JP2003246830A - Solvent-free, moisture-curable hot-melt urethane resin composition excellent in durability, foam, and sheet structure using the same - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To provide a solventless moisture-curable hot-melt urethane resin composition capable of obtaining a high-performance porous layer having both excellent adhesiveness and durability (particularly hydrolysis resistance and heat resistance); There are provided a foam using the same, a sheet structure having a foam layer on a base material, and a sheet structure in which a foam layer and a leather-like film layer are integrated on the foam layer on the base material. SOLUTION: A softening point of a prepolymer (A) having a polycarbonate polyol as an essential component in a polyol component constituting a hot melt urethane prepolymer (A) [hereinafter referred to as a prepolymer (A)] is 30 to 16.
In a heat-melted state, a prepolymer (A) containing an isocyanate group-terminated urethane prepolymer in the range of 0 ° C. and an alkoxysilyl group-terminated urethane prepolymer,
A resin composition comprising an amine-based catalyst (B) and water (C), which is characterized in that a foam is formed after water foaming by mixing an inert gas in some cases.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel solvent-free, moisture-curable hot-melt urethane resin composition having excellent durability (particularly hydrolysis resistance and heat resistance), which is useful, and a foam thereof. Relates to a sheet structure using. More specifically, in addition to synthetic leather and artificial leather, adhesives, adhesives, sealing agents, paints, coating agents, films,
The present invention relates to a solventless moisture-curable hot-melt urethane resin composition used for a wide range of applications such as a sheet, a heat insulating material, a sound absorbing material, and a cushioning material, a foam, and a sheet structure using the same.

[0002]

2. Description of the Related Art Polyurethane resins have hitherto been widely used for artificial leather and synthetic leather. In the broad sense, artificial leather or synthetic leather refers to a sheet-like material obtained by combining a polyurethane resin composition with a non-woven fabric, a woven fabric, a knitted fabric, or the like, but is generally classified as follows. Has been done.

That is, "artificial leather" refers to a sheet-like material in which a polyurethane resin composition is filled or laminated in a non-woven fabric, and its production method is generally dimethylformamide (hereinafter referred to as "polyurethane resin composition"). , DMF) is impregnated or coated with a non-woven fabric, and the polyurethane resin is coagulated into a porous state in a water coagulation bath or a coagulation bath consisting of a mixed solution of DMF and water. A method of passing through a drying step, a so-called wet processing method is adopted.

If necessary, the surface of the sheet-like material thus obtained may be made smooth by laminating or coating the surface of the sheet-like material, or the surface of the sheet-like material may be buffed. By doing so, the method of doing with a nubuck or suede tone is also used.

On the other hand, the "synthetic leather" is generally classified into dry synthetic leather and wet synthetic leather.
A sheet-shaped product in which a polyurethane resin composition is laminated is referred to. As a method of manufacturing dry synthetic leather, generally,
First, a polyurethane resin solution for the skin is mixed with a pigment, a solvent, an additive and the like, coated on a release paper and dried to obtain a polyurethane resin for the skin. Next, a two-component polyurethane resin and an isocyanate are applied as an adhesive to the above-prepared polyurethane resin for the skin, and a raised fabric is pressure-bonded before drying and then dried and aged. As a method for producing wet synthetic leather, generally, a DMF solution of a polyurethane resin composition is impregnated or coated on a woven fabric or a knitted fabric, which is formed by a water coagulation bath or a DMF-water mixed solution. In the coagulation bath, after the polyurethane resin is coagulated into a porous form, it is obtained by a method of undergoing a washing step and a drying step.
The so-called wet processing method is mainly adopted.

Further, if necessary, the surface of the sheet-like material thus obtained is subjected to laminating or coating to make it smooth so that the sheet-like material can be made smooth. By buffing the surface of, the method of making it nubuck or suede is also used.

Since a solvent type urethane resin is used in these processing methods, it is indispensable to dry the solvent and extract the solvent during the processing process. There are various problems such as the energy cost required to evaporate the solvent, and the demand for the shift from solvent-based resins to solvent-free resins and processing methods has recently increased.

[0008] In order to meet the above requirements, a water-based method has been studied as a solvent-free method, but its practical use is limited due to poor water resistance and durability. Also,
The use of a solvent-free liquid crosslinked resin is also a solvent-free method, but since the expression of the cohesive force depends on the crosslinking, there is a problem that it is difficult to adjust the expression of the cohesive force during processing such as coating and laminating. For example, if heating is used to accelerate cross-linking and increase the development of cohesive force in order to increase productivity during processing, the time that can be processed such as coating and laminating becomes too narrow, which tends to hinder production. If the temperature at the time of processing is lowered in order to extend the range of processing time, there is a fear that the cross-linking becomes too slow, the expression of cohesive force is delayed, and the productivity is lowered, which makes it difficult to apply to synthetic leather processing.

Further, "reactive hot melt", which is used as an adhesive or a coating material by heating and melting a solid reactive resin at room temperature, is well known, but artificial leather and synthetic leather used for automobiles and furniture applications are well known. When used for the foam layer of
Excellent durability (particularly hydrolysis resistance and heat resistance) was required.

Further, "solventless moisture-curable (reactive) hot melt", which is used for adhesives and coating materials by heating and melting a solid reactive resin at room temperature, is well known. Heretofore, as an example of foaming a reactive hot melt, a method of introducing an inert gas into a reactive hot melt in a molten state under pressure has been disclosed (JP-A-3-6281). It has the drawback that it will not foam unless it is pressurized and released to ambient pressure.

Further, in the reactive hot melt composition, adhesion and durability (especially hydrolysis resistance and heat resistance)
There has been a demand for the development of a composition having excellent properties such as. Therefore, first, the inventors of the present invention filed Japanese Patent Application 2001-344.
In 706, it was found that it is possible to improve the hydrolysis resistance, but it was studied to impart more excellent heat resistance.

[0012]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a solventless moisture-curable hot-melt polyurethane resin composition, a foam, a sheet structure having a foam layer, and a foam layer and leather for the foam layer. When used in a sheet structure that integrates such film layers, a high-performance porous layer with excellent adhesion and durability (especially hydrolysis resistance and heat resistance) based on moisture curing reaction is obtained. Solvent-free moisture-curable hot-melt urethane resin composition, foam obtained using the same, sheet structure having foam layer on substrate, foam layer on substrate and leather-like material on the foam layer To provide a sheet structure in which the film layers of (1) are integrated.

[0013]

Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the above problems, and as a result, construct a hot melt urethane prepolymer (A) [hereinafter referred to as prepolymer (A)]. In the polyol component, a prepolymer (A) containing a polycarbonate polyol as an essential component has a softening point in the range of 30 to 160 ° C., and a prepolymer containing an alkoxysilyl group-terminated urethane prepolymer ( A) in a molten state by heating, an amine-based catalyst (B), and water (C),
In some cases, after foaming with water by mixing with an inert gas, a foam is formed and cooled and solidified, and further when cross-linking cured, or when a foam layer is formed by coating on a substrate to form a foam layer, cooling solidification and further cross-linking curing. When applied by further forming a foamed layer between the leather-like film layer and the base material and similarly solidifying by cooling and further curing by crosslinking, excellent adhesiveness and durability based on moisture curing reaction It was found that a high-performance foam having both properties (in particular, hydrolysis resistance and heat resistance), and a sheet structure and a leather-like sheet structure having such a foam layer can be obtained, and the present invention has been completed. It was

That is, according to the present invention, an isocyanate group terminal obtained by reacting a polyol component and a polyisocyanate component,
And a solventless moisture-curable hot melt urethane resin composition comprising an alkoxysilyl group-terminated hot melt urethane prepolymer (A), an amine catalyst (B), and water (C), which is a polyol of the prepolymer (A). The present invention provides a solventless moisture-curable hot-melt urethane resin composition, characterized in that a polycarbonate polyol is used as an essential component.

Further, the present invention provides a foam characterized in that the solventless moisture-curable hot-melt urethane resin composition is foamed with water and then cured.

The present invention also provides a foam characterized in that the solventless moisture-curable hot-melt urethane resin composition is mixed with an inert gas in advance, foamed with water, and then cured. To do.

The present invention also provides a substrate and the solventless moisture-curable hot melt urethane resin composition on the substrate.
The present invention provides a sheet structure having a foamed layer which is foamed with water and then cured.

The present invention also provides a substrate and the solventless moisture-curable hot melt urethane resin composition on the substrate,
It is intended to provide a sheet structure characterized in that it has a foamed layer which has been mixed with an inert gas in advance, foamed with water and then cured.

The present invention also provides a substrate and the solventless moisture-curable hot melt urethane resin composition on the substrate.
It is intended to provide a sheet structure comprising a foamed layer which is water-foamed and then cured, and a leather-like film layer which is integrated with the foamed layer.

The present invention also provides a substrate and the solventless moisture-curable hot melt urethane resin composition on the substrate,
It is intended to provide a sheet structure characterized in that an inert gas is mixed in advance, water is foamed, and then the foamed layer is cured and a leather-like film layer is integrated with the foamed layer.

Further, the present invention is characterized by having a leather-like film and a foam layer formed by water-foaming the solventless moisture-curable hot-melt urethane resin composition on the film and then curing the same. A sheet structure is provided.

In the present invention, a leather-like film and the solventless moisture-curable hot-melt urethane resin composition on the film are mixed with an inert gas in advance, water-foamed, and then cured. Provided is a sheet structure having a foam layer.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The necessary items for carrying out the present invention will be described below.

First, a solventless moisture curable hot melt urethane resin composition comprising a hot melt urethane prepolymer (A) obtained by reacting a polyol component and a polyisocyanate component, an amine catalyst (B), and water (C). Will be described.

The prepolymer (A) constituting the solvent-free, moisture-curable hot-melt urethane resin composition excellent in durability of the present invention is obtained by reacting a polyol component and an isocyanate component. Polycarbonate polyol is used as an essential component.

The number average molecular weight of the polycarbonate polyol used in the present invention is not particularly limited, but it is usually preferably in the range of 650 to 10,000.

The content of the polycarbonate polyol in the polyol component of the prepolymer (A) used in the present invention is preferably 20% by weight or more, more preferably 40% by weight or more. Within such a range, a foam having excellent hydrolysis resistance and heat resistance, and a sheet structure using the foam can be obtained.

The softening point of the prepolymer (A) is preferably in the range of 30 to 160 ° C, more preferably 40 to 100 ° C. When the softening point is in this range, a stable and uniform foam without unevenness can be obtained, and the cooling and solidifying time can be optimized, which is preferable.

Further, in the present invention, the prepolymer (A)
May be used in combination with a polyol component other than the polycarbonate polyol, and the types of the polyol component and the isocyanate component used in combination are not particularly limited.

The method of adjusting the softening point of the prepolymer (A) used in the present invention is not particularly limited, and for example,
Adjustment method by molecular weight (molar ratio of polyol component and polyisocyanate component, use of high molecular weight polyol, use of high molecular polymer, etc.), adjustment method by crystal of ethylene chain of polyester polyol, aromatic of polyol component and polyisocyanate component There are a method of adjusting the structure of the ring, a method of adjusting the amount of urethane bonds, and the like.

Examples of the polyol component other than the polycarbonate that can be used in the present invention include polyester-based polyols, polyether-based polyols, and mixtures or copolymers thereof. Furthermore, acrylic polyols, polyolefin polyols, castor oil polyols and the like can be mentioned.

Examples of polyester polyols usable in the present invention include ethylene glycol and 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, EO or PO adduct of bisphenol A, etc. One or more diols of succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, hexahydroisophthalic acid, etc. Examples thereof include a condensate with one or more dicarboxylic acids. Other examples include ring-opening polymers such as γ-butyrolactone and ε-caprolactone which use the above-mentioned glycol component as an initiator. In the present invention, E
O means ethylene oxide and PO means propylene oxide.

The polyether type polyols usable in the present invention include, for example, 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-
Glycol components such as 1,4-dimethanol, polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane and pentaerythritol, or ethylene oxide, propylene oxide, butylene oxide and styrene oxide starting from the polyester polyol. Or a ring-opening polymer of two or more thereof. Further, ring-opening addition polymers such as γ-butyrolactone and ε-caprolactone to these polyether diols can be mentioned.

Further, known low molecular weight polyols can also be used, for example, 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, EO or PO adduct of bisphenol A, and one or more diols.

The polyisocyanate component used in the present invention is not particularly limited, but for example, phenylene diisocyanate, tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, Examples thereof include aromatic diisocyanates such as naphthalene diisocyanate, and hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, and other aliphatic or alicyclic diisocyanates. Among these, it is preferable to use diphenylmethane diisocyanate (MDI), which has a low vapor pressure at the time of heating, considering that it is used as a hot-melt resin to be used by melting.

The prepolymer (A) referred to in the present invention is an isocyanate group-terminated urethane prepolymer in which an isocyanate group obtained by the reaction of a polyol component and a polyisocyanate component remains, a polyol component, a polyisocyanate compound, and an isocyanate. It comprises an isocyanate group having one or more active hydrogen atoms reacting with a group per molecule and a compound having a hydrolyzable silyl group reacted, and an alkoxysilyl group-terminated urethane prepolymer.

The isocyanate group-terminated urethane prepolymer used in the present invention has a polyol component and a polyisocyanate component having an equivalent ratio of NCO groups of isocyanate to OH groups of polyol (NCO group / OH group equivalent ratio) of 1 or more,
That is, it is obtained by reacting the NCO group in excess.
The NCO group / OH group equivalent ratio is usually preferably 1.1 to
It is in the range of 5.0, and more preferably in the range of 1.5 to 3.0. When the NCO group / OH group equivalent ratio is in such a range, excellent processability, foam retention, and appropriate crosslink density can be obtained.

The isocyanate group- and alkoxysilyl group-terminated urethane prepolymer used in the present invention has a polyol component, a polyisocyanate component, and one or more active hydrogen atoms that react with the isocyanate group per molecule, and is hydrolyzed. It is obtained by reacting a compound having a decomposable silyl group. Usually, the above-mentioned polyurethane prepolymer having an isocyanate group is reacted with one of the active hydrogen atoms capable of reacting with an isocyanate group and a compound having a hydrolyzable silyl group to introduce a hydrolyzable silyl group at the molecular end. The method of burial is used. In addition, by reacting a polyurethane prepolymer having an isocyanate group with at least two or more active hydrogen atoms capable of reacting with the isocyanate group and a compound having a hydrolyzable silyl group, the isocyanate group and the hydrolyzable group are reacted in the molecule. A urethane prepolymer having an alkoxysilyl group is obtained.

The crosslinking reaction of the solventless moisture-curable hot-melt urethane resin composition of the present invention occurs when the isocyanate group or hydrolyzable silyl group in each prepolymer reacts with moisture.

It has at least one active hydrogen atom per molecule which reacts with the isocyanate group used in the present invention,
In addition, the compound having a hydrolyzable silyl group is a functional group having an active hydrogen atom that reacts with an isocyanate group.
There is no particular limitation as long as it is a compound having one or more per molecule and a hydrolyzable silyl group.
Examples of the functional group having an active hydrogen atom include an amino group, a hydroxyl group, and an SH group. Among them, the amino group is preferable from the viewpoint of excellent reactivity with the isocyanate group. On the other hand, the hydrolyzable silyl group includes, for example, a silyl group which is easily hydrolyzed, such as a halosilyl group, an alkoxysilyl group, an acyloxysilyl group, a phenoxysilyl group, an iminooxysilyl group or an alkenyloxysilyl group. However, more specific examples include those represented by the following general formula [1].

[0041]

[Chemical 1]

(In the general formula [1], R ₁ is a hydrogen atom or a monovalent organic group selected from an alkyl group, an aryl group or an aralkyl group, and R ₂ is a halogen atom, an alkoxyl group or an acyloxy group. , A phenoxy group, an iminooxy group or an alkenyloxy group, and n represents an integer of 0 or 1 or 2.)

Among the above hydrolyzable silyl groups, a trimethoxysilyl group, a triethoxysilyl group, a (methyl) dimethoxysilyl group, a (methyl) diethoxysilyl group and the like are preferable from the viewpoint of easy crosslinking.

Examples of the compound containing a group that reacts with an isocyanate group and a hydrolyzable silyl group include γ- (2-aminoethyl) aminopropyltrimethoxysilane and γ- (2-hydroxylethyl) aminopropyl. Trimethoxysilane, γ- (2-aminoethyl)
Aminopropyltriethoxysilane, γ- (2-hydroxylethyl) aminopropyltriethoxysilane, γ
-(2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ- (2-hydroxylethyl) aminopropylmethyldimethoxysilane, γ- (2
-Hydroxylethyl) aminopropylmethyldiethoxysilane or γ- (N, N-di-2-hydroxylethyl) aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-amino Examples include propylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (N-phenyl) aminopropyltrimethoxysilane, and the like.

For preparing the prepolymer (A) used in the present invention, various known and conventional methods may be used without any particular limitation.

In general, in the case of an isocyanate group-terminated urethane prepolymer, it is obtained by dropping a water-free polyol component to the starting isocyanate component and heating it to react until the hydroxyl component of the polyol component disappears. Further, in the case of an isocyanate group- and alkoxysilyl group-terminated urethane prepolymer, an alkoxysilane compound having a group that reacts with an NCO group is added dropwise to the isocyanate group-terminated prepolymer obtained as described above, and heated as necessary. And then react to obtain. This reaction is carried out without a solvent, but in some cases, it is also carried out in an organic solvent and then desolvated. When the reaction is carried out in an organic solvent, various conventionally known organic solvents such as ethyl acetate, n-butyl acetate, methyl ethyl ketone, and toluene can be used, and the organic solvent is not particularly limited as long as it does not inhibit the reaction. In this case, after completion of the reaction, it is necessary to remove the solvent by a solvent removal method represented by reduced pressure heating.

In the present invention, the above prepolymer (A)
However, if necessary, an active hydrogen-containing compound can be used as a chain extender at the time of use within a range that does not impair the original moisture curability.

Examples of the active hydrogen-containing compound include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol and 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-dimethanol, one or more diols such as EO or PO adduct of bisphenol A, and the like. Polyhydric alcohols such as glycol, glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol, or ethylene oxide, propylene oxide, butylene oxide, and styrene oxide, which are initiated with the polyester polyol, as a single or two or more ring-opening polymerizations. And ring-opening addition polymers such as γ-butyrolactone and ε-caprolactone of the above polyether diols can be used. Among these, glycol is preferable in consideration of processing suitability because the reaction with the isocyanate group during processing is slow and the crosslinking rate is easily controlled.

The amount of these active hydrogen-containing compounds used is preferably in the range of 0.1 to 10 parts by weight, more preferably 0.1% by weight, based on 100 parts by weight of the prepolymer (A).
It is in the range of 5 to 5 parts by weight. When the amount of the active hydrogen-containing compound used is in such a range, a good thickening effect can be obtained, foam retention is good, and gelation does not occur during mixing and stirring, which is preferable.

The amine catalyst (B) used in the present invention is, for example, ethylenediamine, 1,3-propylenediamine, 1,2-propylenediamine, hexamethylenediamine, norbornenediamine, hydrazine, pyrerazine, N, N '. -Diaminopiperazine, 2-methylpiperazine, 4,4'-diaminodicyclohexylmethane, isophoronediamine, diaminobenzene, diphenylmethanediamine, methylenebisdichloroaniline, triethylenediamine, tetramethylhexamethylenediamine, triethylamine (TEA), tripropylamine, Trimethylaminoethylpiperazine, N-methylmorpholine, N-ethylmorpholine, di (2,6-dimethylmorpholinoethyl) ether, pentamethyldiethylenetriamine, Oxamethyl tetraethylene tetraamine (HMTETA), dimethylaminoethyl ethanol ether (DMAEE), trimethylaminoethyl ethanolamine (TMAEEA), bisdimethylaminoethyl ether (BDMEE), N, N-dimethylcyclohexylamine (DMCHA), N- Methyldicyclohexylamine (MDCHA) N, N, N ', N'-
Tetramethylethylenediamine (TMEDA) N, N,
N ', N'-tetramethylpropylenediamine (TMPD
A), N, N, N ′, N′-tetramethylhexamethylenediamine (TMHMDA), N, N, N ′, N ″, N ″
-Pentamethylethylene propylene triamine (PME
PTA), N, N, N ′, N ″, N ″ -pentamethyldipropylenetetraamine (PMDPTA), N, N,
N ′, N ″, N ′ ″, N ′ ″-hexamethyldipropyleneethylenetetraamine (HMAPEDA), N, N,
N'-trimethyl-N-aminoethylpyrazine (TM
NAEP), N-hydroxyethylmorpholine (HE
MO), N, N, N ', N'-tetramethyldipropylene ethylene glycol diamine (TMEGDA), N,
Among polyamines such as N, N ′, N ″, N ″ -pentamethyldiethylenetriamine (PMDETA), one kind or a mixture of two or more kinds can be used.

The amount of these amine catalysts (B) used is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the prepolymer (A). . When the amount of the amine-based catalyst (B) used is in such a range, a good thickening effect can be obtained, and foam stickiness is good,
Further, it is preferable because it does not gel during mixing and stirring.

Next, the water (C) used in the hot melt urethane resin composition of the present invention is mixed with the amine catalyst (B) and mixed with the prepolymer (A) and stirred to foam water. It is an essential ingredient.

The amount of water (C) added is the same as that of the prepolymer (A).
It is preferably 0.01 to 5.0 parts by weight, more preferably 0.05 to 1.0 parts by weight, relative to 100 parts by weight.
When the amount of water (C) added is in such a range, the degree of foaming becomes appropriate and the surface condition of the foam becomes good, which is preferable.

In the present invention, if necessary, a foam stabilizer may be used at the time of use within a range that does not impair the original moisture curability. Specific examples include those containing 10 wt% or more of a conventionally known polysiloxane-polyoxyalkylene copolymer used as an organic silicon-based surfactant. Examples of the foam stabilizer include trade names SF2969 and PRX60 manufactured by Toray Dow Corning Silicone Co., Ltd.
7, SF2964, SRX274C, SF2961, S
F2962, SF2965, SF2908, BY10-
123, SF2904, SRX294A, BY10-1
24, SF2935F, SF2945F, SF2944
F, SF2936F, SH193, SH192H, SH
192, SF2909, SH194, SH190, SR
X290A, SRX298, and product names L-580, SZ1127, SZ1111, manufactured by Nippon Unicar Co., Ltd.
SZ1136, SZ1919, SZ1105, SZ11
42, SZ1162, L3601, L5309, L53
66, SZ1306, SZ1311, SZ1313, S
Z1342, L5340, L5420, SZ1605,
SZ1627, SZ1642, SZ1649, SZ16
71, SZ1675, SZ1923 and the like.

The amount of these foam stabilizers used is preferably 0.1 to 20 relative to 100 parts by weight of the prepolymer (A).
Parts by weight, more preferably 0.5 to 10 parts by weight. When the amount of the foam stabilizer used is in such a range, the foam stabilizer is excellent, and the physical mechanical strength of the foam after aging is also excellent, which is preferable.

If necessary, a plasticizer such as bis (2-ethylhexyl) phthalate (DOP), diisononyl adipate (DINA), bis (2-ethylhexyl adipate) (DOA), EO, etc. may be added to the foam stabilizer. A polyether-based surfactant such as a / PO copolymer may be added.

The solvent-free, moisture-curable hot-melt urethane resin composition having excellent durability of the present invention has the above-mentioned crosslinking reactivity, that is, moisture-curability and hot-melt property (that is, it is solid at room temperature, but heat-resistant). A resin that also has the property of being melted to be in a coatable state when added and having a cohesive force again when cooled).

The foam layer referred to in the present invention means an important layer of the multi-layer structure of artificial leather or synthetic leather, which is added to the texture of leather. As a method of obtaining a foam layer,
Wet method using DMF solvent, method using foaming agent,
Known methods include the use of carbon dioxide gas generated by the reaction of isocyanate with water, and the method of mechanical foaming by forced gas mixing.

The foam of the present invention is obtained by water-foaming a solventless moisture-curable hot melt urethane resin composition comprising at least a prepolymer (A), an amine catalyst (B), and water (C). It is characterized by being hardened.

The foam of the present invention is obtained by heating the solventless moisture-curable hot-melt urethane resin composition into a liquid or molten state, and if necessary, previously mixing an inert gas to foam the water. After that, a method of fixing the foamed state by curing using hot melt property and moisture curability is preferable. When an inert gas is mixed, a difference in the coefficient of thermal expansion between water and the inert gas is generated, so that the size of the foam cell can be controlled by the mixing ratio, which is effective.

Examples of the inert gas that can be used for foaming in the present invention include nitrogen, noble gas, carbon dioxide, halogenated hydrocarbon and the like.

The solventless moisture-curable hot-melt urethane resin of the present invention comprises the above-mentioned prepolymer (A) as a main component, and if necessary, a silane coupling agent, a tackifier,
Wax, plasticizer, crosslinking catalyst, stabilizer, filler, pigment,
Additives such as optical brighteners and thermoplastic resins may be added alone or in combination.

The number average molecular weight of the prepolymer (A) thus prepared is not particularly limited, but is preferably 500 to 500 in terms of fluidity and processability.
Within the range of 500000, more preferably 1000-10
It is in the range of 0000.

When preparing the reactive hot melt urethane prepolymer (A), a urethanization catalyst or a stabilizer may be used if necessary. These catalysts, stabilizers and the like can be added at any stage of the reaction, and are not particularly limited.

As the urethanization catalyst, for example, various metal salts represented by potassium acetate, zinc stearate, tin octylate, etc .; or various organometallic compounds represented by dibutyltin dilaurate, etc. And so on. These may be used alone or in combination of two or more.

On the other hand, examples of the above-mentioned stabilizers include stabilizers against ultraviolet rays such as substituted benzotriazoles, and further include stabilizers against thermal oxidation such as substituted phenol derivatives. Each of the stabilizers can be appropriately selected and added according to the purpose, and may be used alone or in combination of two or more kinds.

Also in the case of an alkoxysilyl group terminated urethane prepolymer, various acidic compounds such as malic acid and citric acid, lithium hydroxide, sodium hydroxide, potassium hydroxide, and Various basic compounds such as triethylenediamine, various metal-containing compounds such as tetraisopropyl titanate, di-n-butyltin dilaurate, di-n-butyltin oxide, dioctyltin oxide or di-n-butyltin maleate It is possible to add and use those generally used as an alkoxysilyl group-crosslinking catalyst, such as compounds.

Examples of the silane coupling agent used in the present invention include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrine. Examples thereof include methoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane and γ-chloropropyltrimethoxysilane.

Examples of the filler used in the present invention include calcium carbonate, barium sulfate, kaolin, talc, carbon black, alumina, magnesium oxide,
Examples include inorganic and organic balloons. Furthermore, surface-treated calcium carbonate, fine powder silica, bentonite, sepiolite, etc., which are known as thixotropic agents, can be used. In particular, the addition of a thixotropic agent is preferable from the viewpoint of stabilizing the foam after foaming.

The sheet structure of the present invention is characterized by having a base material and a foam layer obtained by water-foaming the solventless moisture-curable hot-melt urethane resin composition on the base material and then curing the same. And

The sheet structure of the present invention comprises a base material, the solventless moisture-curable hot-melt urethane resin composition on the base material, an inert gas previously mixed therein, and water-foamed.
It is characterized by having a cured foam layer.

The sheet structure of the present invention comprises a base material, a solvent-free moisture-curable hot-melt urethane resin composition on the base material, which is water-foamed and then cured to form a foamed layer and the foamed layer. It is characterized by integrating a leather-like film layer.

The sheet structure of the present invention comprises a base material, the solventless moisture-curable hot-melt urethane resin composition on the base material, an inert gas previously mixed, and water-foamed,
It is characterized in that a cured foam layer and a leather-like film layer are integrated with the foam layer.

The sheet structure of the present invention comprises a leather-like film and a foam layer obtained by water-foaming the solventless moisture-curable hot-melt urethane resin composition on the film and then curing the same. Characterize.

The sheet structure of the present invention comprises a leather-like film, the solventless moisture-curable hot-melt urethane resin composition previously mixed on the film with an inert gas, and water-foamed. It is characterized by having a cured foam layer.

The base material constituting the sheet structure of the present invention includes, for example, non-woven fabrics, woven fabrics, knitted fabrics and other base fabrics generally used for artificial leathers and synthetic leathers, natural leathers, and various plastic sheets. Etc. are not limited at all. Further, generally used for artificial leather or synthetic leather such as non-woven fabric, woven fabric, knitted fabric, etc. impregnated with at least one kind of solvent-based and water-based polyurethane resin, acrylic resin, rubber-based (SBR, NBR, etc.) latex and the like. There is no limitation as long as it is a base cloth or natural leather used.

The leather-like film used in the present invention is not particularly limited as long as it is a polyurethane resin conventionally used for artificial leather or synthetic leather, and usually solvent type and water-based polyurethane resins are separated. It can be obtained by coating on a pattern paper and drying.

The foam obtained in the present invention, the sheet structure having a foam layer, or the sheet structure in which a foam layer and a leather-like film layer are integrated with each other are prepared by melting the prepolymer (A). Then, a solvent-free moisture-curable hot-melt urethane resin composition obtained by mixing an amine catalyst (B) and water (C), and in some cases an inert gas, and water-foaming is used between release papers or a substrate. Between the top and the release paper, or between the base cloth and the leather-like film, the release paper and the water-repellent treated cloth and the film is uniformly laminated and cooled and solidified, and if it is a method that can be crosslinked and processed, there is no particular limitation. Absent. In addition, after the foam is prepared, it may be adhesively processed with a substrate or / and a leather-like film.

Further, the equipment for foaming the resin is not particularly limited as long as it can uniformly mix an inert gas while mixing a predetermined amount thereof, but it is cooled and thickened by stirring at the time of mixing the inert gas to be uniform. It is desirable that the mixture can be heated and kept warm in order to avoid flow failure and application failure or adhesion failure when foaming is not performed or when the base material or film is processed as a foam layer.

The foaming degree of the foamed layer of the foamed product of the present invention can be appropriately adjusted according to its application, and is not particularly limited as long as the texture or the strength is not impaired. For example, for artificial leather use or synthetic leather use, the foaming degree is preferably in the range of 1.5 to 2.5 times. The "foaming degree" here means the ratio of the volume of the resin before foaming (V ₁ ) to the volume of the resin after foaming (V ₂ ), that is, V ₂ / V ₁ .

Surface treatment of the foam or sheet structure of the present invention by known or conventional lamination or coating,
Alternatively, various processing methods such as buffing processing are not limited at all.

As described above, according to the present invention, a solventless moisture-curable hot melt urethane resin composition having excellent adhesiveness, hydrolysis resistance and heat resistance, and foam obtained by using the urethane resin composition. A body and a sheet structure using the body can be provided.

[0083]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is by no means limited to these examples. In the following, parts and%
All are by weight unless otherwise specified.
Various properties of the resin were measured according to the following methods.

[Production Method of Skin Film 1] Crisbon NY324 which is a solvent type urethane resin for synthetic leather skin.
(Manufactured by Dainippon Ink and Chemicals, Inc.)
AC-6001 (manufactured by Dainippon Ink and Chemicals, Inc.), methyl ethyl ketone (MEK), and dimethylformamide (DMF) were used with a knife coater so that the coating amount was 100 g / m ² (wet) on the release paper. After applying evenly, dry at 70 ℃ for 1 minute, then at 120 ℃ 2
After being dried for a minute, a skin film 1 having a thickness of 30 μ was prepared.

[Method of measuring softening point] The softening point of each prepolymer obtained in Examples and Comparative Examples was measured by a differential calorimeter (DS).
C) was used and the temperature was raised at a rate of 5 ° C./min in a nitrogen atmosphere.

[Evaluation of degree of foaming] Prepolymer (A) melted at 120 ° C. and a predetermined amount of amine catalyst (B) and water (C) were mixed and stirred, and resin volume before foaming (V1) and after foaming Of the resin volume (V2), that is, V2 / V1,
The degree of foaming was used. ○: Good foamability ×: Poor foamability

[Measurement Method of Adhesiveness] A hot melt cloth tape was applied to the surface of the sheet structure with the skin film at 130 ° C. for 5 minutes.
After thermocompression bonding for 2 seconds, Tensilon (head speed: 20
The peel strength was measured using 0 mm / min).

[Measurement Method of Hydrolysis Resistance] The sheet structure with the skin film was subjected to a hydrolysis resistance test (jungle test conditions: 70 ° C., relative humidity 95%, kept for 12 weeks), and then a hot-melt cloth was applied to the skin. After thermocompression bonding the tape at 130 ℃ for 5 seconds, Tensilon (head speed: 200mm
/ Min) was used to measure the peel strength to observe the retention rate and the change in appearance after evaluation, and the evaluation was made according to the following criteria. ○: No change in appearance after jungle test ×: Change in appearance after jungle test

[Measurement Method of Heat Resistance] The sheet structure with the skin film was subjected to a heat resistance test (test condition: 120 ° C., holding for 500 hours), and then 1 piece of hot melt cloth tape was applied to the skin.
After thermocompression-bonding at 30 ° C. for 5 seconds, the peel strength was measured using Tensilon (head speed: 200 mm / min), the retention rate and the appearance change after the evaluation were observed, and evaluated according to the following criteria. ○: No change in appearance after the test ×: Change in appearance after the test

Example 1 Method for Manufacturing Structure 1 with Skin Film Polycarbonate diol having a number average molecular weight of 2000 in a 1-liter 4-necked flask (Nippon Polyurethane Co., Ltd.)
Made: 80 parts of Niprolan 980R, abbreviated as PC2000 hereinafter, and 20 parts of polyester polyol having a number average molecular weight of 2000 of adipic acid (abbreviated as AA in the table) and hexanediol (abbreviated as HG in the table). 120 ° C
It was dehydrated by heating under reduced pressure until the water content became 0.05%. Four
After cooling to 0 ° C., 20 parts of 4,4′-diphenylmethane diisocyanate (MDI) was added, the temperature was raised to 90 ° C., and the reaction was continued for 3 hours until the NCO content became constant to obtain prepolymer 1. . 125 ° C with a cone and plate viscometer
Had a viscosity of 6000 mPa · s and an NCO content of 2.0% by weight. The resulting prepolymer 1 was 12
Nitrogen gas was blown in while heating at 0 ° C. to melt and heating at 120 ° C.
OLYCAT-8 (manufactured by Air Products Japan Ltd .;
N, N-dimethylcyclohexylamine (DMCH
It was confirmed from the volume that 0.10 part of A)) and 0.05 part of water were added and mixed to foam about 2 times.
Immediately, apply a thickness of 50μ on the skin film 1,
Polyurethane-impregnated non-woven fabric is laminated and cooled to a temperature of 23
The sheet was allowed to stand for 5 days in an environment of 65 ° C. and 65% relative humidity to obtain a sheet-shaped structure 1 with a surface film. The results of evaluation of the properties of the sheet-shaped structure 1 with a skin film of the present invention are shown in Table 1, and were excellent in adhesiveness, hydrolysis resistance, and heat resistance.

Example 2 Method for Producing Structure 2 with Surface Film 50 parts of PC2000 in a 1-liter 4-necked flask,
The number average molecular weight of adipic acid and hexanediol is 20.
50 parts of the polyester polyol of No. 00 was heated under reduced pressure to 120 ° C. and dehydrated until the water content became 0.05%. 40 ° C
After cooling to 4, after adding 20 parts of 4,4′-diphenylmethane diisocyanate (MDI), the temperature was raised to 90 ° C.,
Prepolymer 2 was obtained by reacting for 3 hours until the NCO content became constant. Viscosity at 125 ° C with a cone and plate viscometer is 5500 mPa · s and NCO content is 1.9% by weight.
Became. The prepolymer 2 thus obtained was heated to 120 ° C. to be melted, and nitrogen gas was blown into the prepolymer 2 while heating at 120 ° C.
It was confirmed from the volume that about 0.12 parts of T-8 and 0.05 part of water were added and mixed to foam about 2 times. Immediately, it was coated on the skin film 1 with a thickness of 50 μm, cooled, and allowed to stand for 5 days in an environment of a temperature of 23 ° C. and a relative humidity of 65% to obtain a sheet-shaped foam 2 with a skin film. The results of evaluation of the properties of the sheet-shaped structure 2 with a skin film of the present invention are shown in Table 1, and were excellent in adhesiveness, hydrolysis resistance, and heat resistance.

Example 3 Method for Producing Structure 3 with Surface Film 20 parts of PC2000 in a 1-liter 4-necked flask,
The number average molecular weight of adipic acid and hexanediol is 20.
80 parts of the polyester polyol of No. 00 was heated under reduced pressure to 120 ° C. and dehydrated until the water content became 0.05%. 40 ° C
After cooling to diphenylmethane diisocyanate (MD
After adding 20 parts of I), the temperature was raised to 90 ° C. and the reaction was continued for 3 hours until the NCO content became constant to obtain a prepolymer 3. Viscosity at 125 ° C with a cone and plate viscometer is
The NCO content was 2.1% by weight at 00 mPa · s. The prepolymer 3 thus obtained was heated to 120 ° C. to be melted, and nitrogen gas was blown into the prepolymer 3 while heating at 120 ° C., to 100 parts of the prepolymer 3, 0.10 part of POLYCAT-8 and 0 parts of water were added. It was confirmed from the volume that about 0.05 times the amount of foaming was obtained by adding and mixing 0.05 part. Immediately, it was applied on the skin film 1 with a thickness of 50 μm, cooled, and allowed to stand for 5 days in an environment of a temperature of 23 ° C. and a relative humidity of 65% to obtain a sheet-like structure 3 with a skin film. The results of evaluation of the properties of the sheet-shaped structure 3 with a surface film of the present invention are shown in Table 1, and it was excellent in adhesiveness, hydrolysis resistance, and heat resistance.

Example 4 Method for Producing Structure 4 with Surface Film The prepolymer 2 obtained in Example 2 was heated and melted at 120 ° C. and then heated at 120 ° C. to give a number average molecular weight of 100.
0 propylene glycol (PPG1000) and dibutylditin dilaurate (DBSNDL) were mixed at a prepolymer 2 / PPG-1000 = 100 / 3.0 / 0.1 weight ratio while blowing nitrogen gas to obtain POLYCAT-
It was confirmed from the volume that 0.18 part of 8 and 0.10 part of water were added and mixed, and about twice the amount was foamed. Foamed prepolymer 1 was obtained. Immediately, it was applied on the skin film 1 with a thickness of 50 μm, cooled, and allowed to stand for 5 days in an environment of a temperature of 23 ° C. and a relative humidity of 65% to obtain a sheet-like structure 4 with a skin film. The results of evaluation of the properties of the sheet-like structure with a surface film 4 of the present invention are shown in Table 1, and it was excellent in adhesiveness, hydrolysis resistance, and heat resistance.

Example 5 Method for Producing Structure 5 with Surface Film 124 parts of the prepolymer 2 obtained in Example 2 was put in a 1-liter 4-neck flask in a molten state, and γ-phenylaminopropyltrimethoxysilane was added. 16 parts of
Prepolymer 4 was obtained by reacting at 2 ° C. for 2 hours, and 1 part of phosphoric acid ester catalyst (AP-1) was added and uniformly mixed. Viscosity at 125 ° C with a cone and plate viscometer is 7,000 mP
It was a.s. The prepolymer 4 thus obtained is heated to 120 ° C. to be melted, and nitrogen gas is blown into the prepolymer 4 while heating at 120 ° C.
It was confirmed from the volume that CAT-8 was foamed about twice as much as 0.10 parts of water and 0.10 parts of water were mixed and mixed. Immediately, it is coated on the skin film 1 with a thickness of 50 μm and cooled, and the temperature is 23 ° C. and the relative humidity is 65%.
After standing for a day, a sheet-shaped structure 5 with a skin film was obtained. The results of characteristic evaluation of the sheet-shaped structure 5 with a surface film of the present invention are shown in Table 1, and the adhesiveness and hydrolysis resistance were excellent.

Comparative Example 1 50 parts of polypropylene glycol (PPG-2000) having a number average molecular weight of 2000 and 50 parts of polyester polyol having a number average molecular weight of 2000 of adipic acid and hexanediol were placed in a 1-liter 4-necked flask. Parts were heated under reduced pressure to 120 ° C. and dehydrated until the water content became 0.05%. After cooling to 40 ℃ 4,
After adding 20 parts of 4′-diphenylmethane diisocyanate (MDI), the temperature was raised to 90 ° C. and the reaction was continued for 3 hours until the NCO content became constant to obtain a prepolymer 5.
Viscosity at 125 ° C measured by cone-plate viscometer is 8000m
The NCO content in Pa · s was 2.0% by weight. The resulting prepolymer 5 is heated to 120 ° C. and melted to obtain 12
Nitrogen gas was blown into the prepolymer 5 while heating at 0 ° C., and 0.10 of POLYCAT-8 was added to 100 parts of the prepolymer 5.
Part and 0.05 part of water were added and mixed, and it was confirmed from the volume that the foaming was about twice. Immediately, it is coated on the skin film 1 with a thickness of 50 μm and cooled to a temperature of 23
It was left for 5 days in an environment of ° C and relative humidity of 65% to obtain a sheet-like structure 6 with a surface film. The results of the characteristic evaluation are shown in Table 2. This product had good initial adhesion,
It was inferior in hydrolysis resistance and heat resistance.

Comparative Example 2 50 parts of PC2000 were added to a 1 liter 4-necked flask, and the number average molecular weight of adipic acid having a number average molecular weight of 2000 and hexanediol was 200.
50 parts of the polyester polyol of No. 0 was heated under reduced pressure to 120 ° C. and dehydrated until the water content became 0.05%. After cooling to 40 ° C., 20 parts of 4,4′-diphenylmethane diisocyanate (MDI) was added, then the temperature was raised to 90 ° C. and NC
Prepolymer 2 was obtained by reacting for 3 hours until the O content became constant. The viscosity at 125 ° C. measured by a cone and plate viscometer was 5500 mPa · s, and the NCO content was 1.9% by weight. The obtained prepolymer 2 was heated to 120 ° C. to be melted, and nitrogen gas was blown into the prepolymer 2 while heating at 120 ° C., and to 100 parts of the prepolymer 2, only 0.05 part of water was added and mixed. , Only about 0.5 times foamed. Immediately, it is coated on the skin film 1 with a thickness of 50 μm and cooled, and the temperature is 23 ° C. and the relative humidity is 65%.
After leaving for one day, a sheet-shaped structure 7 with a surface film was obtained. The results of the characteristic evaluation are shown in Table 2. This product had good hydrolysis resistance and heat resistance, but was inferior in foaming property and had a hard texture.

Comparative Example 3 50 parts of PC2000 and P having a number average molecular weight of 2000 were placed in a 1-liter 4-necked flask.
50 parts of PG was dehydrated by heating at 120 ° C. under reduced pressure until the water content became 0.05%. After cooling to 40 ° C., 20 parts of 4,4′-diphenylmethane diisocyanate (MDI) was added, the temperature was raised to 90 ° C., and the reaction was continued for 3 hours until the NCO content became constant, to obtain prepolymer 2. Viscosity at 125 ° C with a cone-plate viscometer is 5500 mPa · s NC
The O content was 1.9% by weight. The prepolymer 2 thus obtained was heated to 120 ° C. and melted, and nitrogen gas was blown into the prepolymer 2 while heating at 120 ° C., and only 0.10 part of POLYCAT-8 was added to 100 parts of the prepolymer 7. It was mixed, but foamed only about 0.8 times. Immediately, it was applied on the skin film 1 with a thickness of 50 μm, cooled, and allowed to stand for 5 days in an environment of a temperature of 23 ° C. and a relative humidity of 65% to obtain a sheet-like structure 8 with a surface film.
This product had good hydrolysis resistance and heat resistance, but was inferior in foaming property and had a hard texture.

Comparative Example 4 60 parts of polytetramethylene glycol (hereinafter abbreviated as PTMG) having a number average molecular weight of 1400, adipic acid (hereinafter abbreviated as AA) and hexanediol (in a 1-liter 4-necked flask) Below, HG
Abbreviated) and 40 parts of a polyester polyol having a number average molecular weight of 2000 is heated to 120 ° C. under reduced pressure to obtain a water content of 0.0
It was dehydrated to 5%. After cooling to 40 ° C, 4,4'-
After adding 25 parts of diphenylmethane diisocyanate (MDI), the temperature was raised to 90 ° C. and the reaction was continued for 3 hours until the NCO content became constant to obtain prepolymer 8. Viscosity at 125 ° C with a cone-plate viscometer is 8000 mPa · s
The NCO (%) was 2.0. The obtained prepolymer 8 was heated to 120 ° C. and melted, and nitrogen gas was blown into the prepolymer 8 while heating at 120 ° C., to 100 parts of the prepolymer 8, 0.10 parts of POLYCAT-8 and 0 parts of water were added. ．
It was confirmed from the volume that about 05 times foaming was performed by adding 05 parts and mixing. Immediately, it is coated on the skin film 1 with a thickness of 50 μm and cooled, and the temperature is 23 ° C. and the relative humidity is 6
The sheet-like structure 9 with a surface film was obtained by leaving it in a 5% environment for 5 days. This product is. Although the adhesion was good at the initial stage and after the hydrolysis resistance, it was inferior in heat resistance.

[0099]

[Table 1]

[0100]

[Table 2]

[0101]

The solventless moisture-curable hot melt urethane resin composition having excellent durability obtained by the present invention is
If necessary, foaming with water using an inert gas and coating it on the surface material makes it highly flexible,
In addition, since the synthetic leather with excellent adhesiveness and durability (particularly hydrolysis resistance and heat resistance) can be prepared without solvent, the drying process of the solvent, which was indispensable in the case of conventional solvent type urethane resin And the extraction process is unnecessary, and the problems on the human body, the environmental pollution, the energy cost for evaporating the solvent, and the like can be improved. The solvent-free, moisture-curable hot-melt urethane resin composition excellent in durability obtained in the present invention, a foam, and a structure using the same are synthetic leathers for furniture and automobile applications that require high durability. In addition to artificial leather and artificial leather, it is extremely practical in a wide range of applications such as adhesives, pressure-sensitive adhesives, sealing agents, paints, coating agents or films or sheets.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08G 18/18 C08G 18/18 18/38 18/38 Z D06N 3/14 102 D06N 3/14 102 F term (Reference) 4F055 AA01 AA23 BA12 CA14 CA16 FA16 FA20 FA38 GA28 4F100 AH03B AK51B AS00C AT00A BA02 BA03 BA10A BA10C CA30B CB03B DG15 DJ01B EJ08B EJ60B GB33 CA08 CB CA03 CA08 CB CA03 CA08 CB CA03 CA08 CA08 CA03 CA08B CB01 CA04 CA04 CA03 CA08B CB01 CA04 CA08 CA03 CA08B CB01 CA04 CC23 CC26 CC45 CC52 CC61 CC62 CC65 CC67 CD03 CD04 CD16 DA01 DB03 DB07 DF02 DF11 DF12 DF15 DF17 DF20 DF20 DF22 DF29 DG02 DG03 DG04 DG05 DG14 DG15 DG16 HC47 HC52 HC61 HC17 HC22 HC61 HC17 HC22 HC61 HC17 HC22 HC61 HC13 HC07 HC12 HC46 HC13 HC09 JA01 JA02 JA14 KA01 KB02 KD12 KE02 LA08 LA33 NA03 NA08 QC01 QC03 RA03 RA05

Claims (12)

[Claims] 1. A hot melt urethane prepolymer (A) obtained by reacting a polyol component and a polyisocyanate component [hereinafter referred to as prepolymer (A)], an amine catalyst (B), and water (C). A solvent-free, moisture-curable hot-melt urethane resin composition, wherein the polyol component of the prepolymer (A) uses a polycarbonate polyol as an essential component. 2. The solventless moisture-curable hot melt urethane resin composition according to claim 1, wherein the content of the polycarbonate polyol in the polyol component of the prepolymer (A) is 20% by weight or more. 3. The softening point of the prepolymer (A) is 30 to
The solventless moisture-curable hot melt urethane resin composition according to claim 1 or 2, which has a temperature range of 160 ° C. 4. The solventless moisture-curable hot melt urethane resin according to claim 1, wherein the prepolymer (A) is an isocyanate group-terminated and alkoxysilyl group-terminated urethane prepolymer. 5. A foam produced by water-foaming the solventless moisture-curable hot-melt urethane resin composition according to any one of claims 1 to 4 and then curing it. 6. The solventless moisture-curable hot-melt urethane resin composition according to any one of claims 1 to 4 is mixed with an inert gas in advance, water-foamed, and then cured. A foam characterized by: 7. A base material and a foam layer obtained by water-foaming the solventless moisture-curable hot-melt urethane resin composition according to any one of claims 1 to 4 on the base material and then curing the same. A sheet structure comprising: 8. A base material and the solventless, moisture-curable hot-melt urethane resin composition according to claim 1, which is preliminarily mixed with an inert gas, and water is added to the base material. A sheet structure having a foamed layer which is cured after foaming. 9. A base material and a foam layer obtained by water-foaming the solventless moisture-curable hot-melt urethane resin composition according to any one of claims 1 to 4 on the base material and then curing it. And a sheet structure in which a leather-like film layer is integrated with the foam layer. 10. A base material and the solventless moisture-curable hot-melt urethane resin composition according to any one of claims 1 to 4 on which an inert gas is previously mixed, and water is added. A sheet structure comprising a foamed layer that has been foamed and then cured, and a leather-like film layer integrated with the foamed layer. 11. A leather-like film and a solvent-free, moisture-curable hot-melt urethane resin composition according to any one of claims 1 to 4 which is water-foamed and then cured. A sheet structure having a layer. 12. A leather-like film and the solventless moisture-curable hot-melt urethane resin composition according to any one of claims 1 to 4 on which an inert gas is mixed in advance, A sheet structure having a foamed layer which is water-foamed and then cured.