present invention, a specific heat-decomposable foaming agent is used. As a result, a foamed and cured product with excellent texture can be obtained, an excellent foamed state can be maintained even in a thin film, and, even after foaming, no deterioration is caused in the mechanical properties of the foamed and cured product. In addition, foaming can be caused without the influence of water. Thus, even in the case where the moisture-curable hot melt urethane composition is once cooled and solidified from a melted state, or even during moisture curing, by performing a heating treatment again, the foaming of the heat-decomposable foaming agent can be promoted.

Next, the synthetic leather of the present invention will be described.

The synthetic leather of the present invention includes a base fabric (i), an intermediate layer (ii), and a surface skin layer (iii), and the intermediate layer (ii) is a foamed and cured product of the above moisture-curable hot melt urethane composition.

As the base fabric (i), for example, it is possible to use a nonwoven fabric, a woven fabric, or a knitted fabric made of polyester fibers, polyethylene fibers, nylon fibers, acrylic fibers, polyurethane fibers, acetate fibers, rayon fibers, polylactic acid fibers, cotton, hemp, silk, wool, glass fibers, carbon fibers, mixed fibers thereof, or the like, etc.

The surface skin layer (iii) may be formed from a known material by a known method. For example, it is possible to use a solvent-based urethane resin, a water-based urethane resin, a silicone resin, a polypropylene resin, a polyester resin, or the like. As the surface skin layer (iii), in the case where soft texture, bending resistance, and hydrolysis resistance are emphasized, it is preferable to use a polyether-based urethane resin. Among them, in the case where low-temperature flexibility is particularly emphasized, it is more preferable to use a urethane resin obtained using polytetramethylene glycol as a raw material. In addition, in the case where soft texture, heat resistance, and hydrolysis resistance are emphasized, it is preferable to use a urethane resin obtained using a polycarbonate polyol as a raw material. In addition, in order to reduce DMF for environmental responsibility, it is preferable to use a water-based urethane resin.

On the surface skin layer (iii), as necessary, a topcoat layer (iv) may be provided for the purpose of improving the scratch resistance and the like. The topcoat layer (iv) may be formed from a known material by a known method, and the same materials as those usable for forming the surface skin layer (iii) may be used.

Next, the method for producing the synthetic leather of the present invention will be described.

As methods for producing the synthetic leather of the present invention, the following methods can be mentioned, for example:

(a) a method in which the hot melt urethane prepolymer (A) is heat-melted and then mixed with a foaming agent composition (B) containing N,N′-dinitrosopentamethylenetetramine (b1), urea (b2), and a polyol (b3) to give a moisture-curable hot melt urethane composition, the moisture-curable hot melt composition is applied onto a surface skin layer (iii) formed on a release paper, followed by a heating treatment at a temperature equal to or higher than the heat-melting temperature of the hot melt urethane prepolymer (A) to form an intermediate layer (ii), and subsequently a base fabric (i) is attached onto the intermediate layer (ii), thereby producing a synthetic leather;

(b) a method in which the hot melt urethane prepolymer (A) is heat-melted and then mixed with a foaming agent composition (B) containing N,N′-dinitrosopentamethylenetetramine (b1), urea (b2), and a polyol (b3) to give a moisture-curable hot melt urethane composition, the moisture-curable hot melt composition is applied onto a surface skin layer (iii) formed on a release paper, and subsequently a base fabric (i) is attached onto the applied layer of the moisture-curable hot melt composition, followed by a heating treatment at a temperature equal to or higher than the heat-melting temperature of the hot melt urethane prepolymer (A) to form an intermediate layer (ii), thereby producing a synthetic leather;

(c) a method in which the hot melt urethane prepolymer (A) is heat-melted and then mixed with a foaming agent composition (B) containing N,N′-dinitrosopentamethylenetetramine (b1), urea (b2), and a polyol (b3) to give a moisture-curable hot melt urethane composition, the moisture-curable hot melt composition is applied onto a base fabric (i), followed by a heating treatment at a temperature equal to or higher than the heat-melting temperature of the hot melt urethane prepolymer (A) to form an intermediate layer (ii), and subsequently a surface skin layer (iii) side formed on a release paper is attached to the intermediate layer (ii), thereby producing a synthetic leather;

(d) a method in which the hot melt urethane prepolymer (A) is heat-melted and then mixed with a foaming agent composition (B) containing N,N′-dinitrosopentamethylenetetramine (b1), urea (b2), and a polyol (b3) to give a moisture-curable hot melt urethane composition, the moisture-curable hot melt composition is applied onto a base fabric (i), and subsequently a surface skin layer (iii) side formed on a release paper is attached onto the applied layer of the moisture-curable hot melt composition, followed by a heating treatment at a temperature equal to or higher than the heat-melting temperature of the hot melt urethane prepolymer (A) to form an intermediate layer (ii), thereby producing a synthetic leather; etc.

Among them, in terms of the foaming (production) stability of the intermediate layer (ii) and ease of uniformizing the thickness of the intermediate layer (ii), it is preferable to use the production method (b).

The heat-melting temperature of the hot melt urethane prepolymer (A) is in the range of 80 to 120° C., for example.

In the foaming agent composition (B), it is preferable that the (b1) to (b3), preferably as well as the (b4), are stirred and mixed, and the (b1) and (b2), preferably as well as (b4), are uniformly dispersed in the polyol (b3) using a batch stirrer, a static mixer, a rotor stator, a two-roll mill, a three-roll mill, a bead mill, or the like. In addition, before being mixed with the hot melt urethane prepolymer (A), the foaming agent composition (B) may be warmed at a temperature of 25 to 100° C., for example.

As a method for applying the moisture-curable hot melt urethane composition onto the surface skin layer (iii) formed on a release paper, a method that uses an applicator, a roll coater, a spray coater, a T-die coater, a knife coater, a comma coater, or the like can be mentioned, for example.

Incidentally, the applied moisture-curable hot melt urethane composition foams upon the post-heating described below and increases in thickness. Accordingly, the thickness at the time of application is preferably determined considering the foaming degree described below and the like.

Next, a heating treatment is performed at a temperature equal to or higher than the heat-melting temperature of the hot melt urethane prepolymer (A), thereby promoting the foaming and curing of the foaming agent composition (B) (particularly the (b1)), whereby an intermediate layer (ii) is produced. The heating treatment at this time is performed in the range of 100 to 150° C., for example. In terms of ease of suppressing adverse effects on the substrate or deterioration in the properties of the synthetic leather due to the thermal history, the temperature is more preferably in the range of 110 to 140° C. The time of the heating treatment is preferably 1 to 10 minutes, for example.

After the intermediate layer (ii) is formed, the base fabric (i) is attached onto the intermediate layer (ii), whereby a synthetic leather can be obtained. However, before and/or after attaching the base fabric (i), for the purpose of aging the intermediate layer (ii), post-curing may be performed at a temperature of 20 to 80° C. for 1 to 7 days, for example.

The thickness of the intermediate layer (ii) of the synthetic leather obtained by the above method is in the range of 10 to 500 μm, for example. Within this range, an excellent foamed state can be formed. The thickness may be suitably determined according to the intended use of the synthetic leather of the present invention. In addition, in the present invention, an excellent foamed state can be maintained even in a thin film, whose thickness is less than 100 μm, for example, preferably in the range of 20 to 90 μm, more preferably in the range of 30 to 80 μm, and particularly preferably in the range of 50 to 70 μm.

The bubbles remaining in the intermediate layer (ii) are mainly formed by foaming upon the post-heating of the (b1). The foaming degree of the intermediate layer (ii) is preferably 1.2 or more, more preferably in the range of 1.5 to 3, and still more preferably in the range of 1.7 to 2.8. Incidentally, the foaming degree of the intermediate layer (ii) refers to a value calculated from the ratio (V₂/V₁) between the volume of the moisture-curable hot melt urethane composition before foaming (V₁) and the volume after foaming (V₂).

EXAMPLES

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

[Synthesis Example 1] Synthesis of Hot Melt Urethane Prepolymer (A-1)

Subsequently, 25 parts by mass of 4,4′-diphenylmethane diisocyanate was added, then the temperature was raised to 100° C., and the mixture was allowed to react for about 3 hours until the isocyanate group content became constant, thereby giving a hot melt urethane prepolymer having an isocyanate group (A-1) having an NCO % of 3.3.

[Synthesis Example 2] Synthesis of Hot Melt Urethane Prepolymer (A-2)

In a reaction vessel equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 70 parts by mass of polyoxytetramethylene glycol (number average molecular weight: 2,000) and 30 parts by mass of a polyester polyol (2) (reaction product of a 6-mol propylene oxide adduct of bisphenol A and sebacic acid, number average molecular weight: 2,000) were charged, and dehydrated under reduced-pressure conditions until the moisture content reached 0.05 mass % or less. Subsequently, 25 parts by mass of 4,4′-diphenylmethane diisocyanate was added, then the temperature was raised to 100° C., and the mixture was allowed to react for about 3 hours until the isocyanate group content became constant, thereby giving a hot melt urethane prepolymer having an isocyanate group (A-2) having an NCO % of 3.3.

[Synthesis Example 3] Synthesis of Hot Melt Urethane Prepolymer (A-3)

In a reaction vessel equipped with a thermometer, a stirrer, an inert gas feed port, and a reflux condenser, 70 parts by mass of a polycarbonate polyol (“NIPPORAN 980R” manufactured by Nippon Polyurethane Industry Co., Ltd., number average molecular weight: 2,600) and 30 parts by weight of a polyester polyol (1) (reaction product of 1,6-hexanediol and adipic acid, number average molecular weight: 2,000) were charged, and dehydrated under reduced-pressure conditions until the moisture content reached 0.05 mass % or less. Subsequently, 25 parts by mass of 4,4′-diphenylmethane diisocyanate was added, then the temperature was raised to 100° C., and the mixture was allowed to react for about 3 hours until the isocyanate group content became constant, thereby giving a hot melt urethane prepolymer having an isocyanate group (A-3) having an NCO % of 3.2.

[Synthesis Example 4] Synthesis of Hot Melt Urethane Prepolymer (A-4)

In a reaction vessel equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 70 parts by mass of a polycarbonate polyol (“NIPPORAN 980R” manufactured by Nippon Polyurethane Industry Co., Ltd., number average molecular weight: 2,600) and 30 parts by mass of a polyester polyol (2) (reaction product of a 6-mol propylene oxide adduct of bisphenol A and sebacic acid, number average molecular weight: 2,000) were charged, and dehydrated under reduced-pressure conditions until the moisture content reached 0.05 mass % or less.

[Synthesis Example 5] Synthesis of Hot Melt Urethane Prepolymer (A-5)

Subsequently, 18 parts by mass of xylylene diisocyanate was added, then the temperature was raised to 100° C., and the mixture was allowed to react for about 3 hours until the isocyanate group content became constant, thereby giving a hot melt urethane prepolymer having an isocyanate group (A-5) having an NCO % of 3.2.

[Synthesis Example 6] Synthesis of Hot Melt Urethane Prepolymer (A-6)

Subsequently, 25 parts by mass of xylylene diisocyanate was added, then the temperature was raised to 100° C., and the mixture was allowed to react for about 3 hours until the isocyanate group content became constant, thereby giving a hot melt urethane prepolymer having an isocyanate group (A-6) having an NCO % of 3.2.

[Synthesis Example 7] Synthesis of Hot Melt Urethane Prepolymer (A-7)

In a reaction vessel equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 70 parts by mass of a polycarbonate polyol (“NIPPORAN 980R” manufactured by Nippon Polyurethane Industry Co., Ltd., number average molecular weight: 2,000) and 30 parts by mass of a polyester polyol (2) (reaction product of a 6-mol propylene oxide adduct of bisphenol A and sebacic acid, number average molecular weight: 2,000) were charged, and dehydrated under reduced-pressure conditions until the moisture content reached 0.05 mass % or less.

[Synthesis Example 8] Synthesis of Hot Melt Urethane Prepolymer (A-8)

In a reaction vessel equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 70 parts by mass of a polycarbonate polyol (“NIPPORAN 980R” manufactured by Nippon Polyurethane Industry Co., Ltd., number average molecular weight: 2,000) and 30 parts by weight of a polyester polyol (1) (reaction product of 1,6-hexanediol and adipic acid, number average molecular weight: 2,000) were charged, and dehydrated under reduced-pressure conditions until the moisture content reached 0.05 mass % or less.

Example 1

100 parts by mass of the hot melt urethane prepolymer (A-1) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B-1) obtained by mixing 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000), 2.5 parts by mass of N,N′-dinitrosopentamethylenetetramine, and 2.5 parts by mass of urea was mixed with the melted hot melt urethane prepolymer (A-1) and stirred using a batch stirrer.

The mixture was then immediately applied onto a release paper (“ED100K” manufactured by Lintec Corporation) to provide a thickness of 30 μm, and a polyethylene film having a thickness of 20 μm was attached onto the applied surface. They were subjected to a heating treatment at 120° C. for 5 minutes and then allowed to stand for 3 days under the conditions of a temperature of 23° C. and a relative humidity of 65%, thereby giving a foamed and cured product having a thickness of 45 μm.

Examples 2 and 3

Foamed and cured products were obtained in the same manner as in Example 1, except that the thickness of the moisture-curable hot melt urethane composition to be applied was changed as shown in Table 1.

Example 4

100 parts by mass of the hot melt urethane prepolymer (A-1) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B-2) obtained by mixing 5 parts by mass of polyoxypropylene triol (“T-700” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 700), 2.5 parts by mass of N,N′-dinitrosopentamethylenetetramine, and 2.5 parts by mass of urea was mixed with the melted hot melt urethane prepolymer (A-1) and stirred using a batch stirrer.

Example 5

100 parts by mass of the hot melt urethane prepolymer (A-2) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B-1) obtained by mixing 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000), 2.5 parts by mass of N,N′-dinitrosopentamethylenetetramine, and 2.5 parts by mass of urea was mixed with the melted hot melt urethane prepolymer (A-2) and stirred using a batch stirrer.

Example 6

A foamed and cured product was obtained in the same manner as in Example 5, except that the thickness of the moisture-curable hot melt urethane composition to be applied was changed as shown in Table 2.

Example 7

100 parts by mass of the hot melt urethane prepolymer (A-3) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B-1) obtained by mixing 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000), 2.5 parts by mass of N,N′-dinitrosopentamethylenetetramine, and 2.5 parts by mass of urea was mixed with the melted hot melt urethane prepolymer (A-3) and stirred using a batch stirrer.

Example 8

100 parts by mass of the hot melt urethane prepolymer (A-4) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B-1) obtained by mixing 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000), 2.5 parts by mass of N,N′-dinitrosopentamethylenetetramine, and 2.5 parts by mass of urea was mixed with the melted hot melt urethane prepolymer (A-4) and stirred using a batch stirrer.

Example 9

100 parts by mass of the hot melt urethane prepolymer (A-5) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B-1) obtained by mixing 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000), 2.5 parts by mass of N,N′-dinitrosopentamethylenetetramine, and 2.5 parts by mass of urea was mixed with the melted hot melt urethane prepolymer (A-5) and stirred using a batch stirrer.

Example 10

100 parts by mass of the hot melt urethane prepolymer (A-6) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B-1) obtained by mixing 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000), 2.5 parts by mass of N,N′-dinitrosopentamethylenetetramine, and 2.5 parts by mass of urea was mixed with the melted hot melt urethane prepolymer (A-6) and stirred using a batch stirrer.

Example 11

100 parts by mass of the hot melt urethane prepolymer (A-1) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B-3) obtained by mixing 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000), 1.5 parts by mass of N,N′-dinitrosopentamethylenetetramine, and 3.5 parts by mass of urea was mixed with the melted hot melt urethane prepolymer (A-1) and stirred using a batch stirrer.

Example 12

100 parts by mass of the hot melt urethane prepolymer (A-1) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B-4) obtained by mixing 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000), 3.5 parts by mass of N,N′-dinitrosopentamethylenetetramine, and 1.5 parts by mass of urea was mixed with the melted hot melt urethane prepolymer (A-1) and stirred using a batch stirrer.

Example 13

100 parts by mass of the hot melt urethane prepolymer (A-1) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B-5) obtained by mixing 10 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000), 5 parts by mass of N,N′-dinitrosopentamethylenetetramine, and 5 parts by mass of urea was mixed with the melted hot melt urethane prepolymer (A-1) and stirred using a batch stirrer.

Example 14

The mixture was then immediately applied onto a release paper (“ED100K” manufactured by Lintec Corporation) to provide a thickness of 30 μm, and a polyethylene film having a thickness of 20 μm was attached onto the applied surface. They were subjected to a heating treatment at 140° C. for 5 minutes and then allowed to stand for 3 days under the conditions of a temperature of 23° C. and a relative humidity of 65%, thereby giving a foamed and cured product having a thickness of 55 μm.

Example 15

100 parts by mass of the hot melt urethane prepolymer (A-1) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B-6) obtained by mixing 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000), 2.5 parts by mass of N,N′-dinitrosopentamethylenetetramine, 2.5 parts by mass of urea, and 0.5 parts by mass of boric acid was mixed with the melted hot melt urethane prepolymer (A-1) and stirred using a batch stirrer.

Examples 16 and 17

Example 18

100 parts by mass of the hot melt urethane prepolymer (A-1) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B-7) obtained by mixing 5 parts by mass of polyoxypropylene triol (“T-700” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 700), 2.5 parts by mass of N,N′-dinitrosopentamethylenetetramine, 2.5 parts by mass of urea, and 0.5 parts by mass of boric acid was mixed with the melted hot melt urethane prepolymer (A-1) and stirred using a batch stirrer.

Example 19

100 parts by mass of the hot melt urethane prepolymer (A-2) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B-6) obtained by mixing 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000), 2.5 parts by mass of N,N′-dinitrosopentamethylenetetramine, 2.5 parts by mass of urea, and 0.5 parts by mass of boric acid was mixed with the melted hot melt urethane prepolymer (A-2) and stirred using a batch stirrer.

Example 20

Example 21

100 parts by mass of the hot melt urethane prepolymer (A-3) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B-6) obtained by mixing 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000), 2.5 parts by mass of N,N′-dinitrosopentamethylenetetramine, 2.5 parts by mass of urea, and 0.5 parts by mass of boric acid was mixed with the melted hot melt urethane prepolymer (A-3) and stirred using a batch stirrer.

Example 22

100 parts by mass of the hot melt urethane prepolymer (A-4) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B-6) obtained by mixing 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000), 2.5 parts by mass of N,N′-dinitrosopentamethylenetetramine, 2.5 parts by mass of urea, and 0.5 parts by mass of boric acid was mixed with the melted hot melt urethane prepolymer (A-4) and stirred using a batch stirrer.

Example 23

100 parts by mass of the hot melt urethane prepolymer (A-5) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B-6) obtained by mixing 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000), 2.5 parts by mass of N,N′-dinitrosopentamethylenetetramine, 2.5 parts by mass of urea, and 0.5 parts by mass of boric acid was mixed with the melted hot melt urethane prepolymer (A-5) and stirred using a batch stirrer.

Example 24

100 parts by mass of the hot melt urethane prepolymer (A-6) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B-6) obtained by mixing 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000), 2.5 parts by mass of N,N′-dinitrosopentamethylenetetramine, 2.5 parts by mass of urea, and 0.5 parts by mass of boric acid was mixed with the melted hot melt urethane prepolymer (A-6) and stirred using a batch stirrer.

Example 25

100 parts by mass of the hot melt urethane prepolymer (A-1) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B-8) obtained by mixing 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000), 1.5 parts by mass of N,N′-dinitrosopentamethylenetetramine, 3.5 parts by mass of urea, and 0.5 parts by mass of boric acid was mixed with the melted hot melt urethane prepolymer (A-1) and stirred using a batch stirrer.

Example 26

100 parts by mass of the hot melt urethane prepolymer (A-1) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B-9) obtained by mixing 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000), 3.5 parts by mass of N,N′-dinitrosopentamethylenetetramine, 1.5 parts by mass of urea, and 0.5 parts by mass of boric acid was mixed with the melted hot melt urethane prepolymer (A-1) and stirred using a batch stirrer.

Example 27

100 parts by mass of the hot melt urethane prepolymer (A-1) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B-10) obtained by mixing 10 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000), 5 parts by mass of N,N′-dinitrosopentamethylenetetramine, 5 parts by mass of urea, and 1.0 parts by mass of boric acid was mixed with the melted hot melt urethane prepolymer (A-1) and stirred using a batch stirrer.

Example 28

The mixture was then immediately applied onto a release paper (“ED100K” manufactured by Lintec Corporation) to provide a thickness of 30 μm, and a polyethylene film having a thickness of 20 μm was attached onto the applied surface. They were subjected to a heating treatment at 140° C. for 5 minutes and then allowed to stand for 3 days under the conditions of a temperature of 23° C. and a relative humidity of 65%, thereby giving a foamed and cured product having a thickness of 60 μm.

Example 29

100 parts by mass of the hot melt urethane prepolymer (A-1) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B-11) obtained by mixing 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000), 2.5 parts by mass of N,N′-dinitrosopentamethylenetetramine, 2.5 parts by mass of urea, and 2.5 parts by mass of boric acid was mixed with the melted hot melt urethane prepolymer (A-1) and stirred using a batch stirrer.

Comparative Example 1

100 parts by mass of the hot melt urethane prepolymer (A-1) was heated to 100° C. to be thereby melted. Subsequently, a water-foamed composition (X-1) obtained by mixing 0.5 parts by mass of ethylene glycol, 0.1 parts by mass of N,N-dimethylcyclohexylamine, and 0.1 parts of water was mixed with the melted hot melt urethane prepolymer (A-1) and stirred using a batch stirrer.

The mixture was then immediately applied onto a release paper (“ED100K” manufactured by Lintec Corporation) to provide a thickness of 30 μm, and a polyethylene film having a thickness of 20 μm was attached onto the applied surface. They were then allowed to stand for 5 days under the conditions of a temperature of 23° C. and a relative humidity of 65%, thereby giving a foamed and cured product having a thickness of 32 μm.

Comparative Example 2

100 parts by mass of the hot melt urethane prepolymer (A-1) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B′-1) obtained by mixing 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000) and 2 parts by mass of N,N′-dinitrosopentamethylenetetramine was mixed with the melted hot melt urethane prepolymer (A-1) and stirred using a batch stirrer.

Comparative Example 3

100 parts by mass of the hot melt urethane prepolymer (A-1) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B′-2) obtained by mixing 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000) and 2 parts by mass of urea was mixed with the melted hot melt urethane prepolymer (A-1) and stirred using a batch stirrer.

Comparative Example 4

100 parts by mass of the hot melt urethane prepolymer (A-1) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B′-3) obtained by mixing 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000), 2.5 parts by mass of azodicarbonamide, and 2.5 parts by mass of urea was mixed with the melted hot melt urethane prepolymer (A-1) and stirred using a batch stirrer.

Comparative Example 5

100 parts by mass of the hot melt urethane prepolymer (A-1) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B′-4) obtained by mixing 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000), 2.5 parts by mass of 4,4′-oxybis(benzenesulfonyl hydrazide), and 2.5 parts by mass of urea was mixed with the melted hot melt urethane prepolymer (A-1) and stirred using a batch stirrer.

Comparative Example 6

100 parts by mass of the hot melt urethane prepolymer (A-1) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B′-5) obtained by mixing 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000), 2.5 parts by mass of sodium hydrogen carbonate, and 2.5 parts by mass of urea was mixed with the melted hot melt urethane prepolymer (A-1) and stirred using a batch stirrer.

[Measurement Method for Melt Viscosity]

The hot melt urethane prepolymers (A-1) to (A-8) were each melted at 100° C. for 1 hour, then 1 ml was sampled, and the melt viscosity at 100° C. was measured using a cone-plate viscometer (Digital Cone Viscometer “CV-1S, RT Type” manufactured by MST Engineering Co., Ltd., 40P cone, rotor speed: 50 rpm).

[Measurement Method for Foaming Degree of Foamed and Cured Product]

In the examples and comparative examples, the volume (V₁) immediately after adding the melted hot melt urethane prepolymer (A) and the foaming agent composition (B) or water-foamed composition (X) and the volume (V₂) of the cured product after foaming were measured, and the foaming degree was calculated from their ratio (V₂/V₁).

[Evaluation Method for Foamed State]

The foamed and cured products and cured products obtained in the examples and comparative examples were observed using a scanning electron microscope “SU3500” manufactured by Hitachi High-Technologies Corporation (magnification: 200) and evaluated as follows.

“A”: Excellent foamed state can be confirmed.

“B”: Excellent foamed state cannot be confirmed.

[Evaluation Method for Texture]

The textures of the foamed and cured products and cured products obtained in the examples and comparative examples were evaluated based on the tactile impression.

“A”: Extremely high flexibility, and no asperities are confirmed.

“B”: Good flexibility, and no asperities are confirmed.

“C”: Hard, or asperities are confirmed.

[Evaluation Method for Mechanical Properties]

The foamed and cured products and cured products obtained in the examples and comparative examples were each cut into a specimen 100 mm in length and 5 mm in width. Each end of the specimen was held in a chuck. Using a tensile tester “Autograph AG-I” (manufactured by Shimadzu Corporation Co., Ltd.), the specimen was pulled in an atmosphere having a temperature of 23° C. and a humidity of 60% at a crosshead speed of 300 mm/min, and the 100% modulus (MPa), 200% modulus (MPa), stress at break (MPa), and elongation at break (%) of the specimen were measured. The gauge length at this time was 20 mm, and the initial distance between chucks was 20 mm. Incidentally, specimens that were not able to be pulled and evaluated are indicated with “-”.

TABLE 1

Example 1
Example 2
Example 3
Example 4
Example 5
Example 6
Example 7

Urethane

(A-1)
(A-1)
(A-1)
(A-1)
(A-2)
(A-2)
(A-3)

prepolymer
Polyol (a1)

having
PTMG (parts by mass)
70
70
70
70
70
70

isocyanate
PC (parts by mass)

70

group
PEs (1) (parts by mass)
30
30
30
30

30

(A)
PEs (2) (parts by mass)

30
30

Polyisocyanate (a2)

MDI (parts by mass)
25
25
25
25
25
25
25

NCO % (%)
3.3
3.3
3.3
3.3
3.3
3.3
3.2

Melting temperature (° C.)
100
100
100
100
100
100
100

Melt viscosity at 100° C. (mPa · s)
2000
2000
2000
2000
3000
3000
2500

Foaming

(B-1)
(B-1)
(B-1)
(B-2)
(B-1)
(B-1)
(B-1)

agent
N,N′-Dinitrosopentamethylenetetramine
2.5
2.5
2.5
2.5
2.5
2.5
2.5

composition
(b1) (parts by mass)

(B)
Urea (b2) (parts by mass)
2.5
2.5
2.5
2.5
2.5
2.5
2.5

Polyol (b3) (parts by mass)

MN3050 (parts by mass)
5
5
5

5
5
5

T700 (parts by mass)

5

Mass ratio (b1)/(b2)
50/50
50/50
50/50
50/50
50/50
50/50
50/50

Amount of foaming agent composition used per 100
10
10
10
10
10
10
10

parts by mass of (A)(parts by mass)

Post-heating temperature (° C.)
120
120
120
120
120
120
120

Thickness of mixture applied (μm)
30
50
100
30
30
50
30

Thickness of foamed and cured product (μm)
45
100
200
50
50
110
45

Foaming degree of foamed and cured product
1.8
2
2.2
1.7
1.8
2
1.8

Evaluation of foamed state
A
A
A
A
A
A
A

Evaluation of texture
B
B
B
B
B
B
B

Evaluation of mechanical properties

100% Modulus (MPa)
0.4
0.6
1.2
0.5
0.3
0.5
0.8

200% Modulus (MPa)
0.8
1.2
2.4
0.9
0.6
0.8
1.2

Stress at break (MPa)
3.0
4.0
8.0
3.5
2.8
3.0
3.8

Elongation at break (%)
600
580
550
620
680
650
600

Stress at break (MPa)
2.2
2.4
3.5
2.4
2.1
2.5
2.1

Elongation at break (%)
670
680
750
690
670
700
650

TABLE 2

Example 8
Example 9
Example 10
Example 11
Example 12
Example 13
Example 14

Urethane

(A-5)
(A-5)
(A-6)
(A-1)
(A-1)
(A-1)
(A-1)

prepolymer
Polyol (a1)

having
PTMG (parts by mass)

70

70
70
70
70

isocyanate
PC (parts by mass)
70

70

group
PEs (1) (parts by mass)

30

30
30
30
30

(A)
PEs (2) (parts by mass)
30

30

Polyisocyanate (a2)

MDI (parts by mass)
25

25
25
25
25

XDI (parts by mass)

18
18

NCO % (%)
3.2
3.2
3.2
3.3
3.3
3.3
3.3

Melting temperature (° C.)
100
100
100
100
100
100
100

Melt viscosity at 100° C. (mPa · s)
3500
2200
2300
2000
2000
2000
2000

Foaming

(B-1)
(B-1)
(B-1)
(B-3)
(B-4)
(B-5)
(B-1)

agent
N,N′-Dinitrosopentamethylenetetramine
2.5
2.5
2.5
1.5
3.5
5
2.5

composition
(b1) (parts by mass)

(B)
Urea (b2) (parts by mass)
2.5
2.5
2.5
3.5
1.5
5
2.5

Polyol (b3) (parts by mass)

MN3050 (parts by mass)
5
5
5
5
5
10
5

Mass ratio (b1)/(b2)
50/50
50/50
50/50
30/70
70/30
50/50
50/50

Amount of foaming agent composition used per 100
10
10
10
10
10
20
10

parts by mass of (A)(parts by mass)

Post-heating temperature (° C.)
120
120
120
120
120
120
140

Thickness of mixture applied (μm)
30
30
30
30
30
30
30

Thickness of foamed and cured product (μm)
45
45
50
50
45
50
55

Foaming degree of foamed and cured product
1.9
1.8
1.7
1.7
2.2
2
2.5

Evaluation of foamed state
A
A
A
A
A
A
A

Evaluation of texture
B
B
B
B
B
B
B

Evaluation of mechanical properties

100% Modulus (MPa)
0.7
0.5
0.6
0.8
0.4
1.8
0.3

200% Modulus (MPa)
1.0
1.0
1.2
1.5
0.8
3.5
0.7

Stress at break (MPa)
4.0
3.0
3.5
4.5
3.5
8.0
3.0

Elongation at break (%)
670
580
600
550
680
620
620

TABLE 3

Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-

ple 15
ple 16
ple 17
ple 18
ple 19
ple 20
ple 21

Urethane

(A-1)
(A-1)
(A-1)
(A-1)
(A-2)
(A-2)
(A-3)

prepolymer
Polyol (a1)

having
PTMG (parts by mass)
70
70
70
70
70
70

isocyanate
PC (parts by mass)

70

group
PEs (1) (parts by mass)
30
30
30
30

30

(A)
PEs (2) (parts by mass)

30
30

Polyisocyanate (a2)

MDI (parts by mass)
25
25
25
25
25
25
25

NCO % (%)
3.3
3.3
3.3
3.3
3.3
3.3
3.2

Melting temperature (° C.)
100
100
100
100
100
100
100

Melt viscosity at 100° C. (mPa · s)
2000
2000
2000
2000
3000
3000
2500

Foaming

(B-6)
(B-6)
(B-6)
(B-7)
(B-6)
(B-6)
(B-6)

agent
N,N′-Dinitrosopentamethylenetetramine
2.5
2.5
2.5
2.5
2.5
2.5
2.5

composition
(b1) (parts by mass)

(B)
Urea (b2) (parts by mass)
2.5
2.5
2.5
2.5
2.5
2.5
2.5

Boric acid (b4) (parts by mass)
0.5
0.5
0.5
0.5
0.5
0.5
0.5

Polyol (b3) (parts by mass)

MN3050 (parts by mass)
5
5
5

5
5
5

T700 (parts by mass)

5

Mass ratio (b1)/(b2)
50/50
50/50
50/50
50/50
50/50
50/50
50/50

Amount of (b4) used per 100 parts by
20
20
20
20
20
20
20

mass of (b2)

Amount of foaming agent composition used per 100
10.5
10.5
10.5
10.5
10.5
10.5
10.5

parts by mass of (A)(parts by mass)

Post-heating temperature (° C.)
120
120
120
120
120
120
120

Thickness of mixture applied (μm)
30
50
100
30
30
50
30

Thickness of foamed and cured product (μm)
50
120
220
55
55
130
50

Foaming degree of foamed and cured product
2.1
2.4
2.6
2.1
2.2
2.3
2.2

Evaluation of foamed state
A
A
A
A
A
A
A

Evaluation of texture
A
A
A
A
A
A
A

Evaluation of mechanical properties

100% Modulus (MPa)
0.2
0.3
0.4
0.3
0.2
0.3
0.4

200% Modulus (MPa)
0.5
0.6
0.8
0.6
0.4
0.6
0.8

Stress at break (MPa)
2.2
2.4
3.5
2.4
2.1
2.5
2.1

Elongation at break (%)
670
680
750
690
670
700
650

TABLE 4

Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-

ple 22
ple 23
ple 24
ple 25
ple 26
ple 27
ple 28

Urethane

(A-4)
(A-5)
(A-6)
(A-1)
(A-1)
(A-1)
(A-1)

prepolymer
Polyol (a1)

having
PTMG (parts by mass)

70

70
70
70
70

isocyanate
PC (parts by mass)
70

70

group
PEs (1) (parts by mass)

30

30
30
30
30

(A)
PEs (2) (parts by mass)
30

30

Polyisocyanate (a2)

MDI (parts by mass)
25

25
25
25
25

XDI (parts by mass)

18
18

NCO % (%)
3.2
3.2
3.2
3.3
3.3
3.3
3.3

Melting temperature (° C.)
100
100
100
100
100
100
100

Melt viscosity at 100° C. (mPa · s)
3500
2200
2300
2000
2000
2000
2000

Foaming

(B-6)
(B-6)
(B-6)
(B-8)
(B-9)
(B-10)
(B-6)

agent
N,N′-Dinitrosopentamethylenetetramine
2.5
2.5
2.5
1.5
3.5
5
2.5

composition
(b1) (parts by mass)

(B)
Urea (b2) (parts by mass)
2.5
2.5
2.5
3.5
1.5
5
2.5

Boric acid (b4) (parts by mass)
0.5
0.5
0.5
0.5
0.5
1
0.5

Polyol (b3) (parts by mass)

MN3050 (parts by mass)
5
5
5
5
5
10
5

Mass ratio (b1)/(b2)
50/50
50/50
50/50
30/70
70/30
50/50
50/50

Amount of (b4) used per 100 parts by
20
20
20
14
33
20
20

mass of (b2)

Amount of foaming agent composition used per 100
10.5
10.5
10.5
10.5
10.5
21
10.5

parts by mass of (A)(parts by mass)

Post-heating temperature (° C.)
120
120
120
120
120
120
140

Thickness of mixture applied (μm)
30
30
30
30
30
30
30

Thickness of foamed and cured product (μm)
50
50
52
55
48
58
60

Foaming degree of foamed and cured product
2.0
2.0
2.1
2.4
2.0
2.8
2.5

Evaluation of foamed state
A
A
A
A
A
A
A

Evaluation of texture
A
A
A
A
A
A
A

Evaluation of mechanical properties

100% Modulus (MPa)
0.2
0.3
0.3
0.3
0.2
0.2
0.2

200% Modulus (MPa)
0.5
0.6
0.6
0.7
0.4
0.5
0.4

Stress at break (MPa)
2.2
2.3
2.5
3.0
2.1
2.4
2.1

Elongation at break (%)
660
630
620
600
720
680
690

TABLE 5

Compar-
Compar-
Compar-
Compar-
Compar-
Compar-

ative
ative
ative
ative
ative
ative

Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-

ple 29
ple 1
ple 2
ple 3
ple 4
ple 5
ple 6

Urethane

(A-1)
(A-1)

(A-1)

(A-1)

(A-1)
(A-1)

(A-1)

prepolymer
Polyol (a1)

having
PTMG (parts by mass)
70
70
70
70
70
70
70

isocyanate
PEs (1) (parts by mass)
30
30
30
30
30
30
30

group
Polyisocyanate (a2)

(A)
MDI (parts by mass)
25
25
25
25
25
25
25

NCO % (%)
3.3
3.3
3.3
3.3
3.3
3.3
3.3

Melting temperature (° C.)
100
100
100
100
100
100
100

Melt viscosity at 100° C. (mPa · s)
2000
2000
2000
2000
2000
2000
2000

Foaming

(B-11)

(B′-1)
(B′-2)
(B′-3)
(B′-4)
(B′-5)

agent
N,N′-Dinitrosopentamethylenetetramine
2.5

2.5

composition
(b1) (parts by mass)

(B)
Urea (b2) (parts by mass)
2.5

2.5
2.5
2.5
2.5

Boric acid (b4) (parts by mass)
2.5

Polyol (b3) (parts by mass)

MN3050 (parts by mass)
5

5
5
5
5
5

Mass ratio (b1)/(b2)
50/50
—
100/0
0/100
0/100
0/100
0/100

Amount of (b4) used per 100 parts by
100

mass of (b2)

Other

(X-1)

foaming
ethylene glycol (parts by mass)

0.5

agent
N,N-dimethylcyclohexylamine (parts by mass)

0.1

compositions
Water (parts by mass)

0.1

Azodicarbonamide (parts by mass)

2.5

4,4′-Oxybis(benzenesulfonyl hydrazide) (parts

2.5

by mass)

Sodium hydrogen carbonate (parts by mass)

2.5

Amount of foaming agent composition used per 100
12.5
0.7
7.5
7.5
10
10
10

parts by mass of (A)(parts by mass)

Post-heating temperature (° C.)
120
—
120
120
120
120
120

Thickness of mixture applied (μm)
30
30
30
30
30
30
30

Thickness of foamed and cured product (μm)
60
32
40
35
32
33
32

Foaming degree of foamed and cured product
2.8
1.2
1.6
1.1
1.2
1.1
1.0

Evaluation of foamed state
A
B
B
B
B
B
B

Evaluation of texture
A
C
C
C
C
C
C

Evaluation of mechanical properties

100% Modulus (MPa)
0.2
0.5
0.5
0.1
0.5
0.5
0.1

200% Modulus (MPa)
0.5
0.8
0.8
—
0.9
0.8
—

Stress at break (MPa)
2.5
2.0
1.8
0.6
2.0
1.9
0.4

Elongation at break (%)
680
600
350
180
550
600
150

The abbreviations in Tables 1 to 5 will be described.

“PTMG”: Polyoxytetramethylene glycol (number average molecular weight: 2,000)

“PC”: Polycarbonate polyol (“NIPPORAN 980R” manufactured by Nippon Polyurethane Industry Co., Ltd., number average molecular weight: 2,000)

“PEs (1)”: Polyester polyol (1) (reaction product of 1,6-hexanediol and adipic acid, number average molecular weight: 2,000)

“PEs (2)”: Polyester polyol (2) (reaction product of a 6-mol propylene oxide adduct of bisphenol A and sebacic acid, number average molecular weight: 2,000)

“MDI”: 4,4′-Diphenylmethane diisocyanate

“XDI”: Xylylene diisocyanate

“MN3050”: Polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000)

“T700”: Polyoxypropylene triol (“T-700” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 700)

As shown in Tables 1 and 2, it turned out that in the moisture-curable hot melt urethane composition of the present invention, an excellent foamed state can be maintained even in a thin film, and a foamed and cured product with excellent texture can be obtained. In addition, no deterioration was confirmed in the mechanical properties.

In particular, it turned out that in the case where boric acid is used in the foaming agent composition (B) (Examples 15 to 29), a foamed and cured product with excellent texture can be obtained.

Meanwhile, in Comparative Example 1, foaming by a water foaming method was studied. As a result, as shown in FIG. 3, bubbles caused by water foaming did not remain, and there remained only bubbles involved during mixing the components (A) and (B), indicating that it was not possible to maintain an excellent foamed state. In addition, due to this, the texture of the foamed and cured product was not excellent either.

Comparative Example 2 is an example in which urea (b2) was not used in the foaming agent composition (B). As a result, as shown in FIG. 4, foaming was uncontrollable, and bubbles came in contact with the substrate. Accordingly, asperities were felt on the surface of the obtained foamed and cured product, and the texture was poor. In addition, deterioration was confirmed in the elongation at break, etc.

Comparative Example 3 is an example in which N,N′-dinitrosopentamethylenetetramine (b1) was not used in the foaming agent composition (B). As a result, there remained only bubbles involved during mixing the components (A) and (B). The texture of the obtained foamed and cured product was not excellent either.

Comparative Examples 4 to 6 are modes in which N,N′-dinitrosopentamethylenetetramine (b1) was replaced with other heat-decomposable foaming agents. As a result, as shown in FIG. 5, it was confirmed that the generated bubbles collapsed, and it was not possible to maintain an excellent foamed state in a thin film. In addition, due to this, the texture of the foamed and cured product was not excellent either.

[Preparation Example 1] Preparation of Surface Skin Layer (iii-1)

100 parts by mass of a solvent-based polyether urethane resin “CRISVON NB-130” manufactured by DIC Corporation was mixed with 20 parts by mass of a pigment “DILAC BLACK L-6001” manufactured by DIC Corporation and 40 parts by mass of an equal-amount mixture of methyl ethyl ketone/N,N-dimethylformamide, and applied using a comma coater onto a release paper to a wet coating weight of 100 g/m². The applied mixture was then dried at 70° C. for 2 minutes and at 120° C. for 2 minutes, thereby preparing a surface skin layer (iii-1) having a thickness of 30 μm.

[Preparation Example 2] Preparation of Surface Skin Layer (iii-2)

100 parts by mass of a water-based polyether urethane resin “HYDRAN WLS-230” manufactured by DIC Corporation was mixed with 10 parts by mass of a pigment “DILAC BLACK HS-9533” manufactured by DIC Corporation, and applied using a comma coater onto a release paper to a wet coating weight of 100 g/m². The applied mixture was then dried at 70° C. for 2 minutes and at 120° C. for 2 minutes, thereby preparing a surface skin layer (iii-2) having a thickness of 30 μm.

Example 30

100 parts by mass of the hot melt urethane prepolymer (A-1) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B-1) obtained by mixing and stirring 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000), 2.5 parts by mass of N,N′-dinitrosopentamethylenetetramine, and 2.5 parts by mass of urea was stirred with the melted hot melt urethane prepolymer (A-1) using a two-component mixing and stirring machine, thereby giving a moisture-curable hot melt urethane composition.

Subsequently, the obtained moisture-curable hot melt urethane composition was applied onto the surface skin layer (iii-1) using a comma coater to provide a thickness of 30 μm, followed by a heating treatment at 120° C. for 5 minutes, and a nonwoven fabric was attached thereto. They were then allowed to stand for 3 days under conditions of a temperature of 23° C. and a relative humidity of 65%, thereby giving a synthetic leather including a 45-μm-thick intermediate layer (ii).

Examples 31 to 40

Synthetic leathers were obtained in the same manner as in Example 30, except that the hot melt urethane prepolymer (A), the foaming agent composition (B), the heat-melting temperature of the hot melt urethane prepolymer (A), the surface skin layer (iii), the thickness of the moisture-curable hot melt urethane composition to be applied, and the temperature of post-heating were changed as shown in Tables 6 and 7.

Example 41

100 parts by mass of the hot melt urethane prepolymer (A-1) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B-6) obtained by mixing and stirring 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000), 2.5 parts by mass of N,N′-dinitrosopentamethylenetetramine, 2.5 parts by mass of urea, and 0.5 parts by mass of boric acid was stirred with the melted hot melt urethane prepolymer (A-1) using a two-component mixing and stirring machine, thereby giving a moisture-curable hot melt urethane composition.

Examples 42 to 56

Synthetic leathers were obtained in the same manner as in Example 41, except that the hot melt urethane prepolymer (A), the foaming agent composition (B), the heat-melting temperature of the hot melt urethane prepolymer (A), the surface skin layer (iii), the thickness of the moisture-curable hot melt urethane composition to be applied, and the temperature of post-heating were changed as shown in Tables 7 to 9.

Example 57

100 parts by mass of the hot melt urethane prepolymer (A-3) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B-1) obtained by mixing and stirring 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000), 2.5 parts by mass of N,N′-dinitrosopentamethylenetetramine, and 2.5 parts by mass of urea was stirred with the melted hot melt urethane prepolymer (A-3) using a two-component mixing and stirring machine, thereby giving a moisture-curable hot melt urethane composition.

Examples 58 to 67

Synthetic leathers were obtained in the same manner as in Example 57, except that the hot melt urethane prepolymer (A), the foaming agent composition (B), the heat-melting temperature of the hot melt urethane prepolymer (A), the surface skin layer (iii), the thickness of the moisture-curable hot melt urethane composition to be applied, and the temperature of post-heating were changed as shown in Tables 10 and 11.

Example 68

100 parts by mass of the hot melt urethane prepolymer (A-3) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B-6) obtained by mixing and stirring 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000), 2.5 parts by mass of N,N′-dinitrosopentamethylenetetramine, 2.5 parts by mass of urea, and 0.5 parts by mass of boric acid was stirred with the melted hot melt urethane prepolymer (A-3) using a two-component mixing and stirring machine, thereby giving a moisture-curable hot melt urethane composition.

Examples 69 to 83

Synthetic leathers were obtained in the same manner as in Example 68, except that the hot melt urethane prepolymer (A), the foaming agent composition (B), the heat-melting temperature of the hot melt urethane prepolymer (A), the surface skin layer (iii), the thickness of the moisture-curable hot melt urethane composition to be applied, and the temperature of post-heating were changed as shown in Tables 11 to 13.

Comparative Example 7

The composition was then applied onto the surface skin layer (iii-1) using a comma coater to provide a thickness of 30 μm, and a nonwoven fabric was attached to the applied surface. They were then allowed to stand for 5 days under conditions of a temperature of 23° C. and a relative humidity of 65%, thereby giving a synthetic leather including a 32-μm-thick intermediate layer (ii).

Comparative Example 8

100 parts by mass of the hot melt urethane prepolymer (A-1) was heated to 100° C. to be thereby melted. Subsequently, a foaming agent composition (B′-1) obtained by mixing 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 3,000) and 2.5 parts by mass of N,N′-dinitrosopentamethylenetetramine was stirred with the melted hot melt urethane prepolymer (A-1) using a two-component mixing and stirring machine, thereby giving a moisture-curable hot melt urethane composition.

Comparative Examples 9 to 12

Synthetic leathers were obtained in the same manner as in Comparative Example 2, except that the hot melt urethane prepolymer (A), the foaming agent composition (B), the heat-melting temperature of the hot melt urethane prepolymer (A), the surface skin layer (iii), the thickness of the moisture-curable hot melt urethane composition to be applied, and the temperature of post-heating were changed as shown in Table 14.

[Measurement Method for Foaming Degree of Intermediate Layer (ii)]

In the examples and comparative examples, the volume immediately after adding the melted hot melt urethane prepolymer (A) and the foaming agent composition (B) or water-foamed composition (X) (V₁) and the volume of the cured product after foaming (V₂) were measured, and the foaming degree was calculated from their ratio (V₂/V₁).

[Evaluation Method for Foamed State]

The intermediate layers (ii) of the synthetic leathers obtained in the examples and comparative examples were observed using a scanning electron microscope “SU3500” manufactured by Hitachi High-Technologies Corporation (magnification: 200) and evaluated as follows.

“A”: Excellent foamed state can be confirmed.

“B”: Excellent foamed state cannot be confirmed.

[Evaluation Method for Texture]

The textures of the synthetic leathers obtained in the examples and comparative examples were evaluated based on the tactile impression.

“A”: Extremely high flexibility, and no asperities are confirmed.

“B”: Good flexibility, and no asperities are confirmed.

“C”: Hard, or asperities are confirmed.

[Evaluation Method for Hydrolysis Resistance]

Onto the surface skin layers of the synthetic leathers obtained in Examples 30 to 56 and Comparative Examples 7 to 12, a hot melt fabric tape was bonded at 130° C. over 5 seconds. Then, using TENSILON (TENSILON Universal Tester “RTC-1210A” manufactured by Orientec Co., Ltd.), the peel strength was measured by crosshead measurement at 200 mm/min and defined as peel strength in normal state.

Next, the synthetic leathers obtained in the examples and comparative examples were allowed to stand for 5 weeks under conditions of a temperature of 70° C. and a humidity of 95%, and then the peel strength was measured in the same manner and defined as peel strength after hydrolysis resistance test.

[Evaluation Method for Bending Resistance]

Using “MIT Bending Tester” manufactured by Toyo Seiki Seisaku-sho, Ltd., the synthetic leathers obtained in Examples 30 to 56 and Comparative Examples 7 to 12 were subjected to a 300,000-times bending test at room temperature (23° C.) and also to a 100,000-times bending test at low temperature (−10° C.). When the surface did not crack, such a sample is indicated with “T”, while in the case where cracking occurred during the test, the number of bends at that time is shown in the tables.

Next, the synthetic leathers obtained in the examples and comparative examples were allowed to stand for 5 weeks under conditions of a temperature of 70° C. and a humidity of 95%. The bending resistance test was then performed in the same manner, and the bending resistance after hydrolysis resistance test was also evaluated in the same manner.

[Evaluation Method for Durability]

Onto the surface skin layers of the synthetic leathers obtained in Examples 57 to 83, a hot melt fabric tape was bonded at 130° C. over 5 seconds. Then, using TENSILON (TENSILON Universal Tester “RTC-1210A” manufactured by Orientec Co., Ltd.), the peel strength was measured by crosshead measurement at 200 mm/min and defined as peel strength in normal state.

Further, the synthetic leathers obtained in the examples and comparative examples were allowed to stand for 500 hours under conditions of a temperature of 120° C., and then the peel strength was measured in the same manner and defined as peel strength after heat resistance test.

TABLE 6

Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-

ple 30
ple 31
ple 32
ple 33
ple 34
ple 35
ple 36

Base fabric (i)
Nonwoven
Nonwoven
Nonwoven
Nonwoven
Nonwoven
Nonwoven
Nonwoven

fabric
fabric
fabric
fabric
fabric
fabric
fabric

Surface skin layer (iii)
(iii-1)
(iii-1)
(iii-1)
(iii-1)
(iii-1)
(iii-1)
(iii-1)

Intermediate layer (ii)

Urethane

(A-1)
(A-1)
(A-1)
(A-1)
(A-2)
(A-2)
(A-5)

prepolymer
Polytetramethylene glycol (a1)

having
PTMG (parts by mass)
70
70
70
70
70
70
70

isocyanate
Other polyols

group
PEs (1) (parts by mass)
30
30
30
30

30

(A)
PEs (2) (parts by mass)

30
30

Polyisocyanate (a2)

MDI (parts by mass)
25
25
25
25
25
25

XDI (parts by mass)

18

NCO % (%)
3.3
3.3
3.3
3.3
3.3
3.3
3.2

Melting temperature (° C.)
100
100
100
100
100
100
100

Melt viscosity at 100° C. (mPa · s)
2000
2000
2000
2000
3000
3000
2200

Foaming

(B-1)
(B-1)
(B-1)
(B-2)
(B-1)
(B-1)
(B-1)

agent
N,N′-Dinitrosopentamethylenetetramine
2.5
2.5
2.5
2.5
2.5
2.5
2.5

composition
(b1) (parts by mass)

(B)
Urea (b2) (parts by mass)
2.5
2.5
2.5
2.5
2.5
2.5
2.5

Polyol (b3) (parts by mass)

MN3050 (parts by mass)
5
5
5

5
5
5

T700 (parts by mass)

5

Mass ratio (b1)/(b2)
50/50
50/50
50/50
50/50
50/50
50/50
50/50

Amount of foaming agent composition used per 100
10
10
10
10
10
10
10

parts by mass of (A) (parts by mass)

Post-heating temperature (° C.)
120
120
120
120
120
120
120

Thickness of mixture applied (μm)
30
50
100
30
30
50
30

Thickness of foamed and cured product (μm)
45
100
200
50
50
110
45

Foaming degree of foamed and cured product
1.8
2
2.2
1.7
1.8
2
1.8

Evaluation of foamed state
A
A
A
A
A
A
A

Texture
B
B
B
B
B
B
B

Hydrolysis resistance Peel strength (N/cm): Normal state
19.6
31.4
27.4
19.6
21.6
30.6
19.6

: After hydrolysis resistance test
18.8
30.6
26.7
19.2
21.2
30.6
19.6

Bending resistance:

Normal state: −10° C.: 100,000 times
T
T
T
T
T
T
T

23° C. * 300,000 times
T
T
T
T
T
T
T

After hydrolysis resistance test: −10° C.: 100,000 times
T
T
T
T
T
T
T

23° C. * 300,000 times
T
T
T
T
T
T
T

TABLE 7

Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-

ple 37
ple 38
ple 39
ple 40
ple 41
ple 42
ple 43

Base fabric (i)
Nonwoven
Nonwoven
Nonwoven
Nonwoven
Nonwoven
Nonwoven
Nonwoven

fabric
fabric
fabric
fabric
fabric
fabric
fabric

Surface skin layer (iii)
(iii-1)
(iii-1)
(iii-1)
(iii-1)
(iii-1)
(iii-1)
(iii-1)

Intermediate layer (ii)

Urethane

(A-1)
(A-1)
(A-1)
(A-1)
(A-1)
(A-1)
(A-1)

prepolymer
Polytetramethylene glycol (a1)

having
PTMG (parts by mass)
70
70
70
70
70
70
70

isocyanate
Other polyols

group
PEs (1) (parts by mass)
30
30
30
30
30
30
30

(A)
PEs (2) (parts by mass)

Polyisocyanate (a2)

MDI (parts by mass)
25
25
25
25
25
25
25

XDI (parts by mass)

NCO % (%)
3.3
3.3
3.3
3.3
3.3
3.3
3.3

Melting temperature (° C.)
100
100
100
100
100
100
100

Melt viscosity at 100° C. (mPa · s)
2000
2000
2000
2000
2000
2000
2000

Foaming

(B-3)
(B-4)
(B-5)
(B-1)
(B-6)
(B-6)
(B-6)

agent
N,N′-Dinitrosopentamethylenetetramine
1.5
3.5
5
2.5
2.5
2.5
2.5

composition
(b1) (parts by mass)

(B)
Urea (b2) (parts by mass)
3.5
1.5
5
2.5
2.5
2.5
2.5

Boric acid (b4) (parts by mass)

0.5
0.5
0.5

Polyol (b3) (parts by mass)

MN3050 (parts by mass)
5
5
10
5
5
5
5

Mass ratio (b1)/(b2)
30/70
70/30
50/50
50/50
50/50
50/50
50/50

Amount of foaming agent composition used per 100
10
10
20
10
10.5
10.5
10.5

parts by mass of (A) (parts by mass)

Post-heating temperature (° C.)
120
120
120
140
120
120
120

Thickness of mixture applied (μm)
30
30
30
30
30
50
100

Thickness of foamed and cured product (μm)
50
45
50
55
50
120
220

Foaming degree of foamed and cured product
1.7
2.2
2
2.5
2.1
2.4
2.6

Evaluation of foamed state
A
A
A
A
A
A
A

Texture
B
B
B
B
A
A
A

Hydrolysis resistance Peel strength (N/cm): Normal state
23.5
21.6
19.6
17.6
18.8
29.4
26.7

: After hydrolysis resistance test
21.6
21.2
19.6
17.6
18.8
29.0
26.7

Bending resistance:

Normal state: −10° C.: 100,000 times
T
T
T
T
T
T
T

23° C. * 300,000 times
T
T
T
T
T
T
T

After hydrolysis resistance test: −10° C.: 100,000 times
T
T
T
T
T
T
T

23° C. * 300,000 times
T
T
T
T
T
T
T

TABLE 8

Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-

ple 44
ple 45
ple 46
ple 47
ple 48
ple 49
ple 50

Base fabric (i)
Nonwoven
Nonwoven
Nonwoven
Nonwoven
Nonwoven
Nonwoven
Nonwoven

fabric
fabric
fabric
fabric
fabric
fabric
fabric

Surface skin layer (iii)
(iii-1)
(iii-1)
(iii-1)
(iii-1)
(iii-1)
(iii-1)
(iii-1)

Intermediate layer (ii)

Urethane

(A-1)
(A-2)
(A-2)
(A-5)
(A-1)
(A-1)
(A-1)

prepolymer
Polytetramethylene glycol (a1)

having
PTMG (parts by mass)
70
70
70
70
70
70
70

isocyanate
Other polyols

group
PEs (1) (parts by mass)
30

30
30
30
30

(A)
PEs (2) (parts by mass)

30
30

Polyisocyanate (a2)

MDI (parts by mass)
25
25
25

25
25
25

XDI (parts by mass)

18

NCO % (%)
3.3
3.3
3.3
3.2
3.3
3.3
3.3

Melting temperature (° C.)
100
100
100
100
100
100
100

Melt viscosity at 100° C. (mPa · s)
2000
3000
3000
2200
2000
2000
2000

Foaming

(B-7)
(B-6)
(B-6)
(B-6)
(B-8)
(B-9)
(B-10)

agent
N,N′-Dinitrosopentamethylenetetramine
2.5
2.5
2.5
2.5
1.5
3.5
5

composition
(b1) (parts by mass)

(B)
Urea (b2) (parts by mass)
2.5
2.5
2.5
2.5
3.5
1.5
5

Boric acid (b4) (parts by mass)
0.5
0.5
0.5
0.5
0.5
0.5
1

Polyol (b3) (parts by mass)

MN3050 (parts by mass)

5
5
5
5
5
10

T700 (parts by mass)
5

Mass ratio (b1)/(b2)
50/50
50/50
50/50
50/50
30/70
70/30
50/50

Amount of foaming agent composition used per 100
10.5
10.5
10.5
10.5
10.5
10.5
21

parts by mass of (A) (parts by mass)

Post-heating temperature (° C.)
120
120
120
120
120
120
120

Thickness of mixture applied (μm)
30
30
50
30
30
30
30

Thickness of foamed and cured product (μm)
55
55
130
50
55
48
58

Foaming degree of foamed and cured product
2.1
2.2
2.3
2.0
2.4
2.0
2.8

Evaluation of foamed state
A
A
A
A
A
A
A

Texture
A
A
A
A
A
A
A

Hydrolysis resistance Peel strength (N/cm): Normal state
18.8
20.8
29.4
18.8
21.6
19.6
18.8

: After hydrolysis resistance test
18.8
20.8
29.4
18.8
20.8
18.8
18.8

Bending resistance:

Normal state: −10° C.: 100,000 times
T
T
T
T
T
T
T

23° C. * 300,000 times
T
T
T
T
T
T
T

After hydrolysis resistance test: −10° C.: 100,000 times
T
T
T
T
T
T
T

23° C. * 300,000 times
T
T
T
T
T
T
T

TABLE 9

Example 51
Example 52
Example 53
Example 54
Example 55
Example 56

Base fabric (i)
Nonwoven
Nonwoven
Nonwoven
Nonwoven
Nonwoven
Nonwoven

fabric
fabric
fabric
fabric
fabric
fabric

Surface skin layer (iii)
(iii-1)
(iii-2)
(iii-2)
(iii-2)
(iii-2)
(iii-2)

Intermediate layer (ii)

Urethane

(A-1)
(A-1)
(A-1)
(A-1)
(A-1)
(A-2)

prepolymer
Polytetramethylene glycol (a1)

having
PTMG (parts by mass)
70
70
70
70
70
70

isocyanate
Other polyols

group
PEs (1) (parts by mass)
30
30
30
30
30

(A)
PEs (2) (parts by mass)

30

Polyisocyanate (a2)

MD (parts by mass)
25
25
25
25
25
25

NCO % (%)
3.3
3.3
3.3
3.3
3.3
3.3

Melting temperature (° C.)
100
100
100
100
100
100

Melt viscosity at 100° C. (mPa · s)
2000
2000
2000
2000
2000
3000

Foaming

(B-11)
(B-1)
(B-1)
(B-6)
(B-6)
(B-6)

agent
N,N′-Dinitrosopentamethylenetetramine
2.5
2.5
2.5
2.5
2.5
2.5

composition
(b1) (parts by mass)

(B)
Urea (b2) (parts by mass)
2.5
2.5
2.5
2.5
2.5
2.5

Boric acid (b4) (parts by mass)
2.5

0.5
0.5
0.5

Polyol (b3) (parts by mass)

MN3050 (parts by mass)
5
5
5
5
5
5

Mass ratio (b1)/(b2)
50/50
50/50
50/50
50/50
50/50
50/50

Amount of foaming agent composition used per 100
12.5
10
10
10.5
10.5
10.5

parts by mass of (A) (parts by mass)

Post-heating temperature (° C.)
120
120
120
120
120
120

Thickness of mixture applied (μm)
30
30
50
30
50
50

Thickness of foamed and cured product (μm)
60
45
100
50
120
125

Foaming degree of foamed and cured product
2.8
1.5
2.0
1.7
2.4
2.5

Evaluation of foamed state
A
A
A
A
A
A

Texture
A
B
B
A
A
A

Hydrolysis resistance Peel strength (N/cm): Normal state
17.6
19.6
30.6
18.8
29.0
28.2

: After hydrolysis resistance test
17.6
19.2
30.6
18.8
29.0
28.2

Bending resistance:

Normal state: −10° C.: 100,000 times
◯
◯
◯
◯
◯
◯

23° C. * 300,000 times
◯
◯
◯
◯
◯
◯

After hydrolysis resistance test: −10° C.: 100,000 times
◯
◯
◯
◯
◯
◯

23° C. * 300.000 times
◯
◯
◯
◯
◯
◯

TABLE 10

Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-

ple 57
ple 58
ple 59
ple 60
ple 61
ple 62
ple 63

Base fabric (i)
Nonwoven
Nonwoven
Nonwoven
Nonwoven
Nonwoven
Nonwoven
Nonwoven

fabric
fabric
fabric
fabric
fabric
fabric
fabric

Surface skin layer (iii)
(iii-1)
(iii-1)
(iii-1)
(iii-1)
(iii-1)
(iii-1)
(iii-1)

Intermediate layer (ii)

Urethane

(A-3)
(A-3)
(A-3)
(A-3)
(A-7)
(A-7)
(A-8)

prepolymer
Polycarbonate polyol (a1)

having
PC (parts by mass)
70
70
70
70
70
70
70

isocyanate
Other polyols

group
PEs (1) (parts by mass)
30
30
30
30

30

(A)
PEs (2) (parts by mass)

30
30

Polyisocyanate (a2)

MDI (parts by mass)
25
25
25
25
25
25

XDI (parts by mass)

18

NCO % (%)
3.2
3.3
3.3
3.3
3.2
32
3.2

Melting temperature (° C.)
100
100
100
100
100
100
100

Melt viscosity at 100° C. (mPa · s)
2500
2500
2500
2500
2300
2300
2200

Foaming

(B-1)
(B-1)
(B-1)
(B-2)
(B-1)
(B-1)
(B-1)

agent
N,N′-Dinitrosopentamethylenetetramine
2.5
2.5
2.5
2.5
2.5
2.5
2.5

composition
(b1) (parts by mass)

(B)
Urea (b2) (parts by mass)
2.5
2.5
2.5
2.5
2.5
2.5
2.5

Polyol (b3) (parts by mass)

MN3050 (parts by mass)
5
5
5

5
5
5

T700 (parts by mass)

5

Mass ratio (b1)/(b2)
50/50
50/50
50/50
50/50
50/50
50/50
50/50

Amount of foaming agent composition used per 100
10
10
10
10
10
10
10

parts by mass of (A) (parts by mass)

Post-heating temperature (° C.)
120
120
120
120
120
120
120

Thickness of mixture applied (μm)
30
50
100
30
30
50
30

Thickness of foamed and cured product (μm)
45
100
200
50
50
110
45

Foaming degree of foamed and cured product
1.8
2
2.2
1.7
1.8
2
1.8

Evaluation of foamed state
A
A
A
A
A
A
A

Texture
B
B
B
B
B
B
B

Evaluation of Durability Peel strength (N/cm): Normal state
23.5
33.3
27.4
23.5
23.5
31.4
23.5

: After hydrolysis resistance test
23.5
33.3
27.0
23.1
23.5
31.0
23.1

: After heat resistance test
23.5
33.3
26.7
22.7
23.5
31.0
23.1

TABLE 11

Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-

ple 64
ple 65
ple 66
ple 67
ple 68
ple 69
ple 70

Base fabric (i)
Nonwoven
Nonwoven
Nonwoven
Nonwoven
Nonwoven
Nonwoven
Nonwoven

fabric
fabric
fabric
fabric
fabric
fabric
fabric

Surface skin layer (iii)
(iii-1)
(iii-1)
(iii-1)
(iii-1)
(iii-1)
(iii-1)
(iii-1)

Intermediate layer (ii)

Urethane

(A-3)
(A-3)
(A-3)
(A-3)
(A-3)
(A-3)
(A-3)

prepolymer
Polycarbonate polyol (a1)

having
PC (parts by mass)
70
70
70
70
70
70
70

isocyanate
Other polyols

group
PEs (1) (parts by mass)
30
30
30
30
30
30
30

(A)
PEs (2) (parts by mass)

Polyisocyanate (a2)

MDI (parts by mass)
25
25
25
25
25
25
25

XDI (parts by mass)

NCO % (%)
3.3
3.3
3.3
3.3
3.3
3.3
3.3

Melting temperature (° C.)
100
100
100
100
100
100
100

Melt viscosity at 100° C. (mPa · s)
2500
2500
2500
2500
2500
2500
2500

Foaming

(B-3)
(B-4)
(B-5)
(B-1)
(B-6)
(B-6)
(B-6)

agent
N,N′-Dinitrosopentamethylenetetramine
1.5
3.5
5
2.5
2.5
2.5
2.5

composition
(b1) (parts by mass)

(B)
Urea (b2) (parts by mass)
3.5
1.5
5
2.5
2.5
2.5
2.5

Boric acid (b4) (parts by mass)

0.5
0.5
0.5

Polyol (b3) (parts by mass)

MN3050 (parts by mass)
5
5
10
5
5
5
5

Mass ratio (b1)/(b2)
30/70
70/30
50/50
50/50
50/50
50/50
50/50

Amount of foaming agent composition used per 100
10
10
20
10
10.5
10.5
10.5

parts by mass of (A) (parts by mass)

Post-heating temperature (° C.)
120
120
120
140
120
120
120

Thickness of mixture applied (μm)
30
30
30
30
30
50
100

Thickness of foamed and cured product (μm)
50
45
50
55
50
120
220

Foaming degree of foamed and cured product
1.7
2.2
2
2.5
2.1
2.4
2.6

Evaluation of foamed state
A
A
A
A
A
A
A

Texture
B
B
B
B
A
A
A

Evaluation of Durability Peel strength (N/cm): Normal state
31.4
29.4
28.6
27.4
29.4
31.4
29.4

: After hydrolysis resistance test
31.0
29.4
28.2
27.4
29.4
31.4
29.4

: After heat resistance test
31.0
29.4
28.6
27.4
29.4
31.4
29.4

TABLE 12

Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-

ple 71
ple 72
ple 73
ple 74
ple 75
ple 76
ple 77

Base fabric (i)
Nonwoven
Nonwoven
Nonwoven
Nonwoven
Nonwoven
Nonwoven
Nonwoven

fabric
fabric
fabric
fabric
fabric
fabric
fabric

Surface skin layer (iii)
(iii-1)
(iii-1)
(iii-1)
(iii-1)
(iii-1)
(iii-1)
(iii-1)

Intermediate layer (ii)

Urethane

(A-3)
(A-7)
(A-7)
(A-8)
(A-3)
(A-3)
(A-3)

prepolymer
Polycarbonate polyol (a1)

having
PC (parts by mass)
70
70
70
70
70
70
70

isocyanate
Other polyols

group
PEs (1) (parts by mass)
30

30
30
30
30

(A)
PEs (2) (parts by mass)

30
30

Polyisocyanate (a2)

MDI (parts by mass)
25
25
25

25
25
25

XDI (parts by mass)

18

NCO % (%)
3.3
3.3
3.3
3.2
3.3
3.3
3.3

Melting temperature (° C.)
100
100
100
100
100
100
100

Melt viscosity at 100° C. (mPa · s)
2500
2300
2300
2200
2500
2500
2500

Foaming

(B-7)
(B-6)
(B-6)
(B-6)
(B-8)
(B-9)
(B-10)

agent
N,N′-Dinitrosopentamethylenetetramine
2.5
2.5
2.5
2.5
1.5
3.5
5

composition
(b1) (parts by mass)

(B)
Urea (b2) (parts by mass)
2.5
2.5
2.5
2.5
3.5
1.5
5

Boric acid (b4) (parts by mass)
0.5
0.5
0.5
0.5
0.5
0.5
1

Polyol (b3) (parts by mass)

MN3050 (parts by mass)

5
5
5
5
5
10

T700 (parts by mass)
5

Mass ratio (b1)/(b2)
50/50
50/50
50/50
50/50
30/70
70/30
50/50

Amount of foaming agent composition used per 100
10.5
10.5
10.5
10.5
10.5
10.5
21

parts by mass of (A) (parts by mass)

Post-heating temperature (° C.)
120
120
120
120
120
120
120

Thickness of mixture applied (μm)
30
30
50
30
30
30
30

Thickness of foamed and cured product (μm)
55
55
130
50
55
48
58

Foaming degree of foamed and cured product
2.1
2.2
2.3
2.0
2.4
2.0
2.8

Evaluation of foamed state
A
A
A
A
A
A
A

Texture
A
A
A
A
A
A
A

Evaluation of Durability Peel strength (N/cm): Normal state
25.5
27.4
29.4
23.5
26.5
21.2
23.1

: After hydrolysis resistance test
25.5
27.4
29.4
23.5
26.5
21.2
23.1

: After heat resistance test
24.7
27.4
29.4
23.5
26.5
21.2
22.7

TABLE 13

Example 78
Example 79
Example 80
Example 81
Example 82
Example 83

Base fabric (i)
Nonwoven
Nonwoven
Nonwoven
Nonwoven
Nonwoven
Nonwoven

fabric
fabric
fabric
fabric
fabric
fabric

Surface skin layer (iii)
(iii-1)
(iii-2)
(iii-2)
(iii-2)
(iii-2)
(iii-2)

Intermediate layer (ii)

Urethane

(A-3)
(A-3)
(A-3)
(A-3)
(A-3)
(A-7)

prepolymer
Polycarbonate polyol (a1)

having
PC (parts by mass)
70
70
70
70
70
70

isocyanate
Other polyols

group
PEs (1) (parts by mass)
30
30
30
30
30

(A)
PEs (2) (parts by mass)

30

Polyisocyanate (a2)

MDI (parts by mass)
25
25
25
25
25
25

NCO % (%)
3.3
3.3
3.3
3.3
3.3
32

Melting temperature (° C.)
100
100
100
100
100
100

Melt viscosity at 100° C. (mPa · s)
2500
2500
2500
2500
2500
2300

Foaming

(B-11)
(B-1)
(B-1)
(B-6)
(B-6)
(B-6)

agent
N,N′-Dinitrosopentamethylenetetramine
2.5
2.5
2.5
2.5
2.5
2.5

composition
(b1) (parts by mass)

(B)
Urea (b2) (parts by mass)
2.5
2.5
2.5
2.5
2.5
2.5

Boric acid (b4) (parts by mass)
2.5

0.5
0.5
0.5

Polyol (b3) (parts by mass)

MN3050 (parts by mass)
5
5
5
5
5
5

Mass ratio (b1)/(b2)
50/50
50/50
50/50
50/50
50/50
50/50

Other
Ethylene glycol (parts by mass)

foaming
N,N-Dimethylcyclohexylamine (parts by mass)

agent
Water (parts by mass)

compositions

Amount of foaming agent composition used per 100
12.5
0.7
7.5
7.5
10
10

parts by mass of (A) (parts by mass)

Post-heating temperature (° C.)
120
—
120
120
120
120

Thickness of mixture applied (μm)
30
30
30
30
30
30

Thickness of foamed and cured product (μm)
60
32
40
35
32
33

Foaming degree of foamed and cured product
2.8
1.2
1.6
1.1
1.2
1.1

Evaluation of foamed state
A
A
A
A
A
A

Texture
A
B
B
A
A
A

Evaluation of Durability Peel strength (N/cm): Normal state
20.8
21.6
19.6
20.4
18.8
20.0

: After hydrolysis resistance test
20.8
21.2
19.6
20.0
18.8
20.0

: After heat resistance test
20.4
21.2
19.6
19.6
18.8
20.0

TABLE 14

Compar-
Compar-
Compar-
Compar-
Compar-
Compar-

ative
ative
ative
ative
ative
ative

Exam-
Exam-
Exam-
Exam-
Exam-
Exam-

ple 7
ple 8
ple 9
ple 10
ple 11
ple 12

Base fabric (i)
Nonwoven
Nonwoven
Nonwoven
Nonwoven
Nonwoven
Nonwoven

fabric
fabric
fabric
fabric
fabric
fabric

Surface skin layer (iii)
(iii-1)
(iii-1)
(iii-1)
(iii-1)
(iii-1)
(iii-1)

Intermediate layer (ii)

Urethane

(A-1)

(A-1)

(A-1)

(A-1)

(A-1)
(A-1)

prepolymer
Polytetramethylene glycol (a1)

having
PTMG (parts by mass)
70
70
70
70
70
70

isocyanate
Other polyols

group
PEs (1) (parts by mass)
30
30
30
30
30
30

(A)
Polyisocyanate (a2)

MDI (parts by mass)
25
25
25
25
25
25

NCO % (%)
3.3
3.3
3.3
3.3
3.3
3.3

Melting temperature (° C.)
100
100
100
100
100
100

Melt viscosity at 100° C. (mPa · s)
2000
2000
2000
2000
2000
2000

Foaming

(B′-1)
(B′-2)
(B′-3)
(B′-4)
(B′-5)

agent
N,N′-Dinitrosopentamethylenetetramine

2.5

composition
(b1) (parts by mass)

(B)
Urea (b2) (parts by mass)

2.5
2.5
2.5
2.5

Boric acid (b4) (parts by mass)

Polyol (b3) (parts by mass)

MN3050 (parts by mass)

5
5
5
5
5

Mass ratio (b1)/(b2)

100/0
0/100
0/100
0/100
0/100

Other

(X-1)

foaming
Ethylene glycol (parts by mass)
0.5

agent
N,N-Dimethylcyclohexylamine (parts by mass)
0.1

compositions
Water (parts by mass)
0.1

Azodicarbonamide (parts by mass)

2.5

4,4′-Oxybis(benzenesulfonyl hydrazide) (parts

2.5

by mass)

Sodium hydrogen carbonate (parts by mass)

2.5

Amount of foaming agent composition used per 100
0.7
7.5
7.5
7.5
10
10

parts by mass of (A) (parts by mass)

Post-heating temperature (° C.)
—
120
120
120
120
120

Thickness of mixture applied (μm)
30
30
30
30
30
30

Thickness of foamed and cured product (μm)
32
40
35
32
33
32

Foaming degree of foamed and cured product
1.2
1.6
1.1
1.2
1.1
1.0

Evaluation of foamed state
C
B
B
C
C
C

Texture
C
C
C
C
C
C

Hydrolysis resistance Peel strength (N/cm): Normal state
15.7
15.7
14.9
14.9
15.7
11.8

: After hydrolysis resistance test
13.7
13.7
14.9
14.9
15.7
11.8

Bending resistance:

Normal state: −10° C.: 100,000 times
T
T
T
T
T
T

23° C. * 300,000 times
T
T
T
T
T
T

After hydrolysis resistance test: −10° C.: 100,000 times
T
T
T
T
T
T

23° C. * 300,000 times
T
T
T
T
T
T

The synthetic leathers of Examples 30 to 56 are synthetic leathers produced using a hot melt urethane prepolymer in which polyoxytetramethylene glycol was used as a main component of the polyol. It turned out that even in the case where an organic solvent, such as DMF, is not used in the formation of an intermediate layer of a synthetic leather, and the intermediate layer is a thin film, an excellent foamed state can be maintained. In addition, the synthetic leathers of the present invention were excellent in texture, bending resistance, and also hydrolysis resistance.

In addition, the synthetic leathers of Examples 57 to 83 are synthetic leathers produced using a hot melt urethane prepolymer in which a polycarbonate polyol was used as a main component of the polyol. It turned out that even in the case where an organic solvent, such as DMF, is not used in the formation of an intermediate layer of a synthetic leather, and the intermediate layer is a thin film, an excellent foamed state can be maintained. In addition, the synthetic leathers of the present invention were excellent in texture and durability.

Meanwhile, in Comparative Example 7, foaming by a water foaming method was studied. As a result, the foaming degree was low, and it was not possible to maintain an excellent foamed state. This suggests that there remained only bubbles involved during mixing the hot melt urethane prepolymer and the water-foamed composition. In addition, due to this, the texture of the synthetic leather was not excellent either.

Comparative Example 8 is an example in which urea (b2) was not used in the foaming agent composition (B). As a result, foaming was uncontrollable, asperities were felt on the surface of the obtained synthetic leather, and the texture was poor.

Comparative Example 9 is an example in which N,N′-dinitrosopentamethylenetetramine (b1) was not used in the foaming agent composition (B). As a result, the foaming degree was low, suggesting that there remained only bubbles involved during mixing the components (A) and (B). The texture of the obtained synthetic leather was also poor.

Comparative Examples 10 to 12 are modes in which N,N′-dinitrosopentamethylenetetramine (b1) was replaced with other heat-decomposable foaming agents. As a result, the foaming degree was low, and it was not possible to maintain an excellent foamed state in a thin film. In addition, due to this, the textures of the synthetic leathers were not excellent either.

Number	Date	Country
S61-055127	Mar 1986	JP
2003-306523	Oct 2003	JP
2003-306526	Oct 2003	JP
2003277459	Oct 2003	JP
2004-115705	Apr 2004	JP
2009119752	Oct 2009	WO
2014192283	Dec 2014	WO

Moisture curable hot melt urethane composition, method for producing cured foam of same, synthetic leather and method for producing synthetic leather

Information

Patent Number

Date Filed

Date Issued

Inventors

Original Assignees

Examiners

Agents

CPC

Field of Search

CPC

International Classifications

Term Extension

Abstract

Description

Claims

Priority Claims (3)

PCT Information

US Referenced Citations (1)

Foreign Referenced Citations (7)

Non-Patent Literature Citations (2)

Related Publications (1)

Number	Date	Country	Kind
2015-172935	Sep 2015	JP	national
2015-221298	Nov 2015	JP	national
JP2015-221299	Nov 2015	JP	national

Entry
Translation of JP 2003-277459, Mizoguchi, Oct. 2, 2003. (Year: 2003).
Search Report issued in corresponding International Patent Application No. PCT/JP2016/067218, dated Sep. 6, 2016.