JP2019112564A - Composition for foam formation, foam, method for producing foam, and material for leather - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a foamed resin layer made of a foamed cured product of the composition, which has a sufficiently high foaming property and can be efficiently foamed even though it is a composition for forming a foam containing an aqueous polyurethane resin. Foam that can have a sufficient thickness and can impart sufficient texture and material breaking strength to the obtained leather material when a leather material is produced using the composition. To provide a composition for body formation. SOLUTION: A self-emulsifying aqueous polyurethane resin having at least one hydrophilic functional group selected from the group consisting of (A) sulfo group and sulfonate group, (B) forced emulsifying aqueous polyurethane resin, (C) cross-linking. A composition for forming a foam, which comprises an agent, (D) a foaming agent, (E) a thickener, and (F) water. [Selection diagram] None

Description

  The present invention relates to a foam-forming composition, a foam, a method for producing a foam, and a leather material.

  Conventionally, as a substitute for natural leather, an artificial leather provided with a polyurethane resin and a fiber base made of a non-woven fabric, and a synthetic leather provided with a polyurethane resin and a fiber base made of a woven or knitted fabric have been manufactured. Such artificial leathers and artificial leathers such as synthetic leathers are, for example, those obtained by applying an organic solvent solution of a polyurethane resin to a fiber substrate by impregnation or coating, a poor solvent for the polyurethane resin, and the organic solvent It is manufactured by a method called wet coagulation, in which coagulation is carried out through a coagulation solution (usually water) compatible with the above and then washed with water and dried.

  However, organic solvents, which are often used in such wet coagulation methods, are strongly flammable and have a risk of fire, and there are also concerns about deterioration of working environment and environmental pollution such as air and water quality. In order to solve such problems, although a manufacturing method incorporating a step of recovering the generated organic solvent has been implemented, there still remains the problem that a large amount of disposal cost and labor are required. Therefore, in recent years, studies have been made to transfer the polyurethane resin adhering to the fiber base material from the organic solvent type to the aqueous polyurethane resin. Then, a foam is formed by laminating a foamed layer made of a foamed cured product of an aqueous polyurethane resin on a base material as a material (a material for leather) for forming a pseudoleather like artificial leather, synthetic leather, etc. It has been proposed that various methods for producing such foams have been proposed.

  For example, in JP 2005-273083 A (patent document 1), a functional group selected from the group consisting of a carboxyl group, a hydroxyl group, an amino group, an imino group and a combination thereof is contained in a molecular skeleton in a fiber base material. A foam base (A layer) having a foam coating layer formed by foaming a foam-forming composition containing a water-based polyurethane resin having a solid content concentration of 55% or more, and a skin formed using the water-based polyurethane resin There is disclosed a method of obtaining a foam by adhering a layer (C layer) with a water-based polyurethane resin and an adhesive (B layer) containing a polyisocyanate-based crosslinking agent by a dry lamination method. However, in such a conventional foam manufacturing method as described in Patent Document 1, the foaming ratio of the composition for forming a foam to be used can not be made sufficiently high, and such a foam forming composition is used. When the artificial leather-like material (artificial leather, synthetic leather, etc.) was manufactured using the foam obtained by using the composition as a leather material, it could not be made to have sufficient texture.

  Further, in JP-A-2006-070232 (Patent Document 2), a carboxyl group is formed on a part of the molecular chain of an aqueous urethane main agent consisting of a polyether urethane-based or polycarbonate-based aqueous urethane alone or a mixture or copolymer thereof. At least a foaming agent, a foam stabilizer, an oxazoline-based crosslinking agent, and a thickener while stirring a heat-sensitive gelled aqueous urethane dispersion which is introduced and forcedly dispersed in water together with a high cloud point surfactant. No. 4,798,798 and the like. There is described a method for producing a foam characterized in that the composition for forming a foam obtained by adding is mechanically foamed and then applied to a substrate, followed by drying and heat treatment one or more times. However, in such a conventional foam manufacturing method as described in Patent Document 2, the material fracture strength of the resulting foam can not be made sufficient, and the skin layer (base material) Also, the adhesion between the resin and the foam layer could not be made sufficient.

  Furthermore, WO 2012/008336 (patent document 3) contains (A) an aqueous emulsion polyurethane resin, (B) an ammonium salt, and (C) a nonionic thickener, and (B) component Preparing a foam-forming composition comprising the aqueous dispersion (I) in an amount of 0.25 to 10 parts by mass with respect to 100 parts by mass of the solid content of the component (A), A step (2) of applying the aqueous dispersion (I) to at least one surface of the substrate to form a coating, and a step (3) of subjecting the coating to thermal gelation treatment to form a gelled film A step (4) of drying and solidifying the gelled film to form a film, and in the step (1), foaming ratio of the obtained aqueous dispersion (I) is 1.1 to 2.5 A method is disclosed for making double-foamed foam. However, in the conventional method for producing a foam as described in Patent Document 3, a foam forming composition comprising the aqueous dispersion (I) is foamed to form a coating film and then cured. In the case where the shrinkage of the coating film is large, the thickness of the foam layer is not sufficient, and the resulting foam is used as a leather material to produce a pseudoleather-like material (artificial leather, synthetic leather, etc.) In addition, it was not possible to have a sufficient texture.

  In addition, WO 2014/162986 (patent document 4) is a composition for forming a foam, which is a raw material containing either an aliphatic isocyanate or a melamine derivative, a urethane emulsion, and an anionic foam stabilizer. Are foamed by a mechanical floss method to form the floss of the raw material, and a method for producing a polyurethane foam is disclosed in which the floss is heated and dried. However, in the conventional foam manufacturing method as described in Patent Document 4, the foamability of the composition for forming a foam to be used is not sufficient, and, for example, the foaming ratio is 3 times or more. In the case where it is intended to foam in such a way, it takes a considerably long time (eg, it takes a long time to become 20 minutes or more even if the expansion ratio is tripled, Furthermore, the time until the foaming ratio is quadrupled requires a long time exceeding 20 minutes). Moreover, in the conventional foam manufacturing method as described in Patent Document 4, when the blending amount of the foaming agent is temporarily increased in order to enhance the foamability of the raw material, the strength of the foam is reduced. There was a problem of

JP 2005-273083 A JP, 2006-070232, A International Publication No. 2012/008336 International Publication No. 2014/162986

  The present invention has been made in view of the problems of the prior art, and is a foam-forming composition containing an aqueous polyurethane resin, which has a sufficiently high foamability and can be efficiently foamed. In addition to the above, it is also possible to make the thickness of the foamed resin layer made of the foamed cured product of the composition sufficient, and, in addition, when the composition is used to manufacture a leather material, Foam-forming composition capable of imparting sufficient feeling and material fracture strength; Method of producing foam using the foam-forming composition; and foam-cured product of the foam-forming composition It is an object of the present invention to provide a foam comprising the foamed resin layer; and a leather material comprising the foam.

  As a result of intensive studies to achieve the above object, the present inventors have found that (A) a self-emulsifying aqueous polyurethane resin having at least one hydrophilic functional group selected from the group consisting of sulfo group and sulfonate group Composition for foam formation obtained by containing (B) forced emulsification type aqueous polyurethane resin, (C) crosslinking agent, (D) foaming agent, (E) thickening agent, and (F) water While the composition is a composition containing an aqueous polyurethane resin, the foamability becomes sufficiently high to be able to foam efficiently, and the foamed resin layer made of a foamed cured product of the composition has a sufficient thickness It has also been found that when the leather material is manufactured using the composition, it is possible to impart sufficient texture and material fracture strength to the obtained leather material, and the present invention To complete Led was.

  That is, the foam-forming composition of the present invention comprises (A) a self-emulsifying aqueous polyurethane resin having at least one hydrophilic functional group selected from the group consisting of a sulfo group and a sulfonate group, (B) forced emulsification Type aqueous polyurethane resin, (C) crosslinking agent, (D) foaming agent, (E) thickening agent, and (F) water.

  In the composition for foam formation of the said this invention, it is preferable to further contain (G) an emulsifier.

  The component (D) (foaming agent) according to the present invention preferably comprises at least one of the following compound (D1), the following compound (D2) and the following compound (D3), It is more preferable to consist of at least one of the following compounds (D1), at least one of the following compounds (D2), and at least one of the following compounds (D3). In addition, compounds (D1) to (D3) suitably used for such (D) component (foaming agent) are shown below.

[Compound (D1)]
The following general formula (1):
R ¹ COOX ・ ・ ・ (1)
(Wherein R ¹ has an alkyl group having 11 to 29 carbon atoms which may have a hydroxyl group, an alkenyl group having 11 to 29 carbon atoms which may have a hydroxyl group, and a hydroxyl group, Or any group selected from the group consisting of alkynyl groups having 11 to 29 carbon atoms, and X is selected from the group consisting of H, Na, K and an ammonium ion which may have a substituent. It is either.)
A compound represented by

[Compound (D2)]
The following general formula (2):

(Wherein, each of two A's is independently selected from the group consisting of groups represented by formulas: R ² O—, R ² N (H) —, (R ² ) ₂ N— and XO— And at least one of the two A's is selected from the group consisting of groups represented by the formula: R ² O—, R ² N (H) — and (R ² ) ₂ N— R ² is an alkyl group having 8 to 30 carbon atoms which may have a hydroxyl group, an alkenyl group having 8 to 30 carbon atoms which may have a hydroxyl group, and a hydroxyl group which satisfy the condition that any of them is satisfied. X 8 is H, Na, K, and an ammonium ion which may have a substituent. It is one selected from the group.)
A compound represented by

[Compound (D3)]
The following general formula (3):
R ³ C (O) N (R ⁴ )-(CH ₂ ) _n -B (3)
(Wherein R ³ has an alkyl group having 7 to 29 carbon atoms which may have a hydroxyl group, an alkenyl group having 7 to 29 carbon atoms which may have a hydroxyl group, and a hydroxyl group, R ⁴ is any one selected from the group consisting of an alkynyl group having 7 to 29 carbon atoms, and R ⁴ is any one selected from the group consisting of H and an alkyl group having 1 to 3 carbon atoms, n Is an integer of 1 to 3, B is any one selected from the group consisting of groups represented by the formula COOX and SO ₃ X, and X is H, Na, K and a substituent Is selected from the group consisting of ammonium ions which may have
A compound represented by

  Furthermore, in the composition for foam formation of the said this invention, it is preferable to further contain (H) thermosensitive gelling agent.

  The method for producing a foam according to the present invention further comprises the steps of obtaining a foam composition obtained by foaming the composition for forming a foam according to the present invention, applying the foam composition to a substrate, drying and curing it. And obtaining a foam having a foamed resin layer formed of a foamed cured product of the composition for forming a foam formed on a material.

  In the foam manufacturing method of the present invention, the composition for forming a foam is an aqueous dispersion (I) of an aqueous polyurethane resin in which the content of the component (A) is 50 to 70% by mass, Aqueous dispersion (II) of an aqueous polyurethane resin containing the component (B) and an emulsifier and having a content of the component (B) of 30 to 70% by mass, the component (C), the component (D) And it is preferable that it is what was obtained by mixing the said (E) component.

  Moreover, in the manufacturing method of the foam of the said this invention, it is preferable to foam the said composition for foam formation by the expansion ratio of 1.5-5 times in the process of obtaining the said foaming composition.

The foam of the present invention is
A substrate,
A foamed resin layer composed of a foamed and cured product of the composition for forming a foam according to the present invention, laminated on the substrate;
And the like.

  The leather material of the present invention comprises the foam of the present invention.

  According to the present invention, while being a foam-forming composition containing an aqueous polyurethane resin, the foamability is sufficiently high, and it is possible to foam efficiently, and the foam is formed of a foam-cured product of the composition. It is also possible to make the thickness of the resin layer sufficient, and furthermore, when a leather material is manufactured using the composition, giving sufficient texture and material fracture strength to the obtained leather material Foamable composition; a method for producing a foam using the foam-forming composition; a foam comprising a foamed resin layer comprising a foamed cured product of the foam-forming composition; It is possible to provide a leather material provided with a body.

  Hereinafter, the present invention will be described in detail in line with its preferred embodiments.

[Composition for forming foam]
The foam-forming composition of the present invention comprises (A) a self-emulsifying aqueous polyurethane resin having at least one hydrophilic functional group selected from the group consisting of a sulfo group and a sulfonate group, (B) a forced emulsifying type aqueous It is characterized by containing a polyurethane resin, (C) crosslinking agent, (D) a foaming agent, (E) a thickener, and (F) water. Hereinafter, first, each component is divided and demonstrated.

<(A) Component: Self-Emulsification Type Aqueous Polyurethane Resin>
The self-emulsifying aqueous polyurethane resin contained as the component (A) in the present invention is a self-emulsifying aqueous polyurethane resin having at least one hydrophilic functional group selected from the group consisting of a sulfo group and a sulfonate group ( Hereinafter, in some cases, such component (A) is simply referred to as "self-emulsifying type aqueous polyurethane resin"). Here, with respect to the self-emulsifiable aqueous polyurethane resin (component (A)), "aqueous" refers to an emulsion dispersion (solvent: water) having a concentration of 40% by mass of the polyurethane resin in water. It means that it is possible to make it in such a state that separation or sedimentation is not observed even if it is allowed to stand at 20 ° C for 12 hours.

  Such a self-emulsifying aqueous polyurethane resin (component (A)) has at least one hydrophilic functional group selected from the group consisting of a sulfo group and a sulfonate group. Thus, since the self-emulsifying aqueous polyurethane resin (component (A)) according to the present invention has at least one hydrophilic functional group selected from the group consisting of sulfo group and sulfonate group, the emulsifier (resin is emulsified) It has self-emulsifiability that can be emulsified and dispersed in water without using a surfactant). Thus, the self-emulsifying aqueous polyurethane resin (component (A)) is an aqueous polyurethane resin of a type capable of being emulsified and dispersed in water without using an emulsifier (surfactant for emulsifying the resin), That is, it is an aqueous polyurethane resin of a type capable of self-emulsification (a type having self-emulsifiability).

Such a self-emulsifying aqueous polyurethane resin (component (A)) has a hydrophilic functional group consisting of a sulfo group and / or a sulfonate group, and can be emulsified and dispersed without using a surfactant. Any resin may be used, and in addition to the sulfo group and / or the sulfonate group, it may have other hydrophilic functional groups such as a carboxy group, a carboxylate group and a quaternary ammonium group. In the present invention, “sulfo group” refers to a group represented by the formula: —SO ₃ H, “sulfonate group” refers to a group represented by the formula: —SO ₃ ^— , “carboxy group” the formula refers to a group represented by -COOH, the term "carboxylate group" formula: -COO ^- refers to a group represented by.

  Such a self-emulsifying aqueous polyurethane resin (component (A)) has, in addition to the sulfo group and / or the sulfonate group, other hydrophilic functional groups such as a carboxy group, a carboxylate group and a quaternary ammonium group. In the above case, the content of sulfo group and / or sulfonate group in all hydrophilic functional groups including other hydrophilic functional groups is preferably 70 to 100 mol%, and is 80 to 100 mol%. Is more preferable, and 90 to 100 mol% is particularly preferable. When the content ratio of such a sulfo group and a sulfonate group is less than the above lower limit, it is difficult to increase the concentration of the resin (high solid differentiation) when producing an aqueous dispersion of a polyurethane resin, and the obtained foam It tends to be difficult to achieve the desired performance in the forming composition.

  In addition, as such a self-emulsifying type aqueous polyurethane resin (component (A)), it is possible to obtain a higher peel strength while making it possible to foam at a higher foaming ratio, and it is possible to obtain the above-mentioned hydrophilicity. It is preferable that it is an aqueous polyurethane resin having only at least one type of functional group selected from the group consisting of a sulfo group and a sulfonate group in the resin skeleton as the functional group.

Furthermore, as such a self-emulsifying type aqueous polyurethane resin (component (A)), a sulfo group can be obtained from the viewpoint that higher peel strength can be obtained while enabling foaming at a higher expansion ratio. The content of at least one hydrophilic functional group selected from the group consisting of and sulfonate groups is preferably 0.1 to 15 meq. Per 100 g of the polyurethane resin. From the same viewpoint, when the component (A) contains a carboxy group or a carboxylate group as a hydrophilic functional group (anionic group) together with a sulfo group and / or a sulfonate group, these hydrophilic groups The content of functional groups is preferably 0.1 to 15 milliequivalents per 100 g of polyurethane resin. The content of the hydrophilic functional group per 100 g of the polyurethane resin is, for example, per 100 g of the polyurethane resin when a carboxy group and / or a carboxylate group is contained together with the sulfo group and / or the sulfonate group as the hydrophilic functional group. The content of the hydrophilic functional group can be determined by calculating the total of the SO ₃ amount and the COO amount per 100 g of the polyurethane resin (in addition, only the sulfo group and / or the sulfonate group may be used as the hydrophilic functional group). When it is contained, it can be obtained by calculating the total of the SO ₃ amount per 100 g of polyurethane resin).

  Such a self-emulsifying aqueous polyurethane resin (component (A)) is not particularly limited, but, for example, (a) organic polyisocyanate, (b) polyol, (c) sulfo group and / or sulfonate group The sulfo group- and / or sulfonate group-containing isocyanate group-terminated prepolymer obtained by reacting a compound having at least one active hydrogen and at least one hydrogen is self-emulsified in water, and then the (d) chain extender is It is preferable that it is an aqueous polyurethane resin having a sulfo group and / or a sulfonate group which is obtained by chain extension reaction. Such components (a) to (d) will be described separately.

(A) Organic Polyisocyanate Organic polyisocyanate (component (a) above) used as a raw material of such aqueous polyurethane resin is not particularly limited, and is an aliphatic polyisocyanate having two or more isocyanate groups, two The alicyclic polyisocyanate which has the above isocyanate group, and the aromatic polyisocyanate which has 2 or more isocyanate groups can be used.

  Examples of such aliphatic polyisocyanate compounds having two or more isocyanate groups include aliphatic diisocyanate compounds such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate. Further, as the alicyclic polyisocyanate having two or more isocyanate groups, for example, isophorone diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, cyclohexylmethane diisocyanate, norbornane diisocyanate, 1,3-bis (isocyanatomethyl) And cycloaliphatic diisocyanate compounds such as cyclohexane. Furthermore, examples of the aromatic polyisocyanate having two or more isocyanate groups include aromatic diisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, and the like. . The organic polyisocyanate used as such a component (a) is an aliphatic polyisocyanate having two or more isocyanate groups, an alicyclic polyisocyanate having two or more isocyanate groups, and 2 as described above. In addition to polyisocyanate compounds such as aromatic polyisocyanates having one or more isocyanate groups, alkyl-substituted products, alkoxy-substituted products of these polyisocyanate compounds, nitro-substituted products, and pre-products of these polyisocyanate compounds and polyhydric alcohols Polymer type modified product, carbodiimide modified product of these polyisocyanate compounds, urea modified product of these polyisocyanate compounds, Buret modified product of these polyisocyanate compounds, dimerization or tris of these polyisocyanate compounds Over reaction products, and the like may be appropriately used. One of such organic polyisocyanates (component (a)) may be used alone, or two or more thereof may be used in combination.

  Further, among such organic polyisocyanates, aliphatic polyisocyanate compounds and alicyclic polyisocyanate compounds are preferable from the viewpoint of resistance to yellowing, thermal stability and light stability of a film to be formed, and hexamethylene diisocyanate, Isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexylmethane diisocyanate, norbornane diisocyanate and 1,3-bis (isocyanatomethyl) cyclohexane are more preferred.

(B) Polyol The polyol (component (b)) used as a raw material of such an aqueous polyurethane resin is not particularly limited as long as it has two or more hydroxyl groups, and is used as a raw material of a polyurethane resin Well-known polyols which can be used can be used suitably. As such a polyol (component (b)), for example, polyester polyol, polycarbonate polyol, polyether polyol, polyether ester polyol having an ether bond and an ester bond, and the like can be suitably used.

  Examples of the polyester polyol include polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyhexamethylene isophthalate adipate diol, polyethylene succinate diol, polybutylene succinate diol, polyethylene sebacate diol, and polybutylene sebacate. Diol, poly-ε-caprolactone diol, poly (3-methyl-1,5-pentylene) adipate diol, polycondensate of 1,6-hexanediol and dimer acid, 1,6-hexanediol, adipic acid and dimer acid And polycondensates of nonanediol and dimer acid, copolycondensates of ethylene glycol and adipic acid and dimer acid, and the like.

  As said polycarbonate polyol, polycarbonate diol manufactured using a diol and carbonic acid diester as a raw material and using a transesterification catalyst can be mentioned, for example. Examples of the diol include diols having 1 to 20 carbon atoms which may contain a hetero atom, and may be linear or branched chain groups, cyclic groups, or diols of any structure. Moreover, as said hetero atom, an oxygen atom, a sulfur atom, a nitrogen atom etc. are mentioned. Moreover, as said carbonic diester, an alkyl carbonate, an aryl carbonate, and an alkylene carbonate etc. are mentioned, for example. As such polycarbonate diols, commercially available products may be appropriately used. For example, BENEBiOL NL series manufactured by Mitsubishi Chemical Co., Ltd., Duranol series manufactured by Asahi Kasei Corp., Kuraray polyol series manufactured by Kuraray Co., Ltd., etc. may be mentioned. be able to.

  Examples of the polyether polyols include diols which are homo- or co-addition polymers of C 2 -C 4 alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, trimethylene oxide and tetramethylene oxide; And polyols obtained by random or block addition of the above-mentioned C 2 -C 4 alkylene oxide to a polyhydric alcohol such as trimethylolpropane.

  Such polyols (component (b)) may be used alone or in combination of two or more. The weight average molecular weight of such a polyol is preferably 500 to 5,000, and more preferably 1,000 to 3,000. Moreover, it is preferable to use a polycarbonate polyol and / or a polyether polyol as said polyol from a viewpoint that sufficient durability can be provided to a base material by the polyurethane resin obtained.

(C) Compound Having a Sulfo Group and / or a Sulfonate Group and Two or More Active Hydrogens As a compound having a sulfo group and / or a sulfonate group and two or more active hydrogens (component (c)), for example, 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2- (2-aminoethylamino) ethanesulfonic acid, ethylenediaminepropylsulfonic acid, ethylenediaminebutylsulfonic acid, 1,2- or Diaminosulfonic acid such as 1,3-propylenediamine-β-ethylsulfonic acid, 2- (3-aminopropylamino) -ethanesulfonic acid, 2,4-diaminobenzenesulfonic acid; and salts thereof (eg alkali metal Salt etc.).

  In addition, examples of the compound having a sulfo group and / or a sulfonate group and two or more active hydrogens include dihydroxy sulfonic acids such as an adduct of sodium bisulfite to 2-butene-1,4-diol; a sulfo group and Polyester polyols having pendant hydrophilic functional groups obtained by reacting diols having at least one hydrophilic functional group selected from the group consisting of sulfonate groups with aromatic dicarboxylic acids, aliphatic dicarboxylic acids and the like; Etc. These (c) components can also be used individually or in combination of 2 or more types.

  Furthermore, in the case of introducing a carboxy group and / or a carboxylate group into the obtained aqueous polyurethane resin, a compound having a carboxy group and / or a carboxylate group and two or more active hydrogens together with the component (c) It is preferred to use. As a compound having such a carboxy group and / or carboxylate group and two or more active hydrogens, for example, 2,2-dimethylol lactic acid, 2,2-dimethylol propionic acid, 2,2-dimethylol butane Examples of the acid include dihydroxycarboxylic acid such as acid and 2,2-dimethylolvaleric acid.

(D) Chain Elongation Agent The chain elongation agent (component (d)) used as a raw material of such an aqueous polyurethane resin is not particularly limited, but, for example, a polyamine compound having two or more amino groups and / or imino groups Can be mentioned.

  Examples of such polyamine compounds having two or more amino groups and / or imino groups include ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, diaminocyclohexylmethane, piperazine, hydrazine, 2-methylpiperazine, isophoronediamine , Diamines such as norbornane diamine, diaminodiphenylmethane, tolylene diamine, xylylene diamine; polyamines such as diethylene triamine, triethylene tetramine, tetraethylene pentamine, iminobispropylamine, tris (2-aminoethyl) amine; Amide amines derived from amines and monocarboxylic acids; water-soluble amine derivatives such as monoketimines of diprimary amines; boric acid dihydrazide, malonic acid dihydrazide, 琥珀Dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide, 1,1'-ethylenehydrazine, 1,1'-trimethylenehydrazine, 1,1 '-(1 And hydrazine derivatives such as (4-butylene) dihydrazine. As such polyamine compounds having two or more amino groups and / or imino groups, one type may be used alone, or two or more types may be used in combination.

<Method of Preparing Self-Emulsifying Aqueous Polyurethane Resin>
The self-emulsifiable aqueous polyurethane resin (component (A): hereinafter referred to as “self-emulsifiable aqueous polyurethane resin having a sulfo group and / or sulfonate group” as the case may be) component (a), component (b) (C) The component (c) is reacted to prepare a sulfonate group-terminated prepolymer neutralized with a sulfo group and / or a sulfonate group, and after self-emulsification in water, a chain is formed using a chain extender (d) It is obtained by the elongation reaction. Thus, the polyurethane resin having a sulfo group and / or a sulfonate group is a self-neutralized product of an isocyanate group-terminated prepolymer having a sulfonate group (hereinafter, sometimes referred to as "SU isocyanate group-terminated prepolymer neutralized material"). The polyurethane resin can be obtained by emulsification dispersion in water by emulsification and chain extension reaction, and according to such a preparation method, such a polyurethane resin is suitably used as an emulsion dispersion of a polyurethane resin (water dispersion (I) described later) Can be obtained as Although such a self-emulsification type aqueous polyurethane resin may be used by taking out only the resin component from the above-mentioned emulsion dispersion, it is easier to prepare the composition, and therefore, it is possible to use an emulsion dispersion of polyurethane resin. It is preferable to utilize for preparation of a composition in a state.

The SU isocyanate group-terminated prepolymer neutralized product is a sulfonate group (--having a sulfo group derived from a compound having a sulfo group and / or a sulfonate group and two or more active hydrogens (component (c)) neutralized (- It is an isocyanate group-terminated prepolymer neutralized product having SO ₃ ⁻ ), and the (a) organic polyisocyanate, the (b) polyol and (c) a sulfo group and / or a sulfonate group and two or more active hydrogens. It is obtained by reacting the compound which it has. The specific method for obtaining such a SU isocyanate group-terminated prepolymer is not particularly limited, and, for example, by a conventionally known one-stage so-called one-shot method, multistage isocyanate polyaddition reaction method, etc. It can be manufactured. It is preferable that the reaction temperature at this time is 40-150 degreeC.

  Moreover, in such a reaction, a low molecular weight chain extender having two or more active hydrogen atoms can be used, if necessary. The low molecular weight chain extender preferably has a molecular weight of 400 or less, and more preferably 300 or less. Moreover, as the low molecular weight chain extender, for example, low molecular weight polymers such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, sorbitol and the like And low molecular weight polyamines such as ethylenediamine, propylenediamine, hexamethylenediamine, diaminocyclohexylmethane, piperazine, 2-methylpiperazine, isophorone diamine, diethylenetriamine and triethylenetetramine. Furthermore, as the low molecular weight chain extender, one type may be used alone, or two or more types may be used in combination.

  Furthermore, during the reaction, if necessary, a reaction catalyst such as dibutyltin dilaurate, stannas octoate, dibutyltin 2-ethylhexanoate, triethylamine, triethylenediamine, N-methylmorpholine, etc. is added. Can. In addition, an organic solvent that does not react with an isocyanate group can be added during or after the reaction. Examples of the organic solvent include acetone, methyl ethyl ketone, toluene, tetrahydrofuran, dioxane, dimethylformamide, N-methyl pyrrolidone, ethyl acetate, methyl isobutyl ketone and the like.

  The neutralization of the sulfo group derived from the compound (c) having a sulfo group and two or more active hydrogens may be simultaneous with the preparation of the isocyanate group-terminated prepolymer, even before or after the preparation. It may be Such neutralization can be appropriately performed using a known method, and the compound used for such neutralization is not particularly limited, and examples thereof include trimethylamine, triethylamine, tri-n-propylamine and tributylamine. And amines such as N-methyl-diethanolamine, N, N-dimethylmonoethanolamine, N, N-diethylmonoethanolamine and triethanolamine; potassium hydroxide; sodium hydroxide; ammonia and the like. Among these, tertiary amines such as trimethylamine, triethylamine, tri-n-propylamine and tributylamine are particularly preferable.

  There is no particular limitation on the method of emulsifying and dispersing the above-described SU isocyanate group-terminated prepolymer in water, and examples thereof include a method using an emulsifying device such as a homomixer, homogenizer, and disper. Further, when the neutralized product of the above-described SU isocyanate group-terminated prepolymer is emulsified and dispersed in water, the prepolymer neutralized product is emulsified in water by self-emulsification in a temperature range of room temperature to 40 ° C. without using an emulsifier. It is preferable to disperse to minimize the reaction between the isocyanate group and water. Furthermore, when emulsifying and dispersing in this manner, reaction inhibitors such as phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, p-toluenesulfonic acid, adipic acid, benzoyl chloride and the like are added as necessary. be able to.

  In the chain extension reaction of the neutralized product of the SU isocyanate group-terminated prepolymer, is it possible to add a polyamine compound having two or more of the (d) amino group and / or imino group to the neutralized product of the SU isocyanate group-terminated prepolymer? Or it can carry out by adding the said SU isocyanate group terminal prepolymer neutralized material to the polyamine compound which has 2 or more of said (d) amino group and / or imino group. Such a chain extension reaction is preferably carried out at a reaction temperature of 20 to 40 ° C., and is usually completed in 30 to 120 minutes.

  In the method for preparing an aqueous polyurethane resin having such a sulfo group and / or a sulfonate group, the emulsifying dispersion and the chain extension reaction may be simultaneous, and the above-described SU isocyanate group-terminated prepolymer neutralized product May be emulsified and dispersed, or may be emulsified and dispersed after chain elongation reaction. Moreover, when using the above-mentioned organic solvent when manufacturing a SU isocyanate group terminal prepolymer neutralized material, it is preferable to remove an organic solvent by pressure reduction etc., for example, after chain extension reaction or emulsification dispersion. Furthermore, although a polyurethane resin can be obtained as an emulsion dispersion of a polyurethane resin by such a preparation method, such an emulsion dispersion may further contain an emulsifier. As such an emulsifying agent, the same one as the emulsifying agent to be used when preparing the forced emulsification type aqueous polyurethane resin described later can be appropriately used.

<(B) Forced emulsification type aqueous polyurethane resin>
The forced emulsification type aqueous polyurethane resin contained as the component (B) in the present invention does not have a hydrophilic functional group (such as a sulfo group, a sulfonate group, a carboxy group, a carboxylate group, a quaternary ammonium group). In order to emulsify, it is necessary to add an emulsifier (surfactant), and it is an aqueous polyurethane resin of a type (forced emulsification type) which can be forcibly emulsified by the emulsifier (surfactant). Thus, the forced emulsification type aqueous polyurethane resin (component (B)) is a type which does not have self-emulsifiability and which can be forcibly emulsified by an emulsifier (surfactant) (forced (forced) Emulsion type) aqueous polyurethane resin. Incidentally, in such a forced emulsifying type aqueous polyurethane resin, "aqueous" is obtained by forcibly emulsifying using an emulsifying agent (surfactant) so that the concentration of the polyurethane resin in water becomes 40% by mass. This means that the emulsified dispersion (solvent: water) can be in such a state that separation or sedimentation can not be observed even if it is allowed to stand at 20 ° C. for 12 hours.

  As such a forced emulsifying type aqueous polyurethane resin, for example, an isocyanate group-terminated prepolymer obtained by reacting the component (a) (organic polyisocyanate) with the component (b) (polyol) is used as an emulsifier (interface It is preferable that it is a forced emulsifying type aqueous polyurethane resin obtained by emulsion-dispersing in water in the presence of an activator) and then performing chain elongation reaction using a chain extender (d).

<About the preparation method of forced emulsification type aqueous polyurethane resin>
When preparing such a forced emulsifying type aqueous polyurethane resin, first, the component (a) (organic polyisocyanate) and the component (b) (polyol) are reacted to form an isocyanate group-terminated prepolymer (at the end) (Urethane prepolymer having an isocyanate group) is prepared. The method for preparing such an isocyanate group-terminated prepolymer (urethane prepolymer having an isocyanate group at the end) is not particularly limited, and the component (c) (sulfo group and / or sulfonate group and two or more groups) A method similar to the method for obtaining the above-mentioned SU isocyanate-terminated prepolymer neutralized product can be adopted except that the compound having an active hydrogen) is not used.

  In addition, when preparing a forced emulsification type aqueous polyurethane resin, after preparing a urethane prepolymer having an isocyanate group at the end as described above, the urethane prepolymer is subjected to emulsification dispersion and chain elongation reaction to produce a forced emulsification type An aqueous polyurethane resin is obtained. Thus, there is no particular limitation on the method for obtaining a forced emulsification type aqueous polyurethane resin by subjecting the urethane prepolymer having an isocyanate group at the end to emulsion dispersion and chain extension reaction, and the above-mentioned SU isocyanate group terminated prepolymer neutralized In the method for producing a polyurethane resin having a sulfo group and / or a sulfonate group, except that it is necessary to use a urethane prepolymer having an isocyanate group at the end, and it is necessary to use an emulsifier at the time of emulsifying and dispersing. A method similar to the one described can be employed. That is, in place of the neutralized product of the SU isocyanate group-terminated prepolymer, a urethane prepolymer having an isocyanate group at the end is used, and an emulsifier is dispersed when the urethane prepolymer having an isocyanate group at the end is emulsified and dispersed in water. It may be used to emulsify and disperse as well as the chain elongation reaction, and as the method of the emulsification dispersion and the chain elongation reaction, it is the same as the method described in the method of producing the polyurethane resin having a sulfo group and / or a sulfonate group. The method of can be adopted.

  Moreover, it is preferable to use a nonionic surfactant as an emulsifier used when carrying out emulsification dispersion of the urethane prepolymer which has an isocyanate group in such a terminal. Among such nonionic surfactants, polyoxyethylene distyryl phenyl ether type nonionic surfactant, polyoxyethylene propylene distyryl phenyl ether type nonionic surfactant, polyoxyethylene tristyryl ester among the above-mentioned nonionic surfactants. Phenyl ether type nonionic surfactants, polyoxyethylene propylene tristyryl phenyl ether type nonionic surfactants, and pluronic type nonionic surfactants can be particularly preferably used.

  The amount of non-ionic surfactant added as such an emulsifying agent differs depending on the hydrophilicity resulting from the polyoxyethylene group content of the urethane prepolymer which is the material to be emulsified, etc. The amount is preferably 0.5 to 10 parts by mass, and more preferably 1 to 6 parts by mass with respect to 100 parts by mass of the urethane prepolymer. If the amount of the nonionic surfactant as such an emulsifier is less than the lower limit, it tends to be difficult to obtain a sufficiently stable emulsified and dispersed state, while if it exceeds the upper limit, a foam layer is formed. At the same time, the water resistance of the foam layer tends to decrease.

  When such a preparation method is adopted, the forced emulsification type aqueous polyurethane resin is obtained by emulsifying and dispersing the polyurethane resin in water in the presence of an emulsifier of a urethane prepolymer having an isocyanate group at the end and by chain elongation reaction. It can be obtained as a liquid (which can be suitably used as an aqueous dispersion (II) described later). Although such a forced emulsifying type aqueous polyurethane resin may be used by taking out only the resin component from the above-mentioned emulsified dispersion, it is easier to prepare the composition, so in the state of the emulsified dispersion of the polyurethane resin It is preferable to utilize for preparation of a composition.

<(C) Crosslinking agent>
The crosslinking agent used as the component (C) in the present invention is not particularly limited, and a known crosslinking agent capable of crosslinking the polyurethane resin can be appropriately used. For example, an isocyanate crosslinking agent, an oxazoline crosslinking agent, Epoxy based crosslinking agents, aziridine based crosslinking agents, carbodiimide based crosslinking agents, formaldehyde resins, melamine resins and glyoxal resins can be used.

  Among these, an isocyanate-based crosslinking agent is more preferable as such a crosslinking agent (component (C)) from the viewpoint of further improving the peel strength. As such an isocyanate type crosslinking agent, aliphatic, alicyclic or aromatic polyisocyanate can be utilized. As such an isocyanate type crosslinking agent, for example, liquid MDI such as tolylene diisocyanate, diphenylmethane diisocyanate (MDI), polyphenyl polymethyl polyisocyanate, crude MDI, hexamethylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, Examples thereof include hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, trimers that are isocyanurate rings thereof, trimethylolpropane adducts, and compounds obtained by protecting the isocyanate group with a blocking agent.

  Moreover, as such a blocking agent, phenol, ε-caprolactam, 2-butanone oxime, bisulfite, bisulfite, dimethylpyrazole and the like can be mentioned. Among them, dimethylpyrazole having a relatively low thermal dissociation temperature is more preferable. . As such an isocyanate type crosslinking agent, self-emulsifying polyisocyanate having a hydrophilic functional group in the structure can also be used.

  Moreover, as such an isocyanate type crosslinking agent, aliphatic or alicyclic polyisocyanate is preferable among them from the viewpoint of light resistance. In addition, you may utilize a commercial item suitably as such aliphatic or alicyclic polyisocyanate, for example, a hygidur 3100 (made by Sumika Kovestrourethane), aquanate 110, 210 (made by Nippon Polyurethane), NK assist IS-100N, NY-27, NY-30, NY-50 (manufactured by Nikka Chemical Co., Ltd.), TRIXENE AQUA BI220 (manufactured by BAXENDEN), and the like can be appropriately used.

  In addition, such a crosslinking agent (component (C)) can be used for dilution when preparing the composition, from the viewpoint that the drying time can be further shortened, and the shrinkage of the foam during drying can be highly suppressed. It is preferable to add it as it is without adding it.

<(D) Foaming agent>
It does not restrict | limit especially as a foaming agent contained as (D) component in this invention, The well-known foaming agent which can be utilized in order to foam a polyurethane resin can be utilized suitably. As such a foaming agent ((D) component), an anionic surfactant can be used, for example.

  As an anionic surfactant which can be utilized as such a foaming agent (component (D)), for example, a sulfate ester type anionic surfactant, an amino acid type anionic surfactant, a phosphate type anionic surfactant Agents, carboxylic acid anionic surfactants, sulfonic acid anionic surfactants. Further, from the viewpoint of further improving the stability of the composition for forming a foam and enabling the formation of a foam having a fine cell structure, etc., as such an anionic surfactant, neutralization is possible. More preferably, it is in the form of a formulated salt.

  Moreover, as such a sulfate ester type anionic surfactant, an alkyl sulfate, a polyoxyalkylene alkyl ether sulfate, and a polyoxyalkylene alkyl monoalkylol amide sulfate can be mentioned. Furthermore, as such an amino acid based anionic surfactant, there can be mentioned acyl glycinate, acyl sarcosinate, acyl alaninate, acyl alkyl alaninate, acyl taurate, acyl alkyl taurate and acyl glutamate. Moreover, as said phosphoric acid ester type | system | group anionic surfactant, an alkyl phosphoric acid ester salt, a polyoxyalkylene alkyl ether phosphoric acid ester salt, etc. can be mentioned. Further, as the carboxylic acid type anionic surfactant, higher fatty acid salts, polyoxyethylene alkyl ether carboxylates and the like can be mentioned. Furthermore, as the sulfonic acid based anionic surfactant, olefin (C14-16) sulfonate, alkyl sulfosuccinate, polyoxyethylene sulfosuccinate alkyl salt, alkyl ethyl ester sulfonate, sulfosuccinate alkylamide, alkyl Diphenyl ether disulfonate and the like can be mentioned. As such a foaming agent, one type may be used alone, or two or more types may be arbitrarily combined and used. Therefore, as said foaming agent, 1 type of anionic surfactant may be used independently, or 2 or more types may be combined arbitrarily and it may be used.

In addition, the following compounds (D1) to (D3) from the viewpoint that a foam having a fine cell structure can be formed more efficiently as the foaming agent (component (D)) according to the present invention :
[Compound (D1)]
The following general formula (1):
R ¹ COOX ・ ・ ・ (1)
(Wherein R ¹ has an alkyl group having 11 to 29 carbon atoms which may have a hydroxyl group, an alkenyl group having 11 to 29 carbon atoms which may have a hydroxyl group, and a hydroxyl group, Or any group selected from the group consisting of alkynyl groups having 11 to 29 carbon atoms, and X is selected from the group consisting of H, Na, K and an ammonium ion which may have a substituent. It is either.)
A compound (D1) represented by
[Compound (D2)]
The following general formula (2):

(Wherein, each of two A's is independently selected from the group consisting of groups represented by formulas: R ² O—, R ² N (H) —, (R ² ) ₂ N— and XO— And at least one of the two A's is selected from the group consisting of groups represented by the formula: R ² O—, R ² N (H) — and (R ² ) ₂ N— R ² is an alkyl group having 8 to 30 carbon atoms which may have a hydroxyl group, an alkenyl group having 8 to 30 carbon atoms which may have a hydroxyl group, and a hydroxyl group which satisfy the condition that any of them is satisfied. X 8 is H, Na, K, and an ammonium ion which may have a substituent. It is one selected from the group.)
A compound represented by (D2),
[Compound (D3)]
The following general formula (3):
R ³ C (O) N (R ⁴ )-(CH ₂ ) _n -B (3)
(Wherein R ³ has an alkyl group having 7 to 29 carbon atoms which may have a hydroxyl group, an alkenyl group having 7 to 29 carbon atoms which may have a hydroxyl group, and a hydroxyl group, R ⁴ is any one selected from the group consisting of an alkynyl group having 7 to 29 carbon atoms, and R ⁴ is any one selected from the group consisting of H and an alkyl group having 1 to 3 carbon atoms, n Is an integer of 1 to 3, B is any one selected from the group consisting of groups represented by the formula COOX and SO ₃ X, and X is H, Na, K and a substituent Is selected from the group consisting of ammonium ions which may have
A compound (D3) represented by
It is preferred to use any compound of the following.

With regard to the compound (D1) represented by the above general formula (1), R ¹ in the formula (1) has an alkyl group having 11 to 29 carbon atoms which may have a hydroxyl group, or a hydroxyl group It is any group selected from the group consisting of an alkenyl group having 11 to 29 carbon atoms and an alkynyl group having 11 to 29 carbon atoms which may have a hydroxyl group. The alkyl group, the alkenyl group and the alkynyl group which can be utilized as R ¹ in the formula (1) are all those having 11 to 29 carbon atoms. As R ¹ in the formula (1), the stability of the composition for forming a foam is further improved, the foam having a fine cell structure can be formed, and the texture and strength are improved. From the viewpoint of being able to form a higher foam, it is preferably a group not having a hydroxyl group, and among them, an alkyl group having 13 to 23 carbon atoms is preferable, and an alkyl having 15 to 19 carbon atoms is preferable. The group is more preferable, the alkyl group having 16 to 18 carbon atoms is further preferable, and the alkyl group having 17 carbon atoms is particularly preferable.

In addition, X in such formula (1) is any one selected from the group consisting of H, Na, K and an ammonium ion which may have a substituent. As a substituent in the ammonium ion which may have such a substituent, a hydroxyethyl group, a methyl group, an ethyl group etc. are mentioned, for example. As such X, the stability of the composition for forming a foam is further improved, the formation of a foam having a fine cell structure is possible, and the formation of a foam having higher texture and strength is possible. From the viewpoint of being possible, Na, K or an ammonium ion which may have a substituent is preferable, and an ammonium ion (NH ₄ ⁺ ) is particularly preferable.

  Examples of the compound (D1) represented by the general formula (1) include ammonium stearate, ammonium palmitate, ammonium oleate and the like, but the stability of the composition for forming a foam is further improved Ammonium stearate is particularly preferred from the viewpoints of being able to form a foam having a fine cell structure and being able to form a foam with higher texture and strength. In addition, such a compound (D1) may be used individually by 1 type, or may be used combining 2 or more types.

With regard to the compound (D2) represented by the above general formula (2), two A's in the formula (2) are each independently of the formula: R ² O—, R ² N (H) —, (R ² ) ₂ It is any one selected from the group consisting of a group represented by N- and XO-. In addition, in such a compound (D2), a group in which at least one of two A's is a group represented by the formula: R ² O-, R ² N (H)-and (R ² ) ₂ N- It is necessary to satisfy the condition that it is one selected from

As the two A in the formula (2), the stability of the composition for forming a foam is further improved, the foam having a fine cell structure can be formed, and the feel and strength and It is preferable that at least one of A is a group represented by the formula: R ² N (H)-from the viewpoint of being able to form a higher foam, and at least one of the two A More preferably, is a group represented by the formula: R ² N (H)-and the other is a group represented by the formula: XO-.

In addition, in A in such formula (2), R ² is an alkyl group having 8 to 30 carbon atoms which may have a hydroxyl group, or a carbon number 8 to 30 which may have a hydroxyl group. It is any group selected from the group consisting of a C8-C30 alkynyl group which may have an alkenyl group and a hydroxyl group. The alkyl group, the alkenyl group and the alkynyl group which can be utilized as such R ² are all those having 8 to 30 carbon atoms. As such R ² , the stability of the composition for forming a foam is further improved, the formation of a foam having a fine cell structure becomes possible, and the formation of a foam having higher texture and strength It is preferable that it is a group which does not have a hydroxyl group from a viewpoint that it becomes possible, Among these, a C8-C26 alkyl group is preferable, a C10-C20 alkyl group is more preferable, carbon It is particularly preferable that it is an alkyl group of the formula 12-18. When A in the formula (2) is a group represented by the formula: XO-, such X is H, Na, K, and a group consisting of ammonium ions which may have a substituent. It is one that is selected. As X in the group represented by the formula: XO- as such A, the stability of the composition for forming a foam can be further improved, and a foam having a fine cell structure can be formed. Na is more preferably Na from the viewpoint of being able to form a foam with higher texture and strength, that is, when A is a group represented by the formula: XO-, the formula: It is more preferable that it is a group represented by NaO-).

In addition, X in the moiety represented by the formula: -SO ₃ X in such formula (2) is also selected from the group consisting of H, Na, K and ammonium ion which may have a substituent. It is. As such X, from the same viewpoint as the preferable one of R ² , Na, K or an ammonium ion which may have a substituent is preferable, Na and K are more preferable, and Na is Is particularly preferred.

  As the compound (D2) represented by the general formula (2), for example, sulfosuccinic acid monoalkylamide sodium salt (wherein the alkyl group is one having 8 to 30 carbon atoms and 12 to 18 carbon atoms) Are preferable, and sulfosuccinic acid monoalkylamide potassium salt (in which the alkyl group is one having 8 to 30 carbon atoms and one having 12 to 18 carbon atoms is preferable), and among them, a composition for forming a foam is preferable. From the viewpoint of further improving the stability of the foam, enabling the formation of a foam having a fine cell structure, and enabling the formation of a foam with higher texture and strength. Amide sodium salt is more preferred. In addition, such a compound (D2) may be used individually by 1 type, or may be used combining 2 or more types.

With regard to the compound (D3) represented by the above general formula (3), R ³ in the formula (3) has an alkyl group having 7 to 29 carbon atoms which may have a hydroxyl group, or a hydroxyl group It is any group selected from the group consisting of an alkenyl group having 7 to 29 carbon atoms and an alkynyl group having 7 to 29 carbon atoms which may have a hydroxyl group. The alkyl group, the alkenyl group and the alkynyl group which can be utilized as such R ³ are all those having 7 to 29 carbon atoms. As such R ³ , the stability of the composition for forming a foam is further improved, the formation of a foam having a fine cell structure becomes possible, and the formation of a foam having higher texture and strength It is preferable that it is a group which does not have a hydroxyl group from a viewpoint that it becomes possible, and among them, it is preferable that it is a C7-C29 alkyl group, and it is a C7-C21 alkyl group. The alkyl group is more preferably an alkyl group having 9 to 15 carbon atoms, particularly preferably an alkyl group having 9 to 13 carbon atoms, and most preferably an alkyl group having 11 carbon atoms.

Further, R ⁴ in the formula (3) is any one selected from the group consisting of H and an alkyl group having 1 to 3 carbon atoms. As such R ⁴ , the stability of the composition for forming a foam is further improved, the formation of a foam having a fine cell structure becomes possible, and the formation of a foam having higher texture and strength It is preferable that it is a C1-C3 alkyl group from a viewpoint that it becomes possible, It is more preferable that it is a methyl group and an ethyl group, It is especially preferable that it is a methyl group.

  Moreover, n in Formula (3) is an integer in any one of 1-3. As such n, the stability of the composition for forming a foam is further improved, the formation of a foam having a fine cell structure is possible, and the formation of a foam having higher texture and strength is possible. From the viewpoint of being possible, it is more preferable that it is 1 to 2, and it is particularly preferable that it is 2.

Further, B in the formula (3) is any one selected from the group consisting of groups represented by formulas: COOX and SO ₃ X, and X in the formula has H, Na, K and a substituent. It is any one selected from the group consisting of ammonium ions which may be. As such B, the stability of the composition for forming a foam is further improved, the formation of a foam having a fine cell structure is possible, and the formation of a foam having higher texture and strength is possible. It is more preferable that it is a group represented by a formula: COOX from a viewpoint of becoming possible. In addition, as X in the group represented by such formula: COOX and SO ₃ X, from the same viewpoint, it is preferable that it is Na, K or an ammonium ion which may have a substituent, and Na And K are more preferable, and Na is particularly preferable.

  Examples of the compound (D3) represented by the general formula (3) include sodium lauroyl methyl alanine, triethanolamine salt of lauroyl methyl alanine and the like, and among them, the stability of the composition for forming a foam Sodium lauroyl methylalanine is particularly preferable from the viewpoints of being improved, forming a foam having a fine cell structure, and forming a foam having higher texture and strength. . In addition, as such a compound (D3), you may utilize suitably a commercial item (For example, "alanine LN-30 (made by Nikko Chemicals" etc. which is a commercial item of lauroyl methyl alanine sodium etc.) etc. suitably. In addition, such a compound (D3) may be used individually by 1 type, or may be used combining 2 or more types.

  Moreover, as the foaming agent (component (D)) according to the present invention, the stability of the composition for forming a foam can be further improved, and the formation of a foam having a fine cell structure becomes possible. And at least one of the compound (D1) and at least one of the compound (D2) and the compound (D3) from the viewpoint of being able to form a foam with higher strength and strength. It is more preferable to use together, and at least one of compound (D1), at least one of compound (D2), and at least one of compound (D3) are used in combination. Is more preferred.

  In the case where at least one compound (D1) and at least one compound (D2) and compound (D3) are used in combination as such a foaming agent (component (D)), The mass ratio of the content of the compound (D1) and the total content of the compound (D2) and the compound (D3) is (mass ratio ([[compound (D1)]: [sum of compound (D2) and compound (D3)]) Is preferably 1:20 to 20: 1, and more preferably 1: 9 to 9: 1.

  In addition, as such a foaming agent (component (D)), at least one type of compound (D1), at least one type of compound (D2), and at least one type of compound (D3) And the content ratio of the compound (D1), the compound (D2) and the compound (D3) is the mass ratio ([compound (D1)]: [compound (D2)]: [compound (D3) Is preferably 45: 45: 10 to 10: 45: 45, and more preferably 10: 50: 40 to 30: 40:30.

<(E) Thickener>
It does not restrict | limit especially as a thickener contained as (E) component in this invention, The well-known thickener which can be utilized for the water dispersion liquid of a polyurethane resin can be utilized suitably. Among such thickeners (component (E)), at least one selected from the group consisting of associative thickeners and water-soluble polymer thickeners is preferable.

  Examples of such association-type thickeners include, for example, JP-A-54-80349, JP-A-58-213074, JP-A-60-49022, JP-B-52-25840, and JP-A-Hei. 9-67563, JP-A-9-71766 and the like; urethane type associative thickeners; JP-A-62-292879, JP-A-10-121030 and the like, nonionicity Associative thickeners obtainable by copolymerizing a urethane monomer with another acrylic monomer as associative monomer; and associative thickeners having an aminoplast skeleton described in WO9640815 etc., among which nonionic ones can be mentioned. Those having strong properties are more preferable. Among these associative thickeners, polyethylene glycol chain and urethane bond in the molecular chain from the viewpoint of pore density and strength retention in the foam structure (porous structure) when the foam is produced Associative thickeners are preferred. As a commercial item of such an association | meeting type | mold thickener, Neosticker S (made by Nikka Chemical Co., Ltd.), Bislyzer AP-2 (Sanyo Chemical Industries, Ltd.), etc. are mentioned.

  Moreover, as the water soluble polymer thickener, for example, cellulose derivatives such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylhydroxypropylcellulose, carboxymethylcellulose and the like; soluble starch, carboxymethyl starch, methyl starch and the like Starch derivatives of alginic acid such as sodium alginate, alginic acid propylene glycol ester, guar gum, carrageenan, galactan, gum arabic, locust bing gum, quince seed, tragacanth gum, pectin, mannan, starch, xanthan gum, dextran, succinoglucan, curdlan , Natural polysaccharides such as hyaluronic acid and its salts; natural proteins such as casein, gelatin, collagen, albumin, etc .; Kylene glycol, polyoxyethylene glycol distearate, myristoyl polyoxyethylene stearyl ether, polyoxyethylene sorbitan triisostearate, polyoxyethylene methyl glucose (mono, di or tri) laurate, polyoxyethylene methyl glucose (mono, di) Or tri) myristate, polyoxyethylene methyl glucose (mono, di or tri) palmitate, polyoxyethylene methyl glucose (mono, di or tri) stearate, polyoxyethylene methyl glucose (mono, di or tri) isostearate Polyoxyalkylene nonionic polymers such as polyoxyethylene methyl glucose (mono, di or tri) oleate; polyvinyl alcohol, polyvinyl pyrrolidone, Vinyl polymers such as polyvinyl methyl ether, and mixtures thereof, are more preferred strong nature of the nonionic of these. Commercially available products of such water-soluble polymer thickeners include HEC AX-15 (manufactured by Sumitomo Seika Co., Ltd., hydroxyethyl cellulose), Kelzan (manufactured by Three Crystals, polymer polysaccharide (xanthan gum)), etc. It can be mentioned.

<(F) Water>
In the present invention, water is contained as the component (F). Thus, the composition for foam formation of the present invention is a liquid composition containing water as the component (F). Water to be contained as such (F) component is not particularly limited, and ion exchange water or distilled water can be suitably used. In addition, such water (component (F)) is, for example, an emulsion dispersion liquid obtained by emulsifying and dispersing the self-emulsifying type aqueous polyurethane resin (component (A)) in water and / or the forced emulsification type aqueous polyurethane in water Each component of (A) to (D) is mixed in water using an emulsion dispersion obtained by emulsifying and dispersing a resin (component (B)) to prepare a foam-forming composition, and then the emulsion dispersion is carried out. By using the water as it is without distilling off the water in the liquid, the water may be used as it is as the (F) component in the composition for foam formation.

<About composition>
The foam-forming composition of the present invention contains the components (A) to (F) described above. Thus, the foam-forming composition of the present invention comprises a self-emulsifiable aqueous polyurethane resin (component (A)) and the above-described forced emulsifying aqueous polyurethane resin (component (B)) as polyurethane resin components. It is a thing.

  In the foam-forming composition of the present invention, the total amount of the self-emulsifying aqueous polyurethane resin (component (A)) and the forced emulsifying aqueous polyurethane resin (component (B)) [the above-mentioned component (A) and It is preferable that it is 30-60 mass%, and, as for the total amount of the polyurethane resin component which consists of said (B) component, it is more preferable that it is 35-55 mass%. When the content of the polyurethane resin component (the total amount of the component (A) and the component (B)) is less than the lower limit, the thickness, feel and strength of the foamed and cured product obtained using the composition for forming a foam On the other hand, when the content exceeds the upper limit, the viscosity of the composition for forming a foam tends to be high, and the handling tends to be difficult.

  Further, in the polyurethane resin component comprising such self-emulsifying type aqueous polyurethane resin (component (A)) and the forced emulsification type aqueous polyurethane resin (component (B)), the components (A) and (B) are contained In terms of proportion, it is possible to foam with a higher expansion ratio at the time of production of the foam and to obtain a foam having higher peel strength, and to improve the water resistance and foam of the resulting foam. From the viewpoints of preventing migration during body production and imparting a better texture to the foam and providing the composition for forming foam with sufficiently excellent thermal gelation, 90: 10-50: 50 are preferable on the basis of mass ratio ([(A) component]: [(B) component]), and 80: 20-60: 40 are more preferable.

  In the foam-forming composition of the present invention, the content of the crosslinking agent (component (C)) is a self-emulsifying aqueous polyurethane resin (component (A)) and the forced emulsification from the viewpoint of improving peel strength. 0.5 to 30 parts by mass (more preferably 1 to 50 parts by mass) per 100 parts by mass of the total amount of the aqueous polyurethane resin (component (B)) (hereinafter sometimes referred to simply as "total amount of polyurethane resin component") 25 parts by mass) is preferable. If the content of such a crosslinking agent is less than the above lower limit, the peel strength tends to decrease, while if it exceeds the above upper limit, there is little further improvement in performance, and the performance corresponding to the amount and cost of the crosslinking agent. There is a tendency that improvement can not be obtained.

  Furthermore, in the composition for forming a foam according to the present invention, the content of the foaming agent (component (D)) shows a high material fracture strength even at a high foaming ratio, and has a good texture and a thick leather material ( From the viewpoint that it is possible to obtain a leather-like laminate), the total amount of the self-emulsifiable aqueous polyurethane resin (component (A)) and the forced emulsification type aqueous polyurethane resin (component (B)) (polyurethane resin component) The total amount is preferably 0.2 to 40 parts by mass, and more preferably 1 to 20 parts by mass with respect to 100 parts by mass. When the compounds (D1) to (D3) are used as the foaming agent (component (D)), the content of the compounds (D1) to (D3) should be in the following range from the same viewpoint. Is preferred. That is, the content of the compound (D1) is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 7 parts by mass with respect to 100 parts by mass of the total amount of the polyurethane resin component. And 0.2 to 5 parts by mass. The content of the compound (D2) is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, with respect to 100 parts by mass of the total amount of the polyurethane resin component. It is even more preferable that it is .2 to 10 parts by mass. The content of the compound (D3) is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, with respect to 100 parts by mass of the total amount of the polyurethane resin component. It is even more preferable that it is .1 to 5 parts by mass.

  Furthermore, in the composition for forming a foam according to the present invention, the content of the thickener (component (E)) is from the viewpoint that the thickness after drying of the foam can be more sufficiently maintained, The amount is preferably 0.01 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the total amount of the resin component. If the content of the thickener is less than the above lower limit, it tends to be difficult to sufficiently maintain the dried thickness of the foam, while if it exceeds the above upper limit, the strength of the foam is reduced, Water resistance tends to decrease.

  Moreover, in the composition for foam formation of this invention, it is preferable that it is 25-60 mass%, and, as for content of the said water ((F) component), it is more preferable that it is 30-55 mass%. If the water content exceeds the upper limit, the thickness, feel and strength of the foam-cured product obtained using the foam-forming composition tends to decrease, while if it is less than the lower limit, the foam is formed. The viscosity of the composition for use tends to be high and the handling becomes difficult.

  In addition, since the composition for forming a foam according to the present invention can produce a more uniform foam, the components (A) and (B) are more uniformly emulsified in the composition during use. It is preferable to be in a dispersed state (dispersion liquid). From this point of view, the foam forming composition of the present invention preferably further contains an emulsifying agent as the component (G). Such an emulsifier (component (G)) is the same as that described above as "the emulsifier used when emulsifying and dispersing the urethane prepolymer having an isocyanate group at the end" (the preferred one is also the same. Is). By including such an emulsifying agent, it becomes easier to emulsify and disperse the component (B) in water (component (F)), and a foam composed of an emulsified dispersion in which each component is more uniformly dispersed. Compositions for formation can be obtained.

  The content of such an emulsifier (component (G)) is not particularly limited, but is preferably 0.5 to 10 parts by mass, and more preferably 1 to 6 parts by mass with respect to 100 parts by mass of the total amount of polyurethane resin components. It is more preferable that Also, from the viewpoint of more efficiently emulsifying and dispersing the component (B), the content of the emulsifier (component (G) is 0.5 to 10 parts by mass with respect to 100 parts by mass of the component (B). Is preferable, and 1 to 6 parts by mass is more preferable. If the content of such an emulsifier (component (G)) is less than the above lower limit, it tends to be difficult to obtain a foam-forming composition in which the component (B) is dispersed uniformly and stably. If the upper limit is exceeded, the water resistance of the foam-cured product of the foam-forming composition tends to decrease.

  Further, in the foam-forming composition of the present invention, from the viewpoint of sufficiently suppressing the shrinkage of the foam layer at the time of drying and shortening of the drying time being possible, a thermosensitive gelling agent is used as the component (H). Furthermore, it is desirable to contain. The heat-sensitive gelling agent (component (H)) is not particularly limited, and any known heat-sensitive gelling agent (a conventional foam-forming composition containing a so-called aqueous polyurethane resin) A known heat-sensitive gelling agent or the like used for thermalization (heat-sensitive coagulation) can be appropriately used. Examples thereof include sodium salts of inorganic acids, ammonium salts of inorganic acids, water-soluble acrylic polymers and the like. it can.

  Examples of inorganic acids in sodium salts of inorganic acids and ammonium salts of inorganic acids include perchloric acid, carbonic acid, sulfuric acid, persulfuric acid, sulfurous acid, phosphoric acid, nitric acid and the like. Among such inorganic acids, sulfuric acid and phosphoric acid are preferable because they are excellent in the migration preventing effect. Such sodium salts of inorganic acids include, for example, sodium sulfate. Moreover, as the ammonium salt of the inorganic acid, for example, ammonium persulfate, ammonium perchlorate, ammonium carbonate, ammonium sulfate, ammonium hydrogensulfate, ammonium sulfite, ammonium hydrogensulfite, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, Ammonium sulfate, ammonium nitrate and the like can be mentioned. Such a sodium salt of inorganic acid and an ammonium salt of inorganic acid may be used singly or in combination of two or more.

  Further, among such ammonium salts of inorganic acids, from the viewpoint of safety in handling, problems of volatilization during drying, and easy removal by washing with water after drying, and from the viewpoint of being less likely to remain in leather materials At least one selected from the group consisting of ammonium sulfate, diammonium hydrogen phosphate and ammonium dihydrogen phosphate can be suitably used. In addition, although it is possible to use diammonium hydrogen phosphate alone as such an ammonium salt of inorganic acid, it is preferable to use ammonium dihydrogen phosphate and diammonium hydrogen phosphate in combination. .

  The water-soluble acrylic polymer which can be used as the thermosensitive gelling agent (component (H)) is not particularly limited, but the following component (1), the following component (2) and the following component (3) And at least one of the following component (4) and the following component (5).

[Component (1)]
Polymers of at least one monomer selected from the group consisting of acrylic acid, methacrylic acid and maleic acid, alkali metal salts of the polymers, and at least one of amine salts of the polymers.

[Component (2)]
At least one of poly-α-hydroxy acrylic acid, an alkali metal salt of poly-α-hydroxy acrylic acid and an amine salt of poly-α-hydroxy acrylic acid.

[Component (3)]
Acrylic acid, methacrylic acid, maleic acid, alkali metal salts of acrylic acid, alkali metal salts of methacrylic acid, alkali metal salts of maleic acid, amine salts of acrylic acid, amine salts of methacrylic acid and amine salts of maleic acid At least one selected from the group consisting of at least one monomer selected from the group consisting of poly-α-hydroxy acrylic acid, alkali metal salts of poly-α-hydroxy acrylic acid, and amine salts of poly-α-hydroxy acrylic acid At least one of a polymer obtained by radical polymerization of a species and an alkali metal salt of the polymer, and an amine salt of the polymer.

[Component (4)]
Acrylic acid, methacrylic acid, maleic acid, poly-α-hydroxy acrylic acid, alkali metal salt of acrylic acid, alkali metal salt of methacrylic acid, alkali metal salt of maleic acid, alkali metal salt of poly-α-hydroxy acrylic acid, At least one acrylic acid-based monomer selected from the group consisting of amine salts of acrylic acid, amine salts of methacrylic acid, amine salts of maleic acid, and amine salts of poly-α-hydroxyacrylic acid, and 2-acrylamido Polymers obtained by radical polymerization of -2-methylpropane sulfonic acid, styrene sulfonic acid, and sulfonic acid-based monomers such as alkali metals and / or amine salts thereof.

[Component (5)]
Polymer obtained by radical polymerization of acrylic acid type monomer and nonionic type monomer, and polymer obtained by radical polymerization of monomer mixture consisting of acrylic acid type monomer, sulfonic acid type monomer and nonionic type monomer And at least one polymer having a content (total amount) of an acrylic acid-based monomer and a sulfonic acid-based monomer in the monomer mixture of 30% by mass or more.

  As a nonionic monomer in such a component (5), acrylic acid (carbon number 1 to 22) alkyl ester, vinyl acetate, styrene, α-methylstyrene, p-methylstyrene, glycidyl (meth) acrylate, (meth ) Acrylamide, N, N-Dimethyl (meth) acrylamide, diacetone (meth) acrylamide, methylolated diacetone (meth) acrylamide, N-methylol (meth) acrylamide, 3-chloro-2-hydroxypropyl (meth) acrylate, vinyl alkyl Ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, butadiene, isoprene, chloroprene, aziridinyl ethyl (meth) acrylate, aziridinyl (meth) acrylate, polyoxyalkylene (meth) acrylate Methyl polyoxyalkylene (meth) acrylate, 2-ethylhexyl polyoxy alkylene (meth) acrylate, polyoxyalkylene di (meth) acrylate, triallyl cyanurate, allyl glycidyl ether, allyl acetate, N-vinylcarbazole, maleimide, N- (Meth) acrylate having a silicone such as methyl maleimide, (2-dimethylamino) ethyl (meth) acrylate, glycerol (meth) acrylate, alkylene di (meth) acrylate, vinylsilane, trimethoxysilyl (meth) acrylate in the side chain, The (meth) acrylate which has polysiloxane, blocked isocyanate group containing (meth) acrylate, (meth) acrylate which has a urethane bond, etc. can be mentioned.

  As such a water-soluble acrylic polymer (preferably at least one of components (1) to (5)), commercially available products can be appropriately used. For example, Aron A-50P (Toa Gosei Co., Ltd.) Examples thereof include sulfonic acid monomer copolymer-type acrylic thickeners and the like.

  In the foam-forming composition of the present invention, the content of the heat-sensitive gelling agent (component (H)) makes it possible to maintain the dried thickness of the foam more sufficiently, and the composition thereof. From the viewpoint of the stability of the product, relative to 100 parts by mass of the total amount of the self-emulsifying aqueous polyurethane resin (component (A)) and the forced emulsification aqueous polyurethane resin (component (B)) (total amount of polyurethane resin components) It is preferable that it is 0.01-10 mass parts, and it is more preferable that it is 0.05-5 mass parts.

  The foam forming composition of the present invention preferably has a thermosensitive coagulation temperature of 40 to 90 ° C., more preferably 50 to 90 ° C. As a thermosensitive solidification temperature of such a composition for foam formation, 50 g of the composition for foam formation prepared so that solid content might be set to 20 g is added to a 100 mL glass beaker, and the composition for foam formation While stirring the material, the beaker is gradually heated in a hot water bath at 95 ° C., and the temperature at which the content loses fluidity and solidifies is adopted. If the thermosensitive coagulation temperature is less than the lower limit, the foam forming composition becomes unstable and gelates relatively easily during storage, etc. Mass production tends to be difficult, while on the other hand, when the above upper limit is exceeded, such a foam-forming composition is used to form a foamed cured product having sufficient foamability, strength and texture. Tend to be difficult. In addition, such a thermosensitive coagulation temperature appropriately changes the ratio of the (A) component and the (B) component in the polyurethane resin component, and appropriately selects the type and amount of the crosslinking agent, the foaming agent and the thickener. It can be easily adjusted by changing, and further, using an emulsifying agent and a thermosensitive gelling agent as appropriate (using while appropriately changing the type and the amount used).

  In addition, in the foam-forming composition of the present invention, other components (preferably, conventionally used known additives such as the following) may be added, as necessary, to the extent that the effects of the present invention are not affected. You may use it together. As such additive components, for example, various surfactants such as fluorine-based or acetylene glycol-based, n-methylpyrrolidone, and the like, in order to improve the processing suitability and adhesiveness of the foaming layer-forming agent. Stabilizers for solvents such as propylene glycol monomethyl ether acetate, rosin resins, rosin ester resins, terpene resins, terpene resins, terpene phenol resins, tackifiers such as coumarone resins, antioxidants, light stabilizers, UV absorbers, etc. Agents, mineral oil based, silicone based antifoaming agents, plasticizers, coloring agents such as pigments, urethane reaction catalysts may be used in combination.

  Furthermore, you may make the composition for foam formation of this invention contain suitably other resin components other than the above-mentioned (A) component and (B) component in the range which does not impair the effect of this invention. In addition, an aqueous dispersion of the resin component (for example, an emulsion of vinyl acetate, ethylene vinyl acetate, acrylic, etc .; styrene, butadiene, etc.) at the time of preparation of the composition in order to contain such other resin components. And acrylonitrile-butadiene-based latex; polyethylene-based, polyolefin-based ionomer, polyester, polyamide, epoxy-based resin, etc. may be suitably used. Here, an acrylic emulsion is a polymer obtained by radical polymerization of an acrylic acid monomer and a nonionic monomer, or radical polymerization of an acrylic acid monomer, a sulfonic acid monomer and a nonionic monomer. Polymer obtained by emulsifying and dispersing a polymer having a content of an acrylic acid monomer and a sulfonic acid monomer in the monomer mixture of less than 30% by mass in water in the presence of a surfactant. . Such an acrylic emulsion may be obtained by emulsifying and dispersing the produced polymer in water in the presence of a surfactant, or after emulsifying and dispersing a monomer in water in the presence of a surfactant It may be an emulsion polymerized emulsion.

  In the present invention, the (A) self-emulsifying aqueous polyurethane resin, the (B) forced emulsifying aqueous polyurethane resin, the (C) crosslinking agent, the (D) foaming agent, and the (E) thickening agent The method for producing a foam-forming composition containing the (F) water, optionally the (G) emulsifier, and the (H) thermosensitive gelling agent is not particularly limited, and known methods It is possible to use as appropriate. The component (A) and the component (B) are usually obtained as an emulsion dispersion of a resin (water emulsion dispersion: aqueous dispersion of an aqueous polyurethane resin), and the emulsion dispersion (water emulsion dispersion: aqueous) From the viewpoint of production efficiency, the component (A) and the component (B) are commercially available from the viewpoint of production efficiency since they are distributed in the market in the form of a water dispersion of polyurethane resin). The components (C) and (C), the (D) crosslinking agent, the (D) foaming agent, and the (E) thickening agent are used as they are as the emulsified dispersion (water emulsified dispersion: aqueous dispersion of aqueous polyurethane resin). Also, if necessary, mixing the (G) emulsifier and the (H) thermosensitive gelling agent allows the (A) self-emulsifying aqueous polyurethane resin, the (B) forced emulsifying aqueous polyurethane resin, Said (C) crosslinker, said (D) foaming agent, front (E) a thickener, the water (F), if necessary, the (G) an emulsifier, it is preferred to prepare the (H) foam forming composition containing a heat-sensitive gelling agent.

  Further, the composition for forming a foam according to the present invention is an aqueous polyurethane resin in which the content of the component (A) is 50 to 70% by mass because it is easier to set the heat-sensitive coagulation temperature to a desired range. Aqueous dispersion (II) of an aqueous polyurethane resin containing the component (B) and an emulsifier and having a content of the component (B) of 30 to 70% by mass, the above (C) The component (D) and the component (E) are preferably obtained by mixing the component (D) and the component (E). In the foam-forming composition thus obtained, the aqueous polyurethane resin can be used by being emulsified and dispersed in water and mixed, and the polyurethane resin component can be obtained as a foam-forming composition ( The liquid polyurethane resin component ((A) can be made more uniformly dispersed in a liquid composition) and by using the aqueous dispersion (I) and the aqueous dispersion (II). It is also possible to efficiently produce a foam-forming composition (liquid composition) having a high concentration (preferably 40% by mass or more) of components (B) and (B).

  Such an aqueous dispersion (I) is an aqueous dispersion containing 50 to 70% by mass (more preferably 50 to 65% by mass) of the self-emulsifying aqueous polyurethane resin as the component (A) (emulsified and dispersed) It is preferable that it is a liquid. By using such an aqueous dispersion (I), a foam-forming composition of the present invention which can be used to form a foam having intended properties (sufficient texture and strength) It becomes possible to manufacture more efficiently. When the content of such a self-emulsifying aqueous polyurethane resin is less than the above lower limit, it is difficult to obtain a foam having sufficient strength even if a foam is formed using the composition for forming a foam to be obtained On the other hand, when the above upper limit is exceeded, the resulting foam forming composition tends to be less susceptible to thermal gelation, and the texture of the resulting foam tends to decrease. When the above-mentioned preparation method is adopted as a method for preparing a self-emulsifying aqueous polyurethane resin as such an aqueous dispersion (I), an emulsion dispersion of the SU isocyanate group-terminated prepolymer in water by self-emulsification And the emulsion dispersion liquid of the above-mentioned polyurethane resin which can be obtained by chain extension reaction can be utilized as it is. The aqueous dispersion (I) contains a self-emulsifying aqueous polyurethane resin, but may contain an emulsifying agent as appropriate. As the emulsifier to be contained in such aqueous dispersion (I), the same ones as those described as the above-mentioned (G) component can be appropriately used.

  In addition, such aqueous dispersion (II) is an aqueous dispersion containing 30 to 70% by mass (more preferably 30 to 60% by mass) of the forced emulsification type aqueous polyurethane resin which is the component (B). It is preferable that it is an emulsified dispersion. By using such an aqueous dispersion (II), the composition for forming a foam can be more efficiently thermally gelled, and the target foam can be more efficiently formed. It becomes possible. If the content of such a forced emulsifying type aqueous polyurethane resin is less than the above lower limit, it tends to be difficult to heat-sensitize the resulting foam forming composition efficiently, and the foam obtained using this On the other hand, when the upper limit is exceeded, it tends to be difficult to efficiently produce a foam-forming composition. As such aqueous dispersion (II), when the above-mentioned preparation method is adopted as a method for preparing a forced emulsification type aqueous polyurethane resin, to water in the presence of an emulsifier of a urethane prepolymer having an isocyanate group at the end The emulsion dispersion of the above-mentioned polyurethane resin which can be obtained by the emulsion dispersion and chain extension reaction of the above can be used as it is.

  Moreover, as such aqueous dispersions (I) and (II), a viewpoint that higher peel strength can be obtained while enabling foaming at a higher foaming ratio, and a composition for forming a foam of the present invention From the viewpoint of being able to make the product more homogeneous and preparing it more easily, the self-emulsifiable aqueous polyurethane resin (component (A)) in the aqueous dispersions (I) and (II) And the total amount (total amount) of the forced emulsification type aqueous polyurethane resin (component (B)) is 30 to 60% by mass (more preferably 35 to 55% by mass) based on the total amount of the composition for foam formation Thus, it is preferred to utilize the aqueous dispersions (I) and (II).

  In addition, such a foam-forming composition may be prepared by gently stirring the above components so as not to foam during preparation, or the composition may be foamed after preparation of the foam-forming composition. When using for immediate preparation of the body, etc., at the time of preparation, the components are mixed (stirred) so as to foam so as to prepare a composition for forming a foam, which is then foamed to obtain a foamed composition (foamed foam (foamed foam) The composition for forming a foam may be prepared as a composition for forming a foam in a form including Such a foam composition may be prepared by preparing in advance a foam-forming composition comprising a mixture of the components, and mechanically foaming the foam-forming composition. Thus, the foam-forming composition of the present invention may be prepared as a foam composition in the form in which foamed foam is included in the composition.

  The composition for forming a foam of the present invention (which may be in the form of the above-mentioned foam composition) has a viscosity of 500 to 30,000 mPa · s (more preferably 1,000 to 10,000 mPa · s). Those of s) are preferred. If the viscosity is less than the lower limit, it tends to be difficult to sufficiently suppress the disappearance of the foam at the time of foaming, whereby it tends to be difficult to foam with a sufficiently high foaming ratio, on the other hand If the upper limit is exceeded, handling tends to be difficult, and foaming tends to be difficult. In addition, as such viscosity, the value measured by the method of measuring on BM type | mold viscosity meter, 4 rotor, and 60 rpm conditions on temperature conditions of 20 degreeC is employ | adopted.

  As mentioned above, although the composition for foam formation of this invention was demonstrated, the manufacturing method of the foam of this invention, and a foam are demonstrated hereafter.

[Method of producing foam and foam]
The method for producing a foam according to the present invention comprises the steps of obtaining a foam composition obtained by foaming the composition for forming a foam according to the present invention, applying the foam composition to a substrate, drying and curing it. And B. obtaining a foam having a foamed resin layer formed of a foamed and cured product of the foam-forming composition. In addition, the foam of the present invention is characterized by comprising a substrate and a foamed resin layer formed of a foamed and cured product of the composition for forming a foam of the present invention laminated on the substrate. It is. It is preferable that such a foam is a thing obtained by the manufacturing method of the foam of the said invention. Hereinafter, the manufacturing method of the foam of the said this invention is divided and demonstrated for every process.

(Step of obtaining a foaming composition)
In the step of obtaining such a foam composition, a step of obtaining a foam composition obtained by foaming the foam-forming composition of the present invention described above (a step of obtaining a foam composition which is a foam-forming composition in a foamed state) ). In such a step, the foam-forming composition of the present invention in the unfoamed state may be prepared in advance, stirred, and machine-foamed to obtain a foam composition, or (I) Each component to be contained in the composition for forming a foam according to the present invention (the (A) self-emulsifying aqueous polyurethane resin, the (B) forced emulsifying aqueous polyurethane resin, the (C) crosslinking agent, D) A foaming agent, the (E) thickening agent, the (F) water, if necessary, the (G) emulsifier, the (H) thermosensitive gelling agent) are prepared, mixed and stirred Then, a foam forming composition comprising a mixture of each component is prepared while being foamed, and a foam composition in a form in which the foamed foam is contained in the composition (the foam composition is foamed: As a process (II) which obtains one form (foaming form) of the composition for foam formation Good.

  In such a process, as the foam-forming composition, the aqueous dispersion (I), the aqueous dispersion (II), the above component (C), the above component (D) and the above component (E) can be used. The water obtained by mixing (in addition, the water of the component (F) is contained in the composition obtained by the water in the aqueous dispersion (I) and the aqueous dispersion (II) Is preferred.

  In addition, in the case of foaming while preparing the composition in the method (step (II)) of foaming the composition for foam formation (the aqueous dispersion of the components (A) to (E): liquid composition) in this way As a foaming method)), for example, a cream is obtained by mechanically stirring the air while entraining air so as to obtain a predetermined foaming ratio with a common batch type stirrer, such as a Hobart mixer, a hopper, a disperser, etc. It is possible to adopt a method of obtaining as a dispersion which is foamed in the form of As such a foaming method, from the viewpoint of mass production, it is preferable to adopt a method of continuously stirring while feeding a fixed amount of air with an oaks mixer, a pin mixer or the like.

  When foaming in this manner, the foam-forming composition is foamed at a foaming ratio of 1.5 to 5 times (more preferably 2 to 5 times, more preferably 2.5 to 4.5 times). Is preferred. If the expansion ratio is less than the lower limit, it tends to be difficult to form a foam having a sufficiently high texture, while if it exceeds the upper limit, the strength of the resulting foam tends to decrease. It is in. As such a foaming ratio, a value ([volume after foaming] / [volume before foaming]) calculated based on the volume of the composition before and after foaming is adopted.

  As such a foam composition (liquid foam), one having a viscosity of 3,000 to 100,000 mPa · s (more preferably 5,000 to 80,000 mPa · s) is preferable. When such a viscosity is less than the above lower limit, it is difficult to sufficiently suppress the cell breakage when foaming (it becomes difficult to sufficiently suppress the disappearance of the bubbles), and it is possible to foam with a sufficient expansion ratio It tends to be difficult, and the texture of the resulting foam tends to be lowered. On the other hand, when it exceeds the upper limit, handling becomes difficult and coating tends to be difficult. In addition, as such viscosity, the value measured by the method of measuring on BM type | mold viscosity meter, 4 rotor, and 60 rpm conditions on temperature conditions of 20 degreeC is employ | adopted.

(Step of obtaining foam)
In the present invention, in the step of obtaining a foam, the foamed composition obtained in the above step is applied to a substrate, dried and cured, and a foamed resin comprising a foamed cured product of the composition for forming a foam on the substrate. It is a process of obtaining the foam in which the layer was formed.

  Such a base is not particularly limited, and examples thereof include release paper, a material for the skin layer, a fiber base and the like, and an appropriate base is appropriately selected from known bases according to the application and used. Just do it. In addition, you may utilize suitably the thing similar to what is demonstrated in the below-mentioned material for leathers as such skin layer material, a fiber base material, etc.

  Moreover, it does not restrict | limit especially as a method of apply | coating the said foaming composition to a base material, A well-known application method can be utilized suitably, For example, the roll coating method, the gravure coating method, the knife coating method, the reverse coating method, kiss coating Methods, comma coating method, lip coating method, etc. can be mentioned.

  Moreover, the conditions at the time of applying the said foaming composition to a base material in particular are not restrict | limited, However, since the feel and intensity | strength of the foam obtained become higher, the average value of the thickness after drying It is preferable to apply so that it may become 0.7-3.0 mm. In addition, the average value of such thickness observes a cross section using an electron microscope, and based on the electron micrograph of this cross section, measures the thickness of the measurement location of arbitrary plural places (preferably three or more places) It can be determined by calculating its average value.

  In addition, there is no particular limitation on the method of drying and curing after applying the foam composition (for example, a composition comprising the foam forming composition in the form of a mechanically foamed dispersion), for example, hot air drying It is possible to appropriately adopt a method of curing by drying in a conventionally known dryer such as a machine, an infrared irradiation dryer, a microwave irradiation dryer, or a wet heat dryer. The drying conditions in such a drying and curing step may be suitably changed according to the heat resistance temperature of the substrate, and although not particularly limited, it is preferable to set the temperature to 80 to 120 ° C.

  In the present invention, since the composition for forming a foam is used for preparation of a foam, the shrinkage of the foam composition can be sufficiently suppressed in the drying and curing step, and the foam after being cured Since the thickness of the layer can be made sufficient and the foamability of the composition for forming a foam is sufficiently high, the foam is made sufficiently in terms of flexibility and impact resilience of the resulting foam. It is also possible to have a good texture.

  Thus, the foam composition is applied to a substrate and dried and cured to obtain a foam on which a foam resin layer composed of a foam-cured product of the foam-forming composition is formed. be able to. That is, the foam thus obtained is provided with a substrate, and a foamed resin layer formed of a foamed and cured product of the composition for forming a foam of the present invention, laminated on the substrate. . The thickness of such a foamed resin layer is not particularly limited, but an average value of the thickness is 0.7 to 3.0 mm (more preferably 0) because the texture and strength of the resulting foam are higher. Preferably 7 to 2.5 mm). Such a foam can be suitably used as a material for leather (leather agent: leather-like laminate). Hereinafter, the leather material of the present invention will be described.

[Leather material]
The leather material of the present invention comprises the foam of the present invention. As described above, the leather material of the present invention has at least the foam, and thus has a laminated structure and is used as a so-called leather-like laminate.

  As described above, the structure of the leather material of the present invention is not particularly limited as long as it contains the foam of the present invention, and the same structure as a leather material containing a known foam can be obtained. As a construction of such a leather material of the present invention, for example, a material for a skin layer as a base material of the foam (for example, one having a skin layer formed on a release paper (a release paper is peeled to make only the skin layer) And the like (if it is used), the fibrous base material is placed on the surface of the foam opposite to the skin layer (base material) side (on the surface of the foam layer) via the adhesive layer. It may be a stacked structure. As such a fiber base material, a nonwoven fabric and a cloth are mentioned, for example.

  The method for forming such a leather material is not particularly limited, and a known method can be appropriately used. For example, a composition for forming a skin layer is applied to a release paper and dried to form a release paper. To form a foam by applying a foam composition obtained by mechanically foaming the foam-forming composition onto the skin layer (base material) and drying and curing it. Further, a composition for forming an adhesive layer is applied on the surface of a foam layer (foamed resin layer) of the foam, and a fiber base (for example, a non-woven fabric or a fabric) is directly adhered and dried. Release paper transfer method such as a wet lamination method of forming a leather material comprising the above, or a dry lamination method of forming a leather material comprising a laminate by first drying and then bonding the composition for forming an adhesive layer; release paper Set for forming skin layer The material of the present invention is applied and dried to form a skin layer material, and the foam according to the present invention in which a foam resin layer is formed on a fiber base (base) separately using a fiber base as a base A thermal transfer method of forming a leather material comprising a laminate by forming a body and bonding the skin layer material to the foam by heat; on a fiber substrate (substrate) using a fiber substrate as a substrate After forming the foam of the said invention by which the foamed resin layer was formed, the method of apply | coating and drying the composition for skin layer formation directly on this foam, etc. can be mentioned.

  In the case of adopting such a method for forming a leather material, the composition for forming the skin layer is not particularly limited, and it is known that it can be used to form the skin layer of artificial leather or synthetic leather. A resin composition can be suitably utilized and, for example, an aqueous polyurethane resin composition described in JP 2008-248174 A and the like can be suitably utilized. Further, the method for applying the composition for forming a skin layer on a release paper or foam is not particularly limited, but spray method, roll coating method, gravure coating method, knife coating method, reverse coating method, kiss coating method And a direct coating method which is applied by a comma coating method, a lip coating method or the like.

  Furthermore, when applying the composition for forming the skin layer, it is preferable to adjust the viscosity of the composition for forming the skin layer in order to improve processing suitability, and it is preferable to mix the thickener as described above. It is more preferable to adjust the viscosity to 2500 to 15000 mPa · s (BM type viscosity type, 4 rotor, 6 rpm). Moreover, it does not restrict | limit especially as a method to dry after apply | coating the composition for such a skin layer formation, For example, In the conventionally well-known dryer of a hot air dryer, an infrared irradiation dryer, a microwave irradiation dryer, a wet heat dryer And drying may be performed at a temperature of about 70 to 130 ° C. for 10 seconds to 3 minutes.

  In the method of forming such a leather material (leather-like laminate), the release paper transfer is performed from the viewpoint of further improving the quality and physical properties of the obtained leather-like laminate and the physical properties of the obtained skin layer. Among these release paper transfer methods, the dry lamination method is more preferably employed.

Here, the dry lamination method will be described in more detail. Such a composition for forming an adhesive layer is not particularly limited, and a known composition capable of forming an adhesive layer can be appropriately used. And as such a dry laminating method, for example, after mixing a thickener with the composition for adhesive layer formation and setting a viscosity to 2500 to 15000 mPa · s (BM type viscosity type No. 4 rotor, 6 rpm) The composition for forming an adhesive layer is coated on the surface of a foamed resin layer of foam, dried in a dryer at 70 to 130 ° C. for 10 seconds to 3 minutes, and then the coated surface of the composition for forming an adhesive layer and fibers. A method of laminating with a substrate by a nip roll having a temperature of 20 to 150 ° C. and a pressure of 10 to 300 kg / cm ² and then aging at 30 to 70 ° C. for 1 to 3 days for adhesive stability. May be adopted. Thereby, the leather material (leather-like laminated body) of a lamination | stacking state can be obtained.

  In addition, when such a material for leather (leather-like laminate) is configured to include a fiber base, the fiber base may be a fiber base generally used for a material for leather, and there is no particular limitation. Any known one can be used as appropriate. Examples of materials for such fiber base materials include synthetic fibers such as polyamide, polyester and polyacrylic and their improved fibers; natural fibers such as wool, silk, cotton and hemp; semi-synthetic fibers such as acetate and rayon It can be mentioned. Furthermore, as a shape of such a fiber base material, fiber sheet-like shapes, such as a woven fabric, a nonwoven fabric, etc., are mentioned, for example. Furthermore, as such a fiber substrate, a porous body in which a polyurethane resin composition is coated (including foam coating) or impregnated on a fiber sheet-like fiber substrate to form a microporous can be used. In the present invention, it is particularly preferable to use such a porous body. In addition, natural leather materials such as leather can also be used as the fiber base material.

  Further, the thickness and shape of the fibers applied to such a fiber substrate are not particularly limited. Furthermore, it is also possible to use an ultrafine fiber as such a fiber, and for example, any of a sea-island type, split or peelable type, direct spinning type, and orange peel type fiber may be used in ultrafine fiberization. When sea-island fibers are used, as a method of extra-fine thinning, solution extraction method by treating sea component or island component with organic solvent such as toluene, decomposition extraction method by alkali etc., water jet method by high pressure water flow etc. may be mentioned. The method is not particularly limited.

  Such a leather material (leather-like laminate) of the present invention is suitable for use as a material of artificial leather or synthetic leather or itself, and, for example, vehicles, furniture, clothes, shoes, shoes, bags, sandals, It can be particularly suitably used for applications such as artificial leather-like materials used for miscellaneous goods and the like.

  Hereinafter, the present invention will be more specifically described based on examples and comparative examples, but the present invention is not limited to the following examples.

  First, methods for preparing the components used in each example and the like will be described below.

Preparation Example 1: Preparation of material for forming skin layer
<Step of Preparing Aqueous Polyurethane Resin Composition for Forming Epidermal Layer>
First, each component is mixed with the following composition to prepare a liquid composition, and then the liquid composition is allowed to stand for 1 day (24 hours) under a temperature condition of 25 ° C. to form a skin layer. An aqueous polyurethane resin composition was obtained. The viscosity of the composition thus obtained was 3200 mPa · s (BM type viscometer, No. 4 rotor, 60 rpm).
[Composition of aqueous polyurethane resin composition for forming skin layer (use amount of each component)]
Evafanol HA-107C (manufactured by Nikka Chemical Co., Ltd., aqueous dispersion of aqueous polyurethane resin) 100 g
Neo sticker N (made by Nikka Chemical Co., Ltd., association type thickener) 3 g
0.1 g of NXH-6022 (manufactured by Nikka Chemical Co., Ltd., antifoamer).

Process of preparing material for forming skin layer (process of preparing skin layer)
Next, the aqueous polyurethane resin composition for forming a skin layer obtained as described above is applied on a release paper (Asahi Roll Co., Ltd., Asahi Release AR-148) so that the film thickness after drying becomes 30 μm. After coating and drying for 2 minutes at a temperature of 80 ° C. using a pin tenter, it is further dried for 1 minute at a temperature of 120 ° C. to form a skin layer on release paper, and a material for forming a skin layer is obtained. Obtained.

Preparation Example 2 Preparation of Self-Emulsifying Aqueous Polyurethane Resin Having Sulfonate Group (Component (A))
Polycarbonate diol (trade name "ETERNACOLL UH-100" manufactured by Ube Industries, Ltd., weight by weight, 1,6-hexanediol as a raw material, in a four-necked flask provided with a stirrer, a reflux condenser, a thermometer and a nitrogen introduction pipe After charging 213.8 parts by mass of average molecular weight 1,000), 0.002 parts by mass of dibutyltin dilaurate and 75 parts by mass of acetone and uniformly mixing, 73.0 parts by mass of isophorone diisocyanate is added and reacted at 80 ° C. for 90 minutes Thus, an acetone solution of isocyanate group-terminated prepolymer having a content of free isocyanate groups of 2.7% by mass was obtained.

After the solution is cooled to 50 ° C. or less, 625.0 parts by mass of acetone is added to the solution, and then the solution is further cooled to 30 ° C. or less to obtain sodium 2- (2-aminoethylamino) -ethanesulfonate Aqueous solution (45% by weight aqueous solution) such that the amount of sodium 2- (2-aminoethylamino) -ethanesulfonate added is 10.2 parts by mass, and water is immediately stirred using a disper blade 425.7 parts by mass was gradually added to obtain an emulsion dispersion in which an isocyanate group-terminated prepolymer having a sulfonate group was emulsified and dispersed. Then, 33 parts by mass of a polyamine aqueous solution in which ethylene diamine is dissolved in water (concentration of ethylene diamine: 20% by mass, ethylenediamine: 6.6 parts by mass and water: 26.4 parts by mass) is added to the emulsified dispersion, After chain extension reaction for 60 minutes, solvent removal (acetone removal) is performed at 35 ° C. under reduced pressure (95 KPa) conditions, and emulsion dispersion of a self-emulsifiable aqueous polyurethane resin (polycarbonate aqueous urethane resin) having a sulfonate group A liquid (water dispersion) was obtained. The emulsified dispersion thus obtained has a non-volatile content of 60.0% by mass, a content of a self-emulsifiable aqueous polyurethane resin of 60% by mass, and a viscosity of 120 mPa · s (BM viscometer, No. 2 rotor) 60 rpm), the average particle diameter of the polyurethane resin having a sulfonate group was 400 nm. In addition, the obtained polyurethane resin had 8.1 milliequivalents (calculated value) of SO ₃ per 100 g. An emulsion dispersion (solvent: water) having a concentration of 40% by mass is prepared using a part of the obtained emulsion dispersion (water dispersion), and the emulsion dispersion is allowed to stand at 20 ° C. for 12 hours. When placed, no separation or sedimentation was observed in the emulsified dispersion, and it was confirmed that the obtained polyurethane resin was an aqueous resin. In addition, since the obtained aqueous polyurethane resin was in a state of being dispersed in water without using a surfactant, it was also found that it was a self-emulsification type aqueous polyurethane resin.

Preparation Example 3 Preparation of Forced Emulsion-Type Aqueous Polyurethane Resin (Component (B))
A four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing pipe, polycarbonate diol having a number average molecular weight of 3,000 (manufactured by Kuraray Co., Ltd., trade name "Kuraray polyol C-3090") 152. 6 parts by mass, 1.8 parts by mass of trimethylolpropane, 1.8 parts by mass of 1,4-butanediol, polyoxyethylene-polyoxypropylene random copolymer glycol (polyether-based polyol) (trade name: manufactured by ADEKA) Adeka polyether PR-3007 ", number average molecular weight: 3,000, oxyethylene group content: 70% by mass 6.0 parts by mass, 49.2 parts by mass of methyl ethyl ketone as a solvent and uniformly mixed, Furthermore, 34.6 parts by mass of dicyclohexylmethane diisocyanate which is an organic polyisocyanate, a catalyst and 0.02 parts by mass of bismuth tris (2-ethylhexanoate) is added, and the mixture is reacted for 90 minutes so that the temperature is 80 ± 5 ° C., and the content of free isocyanate group in the urethane prepolymer is 1. A methyl ethyl ketone solution of a 34% terminal isocyanate group-containing urethane prepolymer was obtained. Next, 1.0 part by mass of sodium dihydrogen phosphate as a reaction inhibitor, and a polyoxyethylene tristyryl phenyl ether type nonionic surfactant (ethylene oxide 20 molar adduct of tristyrenated phenol) as an emulsifier in the methyl ethyl ketone solution 8 After 9 parts by mass was added and uniformly mixed, 290 parts by mass of water was gradually added and stirred to emulsify and disperse the terminal isocyanate group-containing urethane prepolymer. In the emulsion dispersion thus obtained, 27.3 parts by mass of a 20% aqueous solution of piperazine hexahydrate (5.46 parts by mass as piperazine hexahydrate) as a chain extender and a 20% aqueous solution of diethylenetriamine 3 After adding .75 parts by mass (0.75 parts by mass as diethylenetriamine) and stirring for 90 minutes while making the temperature to be 40 ± 5 ° C., the solvent is removed at 40 ° C. under reduced pressure (95 KPa) ) To obtain an emulsion dispersion (water dispersion) of a forced emulsification type aqueous polyurethane resin (forced emulsification type polycarbonate-based aqueous urethane resin). The emulsified dispersion thus obtained has a non-volatile content of 47.0% by mass, a content of a forced emulsifying aqueous polyurethane resin of 45.0% by mass, and an emulsifier (20 moles of ethylene oxide of tristyrenated phenol) The content of the adduct) was 2.0% by mass, the viscosity (20 ° C.) was 40 mPa · s, and the average particle size of the polyurethane resin was 0.3 μm. The polyurethane resin thus obtained has a hydrophilic functional group such as a sulfo group, a sulfonate group, a carboxy group, a carboxylate group, and a quaternary ammonium group, as is apparent from the type of the monomer. Since it was not necessary and a surfactant was required to be dispersed in water, it was found to be a forced emulsification type polyurethane resin (forced emulsification type polyurethane resin). Moreover, using a part of the obtained emulsified dispersion (water dispersion), an emulsified dispersion (solvent: water, containing the above-mentioned emulsifier) having a concentration of 40% by mass is prepared. When left to stand at ° C for 12 hours, no separation or sedimentation was observed in the emulsified dispersion, and it was confirmed that the obtained polyurethane resin was an aqueous resin.

Preparation Example 4 Preparation of Sulfosuccinic Acid Monoalkylamide Sodium Salt
One mole of Pharmin CS (manufactured by Kao Corporation) was reacted according to a conventional method with respect to one mole of maleic anhydride, and caustic soda (1.1 mole) and water were then added for neutralization to obtain a reaction solution. Then, anhydrous sodium bisulfite (1.2 mol) was added to the obtained reaction liquid, and the mixture was further reacted to obtain a 35% by mass aqueous solution of sulfosuccinic acid monoalkylamide sodium salt.

(Emulsified dispersion etc. used in each example)
Hereinafter, the types (components shown in Tables 1 and 2) and the like of the emulsified dispersion used in each example will be described.

<I> Emulsified Dispersion Liquid [Component for Introducing Component (A)] Used for Introducing the Component (A) (Self-Emulsifying Aqueous Polyurethane Resin) into the Composition: Having the sulfonate group obtained in Preparation Example 2 An emulsion dispersion of a self-emulsifying aqueous polyurethane resin (water dispersion: content of 60% by mass of the component (A) (self-emulsifying aqueous polyurethane resin obtained in Preparation Example 2)).

<Ii> Emulsified Dispersion Liquid [Component for Introducing Component (B)] Used for Introducing Component (B) (Forced Emulsion Type Aqueous Polyurethane Resin) into the Composition Forced emulsification type aqueous solution obtained in Preparation Example 3 45% by mass of emulsion dispersion of polyurethane resin (water dispersion: component (B) (forced emulsion type aqueous polyurethane resin obtained in Preparation Example 3), component (G) (emulsifier: ethylene of tristyrenated phenol) Content 2 mass% of oxide 20 mol adduct: Furthermore, by preparing the composition using such aqueous dispersion, the composition contains not only the (B) component but also the (G) component and Hereinafter, optionally, "ethylene oxide 20 molar adduct of tristyrenated phenol" is simply referred to as "emulsifier (G1)".

<Iii> Component [C for introducing component (C)] used to introduce the component (C) (crosslinking agent) into the composition: Baihydur 3100 (polyether modified aliphatic polyisocyanate, polyether modified aliphatic poly Content of isocyanate (solid content): 100% by mass, Sumika Kobesturourethane: hereinafter, in some cases, "polyether modified aliphatic polyisocyanate" is referred to as "crosslinking agent (C1)".
TRIXENE AQUA BI 220 (aliphatic blocked isocyanate, content of aliphatic blocked isocyanate (solid content) 40% by mass, manufactured by BAXENDEN: hereinafter, in some cases, "aliphatic blocked isocyanate" and "crosslinking agent (C2)" Called).

<Iv> About the component [component for introduction of (D) component] utilized in order to introduce (D) component (foaming agent) into the composition Aqueous solution of ammonium stearate (content of ammonium stearate (solid content) 30% by mass: or less, in some cases, "ammonium stearate" is referred to as "compound (D1)"
An aqueous solution of sulfosuccinic acid monoalkylamide sodium salt obtained in Preparation Example 4 (content of sulfosuccinic acid monoalkylamide sodium salt (solid content) 35% by mass: or less, optionally “sulfosuccinate monoalkylamide sodium salt” Compound (D2) ”
Alaninate LN-30 (N-lauroyl-N-methyl-β-alanine sodium, N-lauroyl-N-methyl-β-alanine sodium content (solid content) 30% by mass, manufactured by Nikko Chemicals: no more, sometimes " N-lauroyl-N-methyl-β-alanine sodium ”is referred to as“ compound (D3) ”.

<V> Component [component for introducing component (E)] used for introducing component (E) (thickener) into the composition [bis (A) (nonionic polymer (association ether based thickening agent)] Agent) Sanyo Kasei Kogyo Co., Ltd. content (solid content) of nonionic polymer: 30% by mass: Hereinafter, the "nonionic polymer" in the neosticker S is sometimes referred to as a "thickener (E1)". )
Hydroxyethylcellulose (HEC Daicel SP 200, manufactured by Daicel Finechem Co., Ltd., content (solid content) 100% by mass of hydroxyethylcellulose: hereinafter, in some cases, “hydroxyethylcellulose” is referred to as “thickener (E2)”.)
Xanthan gum (Sunprint XN, manufactured by Tri Crystal Co., Ltd., content (solid content) 100% by mass of xanthan gum: hereinafter, in some cases, “xanthan gum” is referred to as “thickener (E3)”.).

<Vi> About the component utilized in order to introduce | transduce (H) component (thermosensitive gelling agent) into a composition Sodium sulfate (Hereafter, it is called "thermosensitive gelling agent (H1)" depending on the case.)
Alone A-50P (sulfonic acid monomer copolymer type acrylic thickener, Toagosei Co., Ltd. product, sulfonic acid monomer copolymer type acrylic thickener content (solid content) 95 mass%: or less, sometimes “ The sulfonic acid monomer copolymer type acrylic thickener is referred to as "thermosensitive gelling agent (H2)".

Example 1
First, 50% by mass of the emulsion dispersion of the self-emulsifiable aqueous polyurethane resin having a sulfonate group obtained in Preparation Example 2 as a component for introducing the component (A) (content of the self-emulsifiable aqueous polyurethane resin 60% by mass) And an emulsion dispersion of the forced emulsification type aqueous polyurethane resin obtained in Preparation Example 3 as a component for introducing the component (B) (the content of the forced emulsification type aqueous polyurethane resin is 45% by mass, ethylene of tristyrenated phenol An emulsion dispersion of an aqueous polyurethane resin was obtained by using a table whipper to stir a mixture of these using a proportion of 50 parts by mass of a 20 mol adduct of an oxide (emulsifier).

  Next, 2 parts by mass of an aqueous solution of ammonium stearate (content of ammonium stearate (solid content): 30% by mass) as a component for introducing the component (D) to the emulsion dispersion of the aqueous polyurethane resin, 4 parts by mass of an aqueous solution of sulfosuccinic acid monoalkylamide sodium salt obtained in Preparation Example 4 (content of sulfosuccinic acid monoalkylamide sodium salt (solid content) 35% by mass), alaninate LN-30 (N-lauroyl-N 4 parts by mass of the content (solid content) of methyl-β-alanine sodium (30 mass%) is added, and at the same time, the content of polyhydrodehydropolyurethane 3100 (polyether-modified aliphatic polyisocyanate as a component for component (C) introduction Add 10 parts by mass of 100 parts by mass) and stir for 10 minutes at a rotation speed of 1,000 RPM with a To obtain a mixture.

  Then, 2 parts by mass of bislyzer AP-2 (content of the nonionic polymer (solid content): 30% by mass) is added to the obtained mixed solution as a component for component (E) introduction, and the foam is obtained. After the composition for formation was obtained, the composition for foam formation was further stirred so that the expansion ratio would be 4 times, and dispersed in a creamy mechanical expansion (the expansion ratio 4 times) having a viscosity of 15000 mPas. A liquid [foaming composition (foam forming composition in a foamed state), solvent: water, total of components (A) and (B) in the dispersion: 43% by mass] was obtained. The expansion ratio is a value determined based on the volume of the composition for forming a foam (unfoamed composition) immediately after the addition of the component (E) and the volume of the composition after foaming ([after foaming Volume of the composition] / [volume of the unfoamed composition]).

  Next, the obtained dispersion (foaming composition) was applied onto the surface layer of the skin layer forming material obtained in Preparation Example 1 by a knife coating method using a doctor knife (coating thickness (average thickness) ) Is applied so as to be 1.8 mm and dried using a hot air drier at 120 ° C. for 5 minutes to cure the coating film, thereby forming a foamed resin layer laminated on the skin layer. I got a body. In addition, when the cross section of the perpendicular direction of the foam obtained in this way was measured with the electron microscope, while it is confirmed that the thickness (average thickness) of the foamed resin layer after drying is 1.1 mm. The foamed resin layer was confirmed to be a porous structure having a fine and uniform cell structure.

Then, on the foam formed on the skin layer, an adhesive of the following composition is applied so that the average thickness after drying is 50 μm, and dried using a pin tenter at a temperature of 80 ° C. for 1 minute, and further temperature It dried on condition of 110 degreeC and time 1 minute. After drying in this way, it is immediately bonded to a polyester knit (trade name "Polyester Double Pike" manufactured by Color Dyeing Company, basis weight: 241 g / m ² ), and further, using a calender, at a temperature of 150 ° C. and a pressure of 30 kg / cm 2 Lamination was performed under the conditions. Thereafter, aging was carried out for 2 days in a constant temperature and humidity chamber adjusted to conditions of temperature 45 ° C. and humidity 40% RH, and the release paper was peeled off to obtain a material for leather (leather-like laminate).
[Composition of adhesive (amount of each component used)]
Evafanol HO-38 (manufactured by Nikka Chemical Co., Ltd., main component of two-component aqueous polyurethane resin adhesive): 100 g
Baichur 3100: 10 g
Neo Sticker N (Nikka Chemical Co., Ltd., association type thickener): 1 g.

(Examples 2-14, Comparative Examples 1-3)
The same procedure as in Example 1 was carried out except that the types and amounts of the components used for producing the composition were changed to the types and amounts of the components shown in Tables 1 and 2, respectively. Like laminates were obtained respectively. In Examples 8 and 9, the component for component (H) introduction was simultaneously added with the component for component (A) introduction. Moreover, the symbol "-" in Tables 1-2 indicates that the component is not contained (the content of the component is 0).

[About the characteristics of the material (leather-like laminate) for leather obtained in Examples 1 to 14 and Comparative Examples 1 to 3]
The properties of the materials for leather (leather-like laminates) obtained in Examples 1 to 14 and Comparative Examples 1 to 3 were evaluated as follows. The evaluation results are shown in Tables 3 to 4 respectively. In addition, in Table 3-4, the composition of the composition for foam formation utilized by each Example etc. is shown collectively.

<Evaluation of texture>
The texture of the leather material (leather-like laminate) obtained in each of the examples and the comparative examples was evaluated according to the following criteria according to touch.
Grade 5: Soft and extremely resilient touch, very good texture grade 4: Soft and resilient, full touch, excellent texture grade 3: soft and resilient and feel enough, enough Feeling grade 2: Slightly rough and paper-like (paper-like) feel, slightly poor feeling Class 1: rough-hard and paper-like (paper-like) feel, inadequate feeling.

<Measurement of thickness of foam after drying>
Using the foam obtained in the preparation of the material for leather (leather-like laminate) in each Example and each Comparative Example, the cross section in the vertical direction of the foam is observed with an electron microscope to obtain the foam The average thickness of the foamed resin layer in the body was calculated. Moreover, in the case of the measurement of the average thickness of a foamed resin layer, thickness was each measured in three arbitrary measurement points in a cross section, and the average value was calculated | required. In addition, when the cross-sectional observation of the foamed resin layer formed in each Example etc. was carried out with an electron microscope, respectively, the surface is smooth enough in all and each foamed resin layer is sufficiently high in uniformity of thickness. Since it became, in this measurement, the average value of the thickness of three arbitrary measurement places was employ | adopted as an average thickness of the foamed resin layer formed in each Example and each comparative example. In addition, when the average value of the thickness of the foamed resin layer after drying is 50% or more (0.9 mm or more) of the average value (1.8 mm) of the application thickness, it has a sufficient thickness. It can be evaluated as a good foam.

<Measurement of material fracture strength>
JIS K 685 4-3: 1999 (Adhesive-Peeling strength test method-Part 3: T-type peeling) for the material for leather (leather-like laminate) obtained in each example and each comparative example A test similar to the test described in was carried out to determine the material breaking strength of the material for leather (leather-like laminate). In addition, in the case of a test, the test piece of 2 cm in width was prepared using the material for leather (leather-like laminated body). When such material fracture strength is 2 N / cm or more, it can be evaluated that the material is a good material for leather (leather-like laminate) having a sufficiently high material fracture strength.

<Evaluation of foamability of foam forming composition>
In each example and each comparative example, when obtaining a creamy mechanical foam (foaming magnification: 4 times) dispersion (foaming composition), a component for introducing the component (E) (in Example 1, “Bislyzer AP The time required for the foaming ratio to be 4 times after the addition of -2 ′ ′) is shown in Tables 3 and 4 as “the time required for 4 times foaming”.

  As is clear from the results shown in Tables 3 and 4, in the case of using the foam forming composition of the present invention (Examples 1 to 14), the time (minutes) required for 4 times foaming was all Is 20 minutes or less and the time for foaming to a high magnification such as 4 times is sufficiently short, so that it was confirmed that the foamability of the composition is sufficiently high to be able to foam efficiently. .

  When the foam forming composition of the present invention is used (Examples 1 to 14), the average value of the thickness of the foamed resin layer after drying is the average value of the thickness of the coating before drying (Examples 1 to 14) It is 50% or more (0.9 mm or more) of 1.8 mm), and it was confirmed that a good foam having a sufficient thickness can be obtained. On the other hand, in all of Comparative Examples 1 to 3, the average value of the thickness of the foamed resin layer after drying is 34% or less with respect to the average value (1.8 mm) of the thickness of the coating before drying. It became a size (0.6 mm or less) and could not obtain a foam having a sufficient thickness.

  Moreover, when the foam-forming composition of the present invention is used (Examples 1 to 14), the obtained leather material (material for leather) has a texture sufficiently excellent and the material fracture strength is also good. It was confirmed to be sufficiently advanced. Thus, the composition for forming a foam according to the present invention (Examples 1 to 14) can impart sufficient texture and material fracture strength to a leather material obtained by using the composition. I understood.

  As described above, according to the present invention, although the composition for forming foams containing an aqueous polyurethane resin, the foamability is sufficiently high and it is possible to efficiently foam, and It is also possible to make the thickness of the foamed resin layer made of a foamed cured product sufficient, and when the material for leather is manufactured using the composition, the texture and the material fracture strength sufficient for the material for leather to be obtained And a foam-forming composition capable of providing a foam; a method for producing a foam using the foam-forming composition; and a foam comprising a foamed resin layer comprising a foam-cured product of the foam-forming composition. It is possible to provide a body; and a leather material provided with the foam thereof. Such foam forming compositions of the present invention are, for example, materials of artificial leather (artificial leather and synthetic leather) used for vehicles, furniture, clothes, shoes, shoes, bags, sandals, miscellaneous goods, etc. Especially useful as

Claims (10)

  (A) Self-emulsifiable aqueous polyurethane resin having at least one hydrophilic functional group selected from the group consisting of sulfo group and sulfonate group, (B) forced emulsifying aqueous polyurethane resin, (C) crosslinker, (D A foam-forming composition comprising a foaming agent, (E) a thickener, and (F) water.   The composition for forming a foam according to claim 1, further comprising (G) an emulsifier. The foam according to claim 1 or 2, wherein the component (D) comprises at least one of the following compound (D1), the following compound (D2) and the following compound (D3). Composition for
[Compound (D1)]
The following general formula (1):
R ¹ COOX ・ ・ ・ (1)
(Wherein R ¹ has an alkyl group having 11 to 29 carbon atoms which may have a hydroxyl group, an alkenyl group having 11 to 29 carbon atoms which may have a hydroxyl group, and a hydroxyl group, Or any group selected from the group consisting of alkynyl groups having 11 to 29 carbon atoms, and X is selected from the group consisting of H, Na, K and an ammonium ion which may have a substituent. It is either.)
A compound represented by
[Compound (D2)]
The following general formula (2):
(Wherein, each of two A's is independently selected from the group consisting of groups represented by formulas: R ² O—, R ² N (H) —, (R ² ) ₂ N— and XO— And at least one of the two A's is selected from the group consisting of groups represented by the formula: R ² O—, R ² N (H) — and (R ² ) ₂ N— R ² is an alkyl group having 8 to 30 carbon atoms which may have a hydroxyl group, an alkenyl group having 8 to 30 carbon atoms which may have a hydroxyl group, and a hydroxyl group which satisfy the condition that any of them is satisfied. X 8 is H, Na, K, and an ammonium ion which may have a substituent. It is one selected from the group.)
A compound represented by
[Compound (D3)]
The following general formula (3):
R ³ C (O) N (R ⁴ )-(CH ₂ ) _n -B (3)
(Wherein R ³ has an alkyl group having 7 to 29 carbon atoms which may have a hydroxyl group, an alkenyl group having 7 to 29 carbon atoms which may have a hydroxyl group, and a hydroxyl group, R ⁴ is any one selected from the group consisting of an alkynyl group having 7 to 29 carbon atoms, and R ⁴ is any one selected from the group consisting of H and an alkyl group having 1 to 3 carbon atoms, n Is an integer of 1 to 3, B is any one selected from the group consisting of groups represented by the formula COOX and SO ₃ X, and X is H, Na, K and a substituent Is selected from the group consisting of ammonium ions which may have
A compound represented by   The component (D) is characterized in that it comprises at least one kind of the compound (D1), at least one kind of the compound (D2), and at least one kind of the compound (D3). The composition for forming a foam according to claim 3.   The composition for forming a foam according to any one of claims 1 to 4, further comprising (H) a thermosensitive gelling agent.   A process for obtaining a foam composition obtained by foaming the foam forming composition according to any one of claims 1 to 5, and the foam composition is applied to a substrate and dried and cured to obtain a substrate Obtaining a foam on which a foamed resin layer formed of a foamed cured product of the foam-forming composition is formed thereon.   The foam-forming composition contains an aqueous dispersion (I) of an aqueous polyurethane resin containing 50 to 70% by mass of the component (A), the component (B) and an emulsifier, and B) obtained by mixing an aqueous dispersion (II) of an aqueous polyurethane resin having a content of 30 to 70% by mass, the component (C), the component (D) and the component (E) The method for producing a foam according to claim 6, characterized in that   8. The method for producing a foam according to claim 6, wherein in the step of obtaining the foam composition, the foam-forming composition is foamed at a foaming ratio of 1.5 to 5 times. A substrate,
A foamed resin layer comprising a foamed and cured product of the composition for forming a foam according to any one of claims 1 to 5 laminated on the substrate;
A foam characterized in that it comprises.   A leather material comprising the foam according to claim 9.