JP7441742B2 - Composition for forming foam, foam, method for producing foam, and leather material - Google Patents

Description

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

Conventionally, as substitutes for natural leather, artificial leather comprising a polyurethane resin and a fiber base material made of a nonwoven fabric, and synthetic leather comprising a polyurethane resin and a fiber base material consisting of a woven or knitted fabric have been manufactured. Such pseudo-leather-like materials such as artificial leather and synthetic leather are produced by, for example, applying an organic solvent solution of polyurethane resin to a fiber base material by impregnation or coating. It was produced using a method called the wet coagulation method, in which the material is coagulated by passing it through a coagulating liquid (usually water) that is compatible with the liquid, followed by washing with water and drying.

However, the organic solvents often used in such wet coagulation methods are highly flammable and pose a risk of fire, and there are also concerns about deterioration of the working environment and environmental pollution such as air and water quality. In order to solve these problems, manufacturing methods that incorporate a process for recovering the organic solvents generated have been implemented, but problems such as high disposal costs and labor remain. Therefore, in recent years, studies have been made to shift the polyurethane resin that adheres to the fiber base material from an organic solvent type to an aqueous polyurethane resin. Then, as a material (leather material) for forming pseudo-leather-like objects such as artificial leather and synthetic leather, a foam is used in which a foam layer made of a foamed and cured product of a water-based polyurethane resin is laminated on a base material. It has been proposed, and various methods have been proposed for producing such foams.

For example, JP-A No. 2005-273083 (Patent Document 1) discloses that a fiber base material has 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 in its molecular skeleton. A foamed base material (layer A) on which a foam coating layer is 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. A method is disclosed in which a foam is obtained by adhering a layer (C layer) to a layer (C layer) by a dry lamination method using an adhesive (B layer) containing a water-based polyurethane resin and a polyisocyanate crosslinking agent. However, in the conventional foam manufacturing method as described in Patent Document 1, the foaming ratio of the foam-forming composition used cannot be made sufficiently high; When a foam obtained using the composition is used as a leather material to produce a simulated leather-like material (artificial leather, synthetic leather, etc.), it has not been possible to obtain a material with a sufficient texture.

Furthermore, JP-A No. 2006-070232 (Patent Document 2) discloses that a carboxyl group is added to a part of the molecular chain of an aqueous urethane main ingredient consisting of a polyether-based or polycarbonate-based aqueous urethane alone or a mixture or copolymer thereof. At least a foaming agent, a foam stabilizer, an oxazoline crosslinking agent, and a thickener are added while stirring the heat-sensitive gel type aqueous urethane dispersion that is introduced and forcibly dispersed in water together with a high cloud point surfactant. A method for producing a foam is described, which comprises mechanically foaming a foam-forming composition obtained by adding a foam-forming composition, applying the foam-forming composition to a base material, and performing drying and heat treatment one or more times. However, in the conventional method for producing a foam as described in Patent Document 2, the resulting foam cannot have sufficient material breaking strength, and the skin layer (base material) Adhesion between the foam layer and the foam layer could not be made sufficient.

Furthermore, International Publication No. 2012/008336 (Patent Document 3) contains (A) a water-based emulsion polyurethane resin, (B) an ammonium salt, and (C) a nonionic thickener; A step (1) of preparing a foam-forming composition comprising an aqueous dispersion (I) in which the amount of the aqueous dispersion (I) is 0.25 to 10 parts by mass based on 100 parts by mass of the solid content of component (A); a step (2) of applying the aqueous dispersion (I) to at least one surface of the substrate to form a coating film; and a step (3) of subjecting the coating film to a heat-sensitive gelling treatment to form a gelled film. , a step (4) of drying and solidifying the gelled film to form a film, and in step (1), the obtained aqueous dispersion (I) is heated to a foaming ratio of 1.1 to 2.5. A method for producing a double-expanding foam is disclosed. 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 such cases, the shrinkage of the coating film is large and the thickness of the foam layer is not sufficient, and the resulting foam is used as a leather material to produce pseudo-leather-like materials (artificial leather, synthetic leather, etc.) Therefore, it was not possible to provide a material with a sufficient texture.

Furthermore, International Publication No. 2014/162986 (Patent Document 4) discloses a foam-forming composition which is a raw material containing either an aliphatic isocyanate or a melamine derivative, a urethane emulsion, and an anionic foam stabilizer. A method for producing a polyurethane foam is disclosed in which the raw material is foamed by a mechanical floss method to form a froth, and the floss is heated and dried. However, in the conventional foam manufacturing method as described in Patent Document 4, the foam forming composition used does not have sufficient foaming properties, and for example, the foaming ratio is 3 times or more. It takes a considerable amount of time to achieve foaming (for example, it takes more than 20 minutes to increase the foaming ratio to 3 times). Furthermore, it took a long time, exceeding 20 minutes, for the foaming ratio to increase to four times. Furthermore, in the conventional foam manufacturing method as described in Patent Document 4, if the amount of foaming agent added is increased in order to improve the foamability of the raw material, the strength of the foam decreases. There was a problem with putting it away.

Furthermore, in JP 2019-112564 A (Patent Document 5), (A) a self-emulsifying water-based polyurethane resin having at least one hydrophilic functional group selected from the group consisting of a sulfo group and a sulfonate group; B) A foam-forming composition containing a forced emulsification type aqueous polyurethane resin, (C) a crosslinking agent, (D) a foaming agent, (E) a thickener, and (F) water is disclosed. Although such a foam-forming composition contains an aqueous polyurethane resin, it has sufficiently high foaming properties and can be foamed efficiently. It is also possible to make the foamed resin layer made of the cured product sufficiently thick, and furthermore, when the composition is used to manufacture leather materials, the resulting leather materials have a sufficient level of texture and material. It was possible to impart a high breaking strength. However, even with such a composition for forming a foam as described in Patent Document 5, there is still room for improvement in terms of achieving a higher level of material breaking strength when producing leather materials. there were.

Japanese Patent Application Publication No. 2005-273083 Japanese Patent Application Publication No. 2006-070232 International Publication No. 2012/008336 International Publication No. 2014/162986 JP 2019-112564 Publication

The present invention has been made in view of the problems of the prior art, and provides a composition for forming a foam containing an aqueous polyurethane resin, which has sufficiently high foaming properties and can be foamed efficiently. At the same time, it is possible to make the foamed resin layer made of the foamed and cured product of the composition sufficiently thick, and when the leather material is manufactured using the composition, the resulting leather material has a A composition for forming a foam that can impart sufficient texture and a higher level of material breaking strength; A method for producing a foam using the composition for forming a foam; A composition for forming a foam An object of the present invention is to provide a foam comprising a foamed resin layer made of a foamed cured product; and a leather material comprising the foam.

As a result of extensive research to achieve the above object, the present inventors have discovered that (A) a first self-emulsifying type having at least one hydrophilic functional group selected from the group consisting of a sulfo group and a sulfonate group; an aqueous polyurethane resin, (B) a second self-emulsifying aqueous polyurethane resin having at least one hydrophilic functional group selected from the group consisting of a carboxy group and a carboxylate group, (C) a crosslinking agent, and (D) a crosslinking agent; By containing a foaming agent, (E) a polysaccharide-based thickener, and (F) water, the resulting foam-forming composition has sufficient foaming properties even though it is a composition containing an aqueous polyurethane resin. In addition to making it possible to foam efficiently, it is also possible to make the foamed resin layer made of the foamed cured product of the composition sufficiently thick. The present inventors have discovered that when produced, it is possible to impart a sufficient texture and a higher level of material breaking strength to the resulting leather material, and have completed the present invention.

That is, the foam-forming composition of the present invention comprises (A) a first self-emulsifying aqueous polyurethane resin having at least one hydrophilic functional group selected from the group consisting of sulfo groups and sulfonate groups; ) a second self-emulsifying aqueous polyurethane resin having at least one hydrophilic functional group selected from the group consisting of a carboxy group and a carboxylate group, (C) a crosslinking agent, (D) a foaming agent, (E) It is characterized by containing a polysaccharide thickener and (F) water.

In the foam-forming composition of the present invention, the component (B) (the second self-emulsifying aqueous polyurethane resin) has a structural unit derived from an organic polyisocyanate, and the structural unit has an aromatic It is preferable that a structural unit derived from a polyisocyanate compound is included. Further, the component (B) (the second self-emulsifying aqueous polyurethane resin) according to the present invention has a structural unit derived from an organic polyisocyanate, and a structural unit derived from the organic polyisocyanate. More preferably, 5 to 60 mol% of the total amount is a structural unit derived from an aromatic polyisocyanate compound.

Further, the component (D) (the foaming agent) according to the present invention preferably contains the following compound (D1) and the following compound (D2), and the component (D) preferably contains the following compound (D1). ) and the following compound (D2), it is more preferable to further contain the following compound (D3).

[Compound (D1)]
General formula (1) below:
R ¹ COOX...(1)
(In the formula, 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) X is 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 ammonium ion which may have a substituent. Either one.)
A compound represented by

[Compound (D2)]
General formula (2) below:

(In the formula, each of the two A is independently selected from the group consisting of groups represented by the formula: R ² O-, R ² N(H)-, (R ² ) ₂ N- and XO- and at least one of the two A is selected from the group consisting of a group 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. is any group selected from the group consisting of alkynyl groups having 8 to 30 carbon atoms, which may have one selected from the group).
A compound represented by

[Compound (D3)]
General formula (3) below:
^R3 - _OSO3X ...(3)
(R ³ is any one selected from the group consisting of an alkyl group having 6 to 30 carbon atoms, an alkenyl group having 6 to 30 carbon atoms, and an alkynyl group having 6 to 30 carbon atoms, and X is H, Na, K, and (Any one selected from the group consisting of ammonium ions that may have a substituent.)
A compound represented by

In the foam-forming composition of the present invention, the component (E) (polysaccharide thickener) is at least selected from the group consisting of guar gum, tamarind seed gum, xanthan gum, carboxymethyl cellulose, and carrageenan. Preferably, it consists of one type of polysaccharide.

The method for producing a foam of the present invention also includes a step of obtaining a foam composition by foaming the composition for forming a foam of the present invention, and applying the foam composition to a base material and drying and hardening it to form a base material. This method is characterized by comprising the step of obtaining a foam in which a foamed resin layer made of a foamed and cured product of the foam-forming composition is formed on the material.

Further, in the method for producing a foam of the present invention, in the step of obtaining the foam composition, it is preferable that the foam-forming composition is foamed at a foaming ratio of 1.5 to 5 times.

The foam of the present invention is characterized by comprising a base material and a foamed resin layer laminated on the base material and made of a foamed and cured product of the foam-forming composition of the present invention. .

The leather material of the present invention is characterized by comprising the foam of the present invention described above.

According to the present invention, although it is a foam-forming composition containing an aqueous polyurethane resin, it has sufficiently high foaming properties and can be foamed efficiently, and it is possible to form a foam made of a foamed and cured product of the composition. It is possible to make the resin layer sufficiently thick, and when a leather material is manufactured using the composition, the resulting leather material has a sufficient texture and a higher level of material breaking strength. A foam-forming composition capable of providing a foam-forming 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. ; and a leather material comprising the foam.

Hereinafter, the present invention will be explained in detail based on its preferred embodiments.

[Foam-forming composition]
The foam-forming composition of the present invention comprises (A) a first self-emulsifying aqueous polyurethane resin having at least one hydrophilic functional group selected from the group consisting of sulfo groups and sulfonate groups; a second self-emulsifying aqueous polyurethane resin having at least one hydrophilic functional group selected from the group consisting of groups and carboxylate groups, (C) a crosslinking agent, (D) a foaming agent, and (E) a polysaccharide. It is characterized by containing a system thickener and (F) water. Hereinafter, first, each component will be explained separately.

<(A) Component: First self-emulsifying water-based polyurethane resin>
In the present invention, the first self-emulsifying aqueous polyurethane resin contained as component (A) 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) will be simply referred to as "first self-emulsifying water-based polyurethane resin"). Here, "aqueous" with respect to the first self-emulsifying water-based polyurethane resin (component (A)) means that after preparing an emulsified dispersion (solvent: water) in which the concentration of the polyurethane resin in water is 40% by mass, This means that it is possible to create a state in which no separation or sedimentation is observed even if the emulsified dispersion is allowed to stand at 20° C. for 12 hours.

Such a first 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. As described above, since the self-emulsifying water-based polyurethane resin (component (A)) according to the present invention has at least one hydrophilic functional group selected from the group consisting of sulfo groups and sulfonate groups, it is possible to It has a self-emulsifying property that allows it to be emulsified and dispersed in water without using a surfactant (for oxidation). In this way, the first self-emulsifying aqueous polyurethane resin (component (A)) is a type of aqueous polyurethane resin that can be emulsified and dispersed in water without using an emulsifier (a surfactant for emulsifying the resin). It is a polyurethane resin, that is, a self-emulsifying type (self-emulsifying type) water-based polyurethane resin.

The first self-emulsifying aqueous polyurethane resin (component (A)) is a self-emulsifying type that 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 water-based polyurethane resin may be used, and in addition to a sulfo group and/or a 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, the term "sulfo group" refers to a group represented by the formula: -SO ₃ H, the term "sulfonate group" refers to a group represented by the formula -SO ₃ ^- , and the term "carboxy group" refers to a group represented by the formula -SO 3 -. refers to a group represented by the formula: -COOH, and "carboxylate group" refers to a group represented by the formula: -COO ^- .

In such a first self-emulsifying water-based polyurethane resin (component (A)), in addition to the sulfo group and/or sulfonate group, other hydrophilic functionalities such as a carboxy group, a carboxylate group, and a quaternary ammonium group are present. When the hydrophilic functional group has a group, it is preferable that the content of the sulfo group and/or sulfonate group in all the hydrophilic functional groups including other hydrophilic functional groups is 70 mol% or more, and 80 mol% or more. It is more preferable that the amount is at least 90 mol %, particularly preferably 90 mol % or more. If the content ratio of such sulfo groups and sulfonate groups is less than the above-mentioned lower limit, it will be difficult to increase the resin ratio (high solid differentiation) when producing an aqueous dispersion of polyurethane resin, and the resulting foam It tends to be difficult to make the forming composition exhibit desired performance.

Thus, the first 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, and has a sulfo group and a sulfonate group. The content ratio of at least one selected from the group consisting of sulfonate groups is based on the total amount of all hydrophilic functional groups (sulfo groups, sulfonate groups, and all other hydrophilic functional groups) contained in the resin. It is preferably 70 to 100 mol%, more preferably 80 to 100 mol%, particularly preferably 90 to 100 mol%.

In addition, as such a first self-emulsifying water-based polyurethane resin (component (A)), from the viewpoint that it is possible to foam at a higher expansion ratio and to obtain higher peel strength. , an aqueous polyurethane resin having substantially only at least one functional group selected from the group consisting of a sulfo group and a sulfonate group in the resin skeleton as the hydrophilic functional group (for example, all hydrophilic functional groups (containing at least one hydrophilic functional group selected from the group consisting of sulfo groups and sulfonate groups in a proportion of 98 mol% or more based on the total amount of the resin) is preferable. More preferred is an aqueous polyurethane resin having only at least one functional group selected from the group consisting of a sulfo group and a sulfonate group in its skeleton.

Furthermore, such a first self-emulsifying water-based polyurethane resin (component (A)) can be used from the viewpoint of being able to foam at a higher expansion ratio while also achieving higher peel strength. The content of at least one hydrophilic functional group selected from the group consisting of , sulfo group and sulfonate group is preferably 0.1 to 15 milliequivalents per 100 g of polyurethane resin. From the same point of view, when component (A) contains a sulfo group and/or a sulfonate group as well as a carboxy group and a carboxylate group as hydrophilic functional groups (anionic groups), these hydrophilic The content of functional groups is preferably 0.1 to 15 milliequivalents per 100 g of polyurethane resin. The content of hydrophilic functional groups per 100 g of polyurethane resin is, for example, when the hydrophilic functional groups include a sulfo group and/or a sulfonate group as well as a carboxy group and/or a carboxylate group. It can be determined by calculating the sum of the amount of SO ₃ and _the amount of COO. (can be determined by calculating the total).

The first self-emulsifying aqueous polyurethane resin (component (A)) is not particularly limited, but includes, for example, (a) organic polyisocyanate, (b) polyol, (c) sulfo group and/or Or, after self-emulsifying in water a neutralized prepolymer having a sulfo group and/or a sulfonate group-containing isocyanate group, which is obtained by reacting a compound having a sulfonate group and two or more active hydrogens, (d) chain Preferably, it is an aqueous polyurethane resin having a sulfo group and/or a sulfonate group, which is obtained by a chain extension reaction using an extender. These components (a) to (d) will be explained separately.

(a) Organic polyisocyanate The organic polyisocyanate (component (a) above) used as a raw material for such a water-based polyurethane resin is not particularly limited, and includes aliphatic polyisocyanates having two or more isocyanate groups, two or more isocyanate groups, Alicyclic polyisocyanates having the above isocyanate groups and aromatic polyisocyanates having two 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. Examples of the alicyclic polyisocyanate having two or more isocyanate groups include isophorone diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, cyclohexylmethane diisocyanate, norbornane diisocyanate, 1,3-bis(isocyanatomethyl ) Alicyclic diisocyanate compounds such as cyclohexane and the like can be mentioned. Further, examples of the aromatic polyisocyanate having two or more isocyanate groups include aromatic diisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, toridine diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate. . In addition, the organic polyisocyanate used as the component (a) includes aliphatic polyisocyanates having two or more isocyanate groups, alicyclic polyisocyanates having two or more isocyanate groups, and two or more as described above. In addition to polyisocyanate compounds such as aromatic polyisocyanates having three or more isocyanate groups, alkyl-substituted, alkoxy-substituted, and nitro-substituted products of these polyisocyanate compounds, and preforms of these polyisocyanate compounds and polyhydric alcohols are also available. polymer type modified products, carbodiimide modified products of these polyisocyanate compounds, urea modified products of these polyisocyanate compounds, biuret modified products of these polyisocyanate compounds, dimerization or trimerization reaction products of these polyisocyanate compounds, etc. can also be used as appropriate. Such organic polyisocyanates (component (a)) may be used alone or in combination of two or more.

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

(b) Polyol The polyol (component (b) above) used as a raw material for such aqueous polyurethane resin is not particularly limited as long as it has two or more hydroxyl groups, and any polyol can be used as a raw material for polyurethane resin. Any known polyol that can be used can be used as appropriate. As such a polyol (component (b) above), for example, polyester polyol, polycarbonate polyol, polyether polyol, polyether ester polyol having an ether bond and an ester bond, etc. can be used as appropriate.

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. Diol, poly-ε-caprolactone diol, poly(3-methyl-1,5-pentylene)adipate diol, polycondensate of 1,6-hexanediol and dimer acid, 1,6-hexanediol and adipic acid and dimer acid copolycondensates of nonanediol and dimer acid, copolycondensates of ethylene glycol, adipic acid, and dimer acid, and the like.

Examples of the polycarbonate polyol include polycarbonate diol produced using a diol and carbonic acid diester as raw materials and using a transesterification catalyst. The diol may include a diol having 1 to 20 carbon atoms which may contain a hetero atom, and may have any structure such as a linear or branched chain group or a cyclic group. Further, examples of the heteroatoms include oxygen atoms, sulfur atoms, nitrogen atoms, and the like. Furthermore, examples of the diester carbonate include alkyl carbonates, aryl carbonates, and alkylene carbonates. As such polycarbonate diol, commercially available products may be used as appropriate, and examples include the BENEBiOL NL series manufactured by Mitsubishi Chemical Corporation, the Duranol series manufactured by Asahi Kasei Corporation, and the Kuraray Polyol series manufactured by Kuraray Co., Ltd. be able to.

Examples of the polyether polyol include diols that are homoaddition polymers or coaddition polymers of alkylene oxides having 2 to 4 carbon atoms, such as ethylene oxide, propylene oxide, butylene oxide, trimethylene oxide, and tetramethylene oxide; glycerin; , polyols in which the above-mentioned alkylene oxides having 2 to 4 carbon atoms are randomly or block-added to polyhydric alcohols such as trimethylolpropane.

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

(c) Compounds having a sulfo group and/or sulfonate group and two or more active hydrogens Compounds having a sulfo group and/or sulfonate group and two or more active hydrogens (component (c) above) include, 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 acids such as 1,3-propylenediamine-β-ethylsulfonic acid, 2-(3-aminopropylamino)-ethanesulfonic acid, and 2,4-diaminobenzenesulfonic acid; and their salts (e.g. alkali metal salt, etc.).

In addition, examples of the compound having the sulfo group and/or sulfonate group and two or more active hydrogens include dihydroxysulfonic acid such as an adduct of sodium bisulfite to 2-butene-1,4-diol; A polyester polyol having pendant hydrophilic functional groups obtained by reacting a diol having at least one hydrophilic functional group selected from the group consisting of sulfonate groups with an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, etc.; etc. can also be mentioned. These (c) components can be used alone or in combination of two or more.

Furthermore, when introducing a carboxyl group and/or a carboxylate group into the obtained aqueous polyurethane resin, a compound having a carboxyl group and/or a carboxylate group and two or more active hydrogens is added together with the component (c). It is preferable to use it. Examples of compounds having such a carboxy group and/or carboxylate group and two or more active hydrogens include 2,2-dimethylollactic acid, 2,2-dimethylolpropionic acid, and 2,2-dimethylolbutane. acid, dihydroxycarboxylic acids such as 2,2-dimethylolvaleric acid, and the like.

(d) Chain extender The chain extender (component (d)) used as a raw material for such a water-based polyurethane resin is not particularly limited, but includes, 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, propylene diamine, tetramethylene diamine, hexamethylene diamine, diaminocyclohexylmethane, piperazine, hydrazine, 2-methylpiperazine, and isophorone diamine. , norbornanediamine, diaminodiphenylmethane, tolylenediamine, xylylenediamine; polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, tris(2-aminoethyl)amine; diprimary Amidamines derived from amines and monocarboxylic acids; water-soluble amine derivatives such as monoketimines of di-primary amines; oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid Examples include hydrazine derivatives such as dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide, 1,1'-ethylene hydrazine, 1,1'-trimethylene hydrazine, and 1,1'-(1,4-butylene) dihydrazine. Such polyamine compounds having two or more amino groups and/or imino groups may be used alone or in combination of two or more.

<About the first method for preparing self-emulsifying water-based polyurethane resin>
The first self-emulsifying water-based polyurethane resin (component (A): hereinafter referred to as "self-emulsifying water-based polyurethane resin having a sulfo group and/or sulfonate group") is composed of the component (a), the above ( Component b) and the above component (c) are reacted to prepare a neutralized prepolymer with a sulfo group and/or sulfonate group-containing isocyanate group terminal, and after self-emulsification in water, (d) using a chain extender. Therefore, those obtained by chain elongation reaction can be suitably used.

In this way, a self-emulsifying aqueous polyurethane resin having a sulfo group and/or a sulfonate group is a neutralized product of an isocyanate group-terminated prepolymer having a sulfonate group (hereinafter referred to as a "neutralized product of an SU isocyanate group-terminated prepolymer" as the case may be). According to such a preparation method, such a polyurethane resin can be obtained by self-emulsifying an emulsified dispersion of a polyurethane resin in water and a chain extension reaction. It can be obtained as follows. Note that such a self-emulsifying water-based polyurethane resin may be used by extracting only the resin component from the emulsified dispersion, but since it is easier to prepare the composition, it is possible to use the emulsified dispersion of the polyurethane resin. It is preferable to use it in the preparation of compositions in this state.

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

In addition, 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, particularly preferably 300 or less. In addition, examples of the low molecular weight chain extender include low molecular weight chain extenders such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, and sorbitol. Hydrolic alcohol; low molecular weight polyamines such as ethylene diamine, propylene diamine, hexamethylene diamine, diaminocyclohexylmethane, piperazine, 2-methylpiperazine, isophorone diamine, diethylene triamine, triethylene tetramine and the like. 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, a reaction catalyst such as dibutyltin dilaurate, stannath octoate, dibutyltin-2-ethylhexanoate, triethylamine, triethylenediamine, N-methylmorpholine, etc. may be added as necessary. Can be done. Furthermore, an organic solvent that does not react with isocyanate groups can be added during or after the reaction. Examples of the organic solvent include acetone, methyl ethyl ketone, toluene, tetrahydrofuran, dioxane, dimethylformamide, N-methylpyrrolidone, ethyl acetate, and methyl isobutyl ketone.

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

There is no particular restriction on the method for emulsifying and dispersing the SU isocyanate group-terminated prepolymer neutralized product in water, and examples thereof include methods using emulsifying equipment such as a homomixer, a homogenizer, and a disper. In addition, when emulsifying and dispersing the SU isocyanate group-terminated prepolymer neutralized product in water, the prepolymer neutralized product is emulsified in water by self-emulsification at a temperature range of room temperature to 40°C without using an emulsifier. It is preferable to disperse the isocyanate groups to suppress the reaction between the isocyanate groups and water as much as possible. Furthermore, when emulsifying and dispersing in this way, a reaction inhibitor such as phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, para-toluenesulfonic acid, adipic acid, benzoyl chloride, etc. is added as necessary. be able to.

The chain extension reaction of the neutralized SU isocyanate group-terminated prepolymer can be carried out by adding the polyamine compound (d) having two or more amino groups and/or imino groups to the SU isocyanate group-terminated neutralized prepolymer. Alternatively, it can be carried out by adding the SU isocyanate group-terminated prepolymer neutralized product to the polyamine compound (d) having two or more amino groups and/or imino groups. Such 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 such a method for preparing an aqueous polyurethane resin having a sulfo group and/or a sulfonate group, the emulsification dispersion and the chain extension reaction may be performed simultaneously, and the SU isocyanate group-terminated prepolymer neutralized product The chain extension reaction may be carried out after the emulsification and dispersion, or the emulsification and dispersion may be carried out after the chain extension reaction. Further, when the above-mentioned organic solvent is used when producing the SU isocyanate group-terminated prepolymer neutralized product, it is preferable to remove the organic solvent by vacuum distillation or the like after the chain extension reaction or emulsification dispersion. Furthermore, although the polyurethane resin can be obtained as an emulsified dispersion of a polyurethane resin by such a preparation method, such an emulsified dispersion may further contain an emulsifier. As such an emulsifier, any known emulsifier that can be used when emulsifying a polyurethane resin can be appropriately used, and among them, it is preferable to use a nonionic surfactant. In addition, such nonionic surfactants include polyoxyethylene distyrylphenyl ether type nonionic surfactants, polyoxyethylene propylene distyrylphenyl ether type nonionic surfactants, and polyoxyethylene tristyrylphenyl ether type nonionic surfactants. Particularly preferred are nonionic surfactants, polyoxyethylene propylene tristyrylphenyl ether type nonionic surfactants, and pluronic type nonionic surfactants.

<(B) Second self-emulsifying water-based polyurethane resin>
In the present invention, the second self-emulsifying water-based polyurethane resin contained as component (B) is a self-emulsifying water-based polyurethane resin having at least one hydrophilic functional group selected from the group consisting of a carboxy group and a carboxylate group. (Hereinafter, in some cases, such component (B) will be simply referred to as "second self-emulsifying aqueous polyurethane resin"). Here, "aqueous" with respect to the second self-emulsifying water-based polyurethane resin (component (B)) means that the polyurethane resin is applied after preparing an emulsified dispersion (solvent: water) in which the concentration of the polyurethane resin in water is 40% by mass. This means that it is possible to create a state in which no separation or sedimentation is observed even if the emulsified dispersion is allowed to stand at 20° C. for 12 hours.

Such a second self-emulsifying aqueous polyurethane resin (component (B)) has at least one hydrophilic functional group selected from the group consisting of a carboxy group and a carboxylate group. As described above, since the self-emulsifying water-based polyurethane resin (component (B)) according to the present invention has at least one hydrophilic functional group selected from the group consisting of a carboxy group and a carboxylate group, It has self-emulsifying properties that allow it to be emulsified and dispersed in water without using a surfactant for emulsification. In this way, the second self-emulsifying aqueous polyurethane resin (component (B)) is a type of aqueous polyurethane resin that can be emulsified and dispersed in water without using an emulsifier (a surfactant for emulsifying the resin). It is a polyurethane resin, that is, a self-emulsifying type (self-emulsifying type) water-based polyurethane resin.

Such a second self-emulsifying water-based polyurethane resin (component (B)) has a hydrophilic functional group consisting of a carboxy group and/or a carboxylate group, and is a self-emulsifying resin that can be emulsified and dispersed without using a surfactant. The resin may have other hydrophilic functional groups such as a sulfo group, a sulfonate group, or a quaternary ammonium group in addition to a carboxy group and/or a carboxylate group.

In such a second self-emulsifying water-based polyurethane resin (component (B)), in addition to the carboxy group and/or carboxylate group, other hydrophilic functionalities such as a sulfo group, a sulfonate group, and a quaternary ammonium group are present. When it has a group, the content of carboxy groups and/or carboxylate groups in all hydrophilic functional groups including other hydrophilic functional groups is preferably 70 mol% or more, and 80 mol% or more. It is more preferable that it is, and it is especially preferable that it is 90 mol% or more. If the content ratio of such carboxyl groups and/or carboxylate groups is less than the above-mentioned lower limit, it will be difficult to increase the resin ratio (high solid differentiation) when producing an aqueous dispersion of polyurethane resin. It tends to be difficult to make the composition for forming a foam exhibit the desired performance.

In this way, the second self-emulsifying aqueous polyurethane resin (component (B)) has at least one hydrophilic functional group selected from the group consisting of a carboxy group and a carboxylate group, and has a carboxy group. The content ratio of at least one selected from the group consisting of It is preferably 70 to 100 mol%, more preferably 80 to 100 mol%, particularly preferably 90 to 100 mol%, based on the total amount.

In addition, such a second self-emulsifying water-based polyurethane resin (component (B)) can be used from the viewpoint of being able to foam at a higher expansion ratio while also achieving higher peel strength. , an aqueous polyurethane resin having substantially only at least one functional group selected from the group consisting of a carboxy group and a carboxylate group in the resin skeleton as the hydrophilic functional group (for example, all hydrophilic functional groups are Those containing at least one kind of hydrophilic functional group selected from the group consisting of carboxy group and carboxylate group in a proportion of 98 mol% or more based on the total amount of groups are preferable, and among them, as the hydrophilic functional group More preferably, the aqueous polyurethane resin has only at least one functional group selected from the group consisting of a carboxy group and a carboxylate group in its resin skeleton. In this way, the second self-emulsifying water-based polyurethane resin (component (B)) has only carboxy groups and/or carboxylate groups as hydrophilic functional groups, and contains other anionic groups and quaternary Self-emulsifying water-based polyurethane resins that do not have other ionic hydrophilic functional groups such as ammonium groups are preferred.

Furthermore, from the viewpoint that such a second self-emulsifying water-based polyurethane resin (component (B)) can be foamed at a higher expansion ratio and can also obtain higher peel strength. The content of at least one hydrophilic functional group selected from the group consisting of a carboxy group and a carboxylate group is preferably 2 to 120 milliequivalents, more preferably 2 to 60 milliequivalents, per 100 g of polyurethane resin. More preferred. From the same point of view, when component (B) contains a sulfo group or a sulfonate group as a hydrophilic functional group (anionic group) together with a carboxy group and a carboxylate group, these hydrophilic functional groups The content of is preferably 2 to 120 milliequivalents (more preferably 2 to 60 milliequivalents) per 100 g of polyurethane resin. The content of hydrophilic functional groups per 100 g of polyurethane resin is, for example, when the hydrophilic functional groups include a sulfo group and/or a sulfonate group along with a carboxy group and/or carboxylate group. It can be determined by calculating the sum of the amount of COO and the _amount of SO3 (in addition, if it contains only carboxy groups and/or carboxylate groups as hydrophilic functional groups, the amount of COO per 100 g of polyurethane resin ).

Such a second self-emulsifying aqueous polyurethane resin (component (B)) is not particularly limited, but includes, for example, (a) organic polyisocyanate, (b) polyol, (e) carboxyl group and/or Alternatively, after self-emulsifying in water a neutralized prepolymer having a carboxy group and/or a carboxylate group-containing isocyanate group, which is obtained by reacting a compound having a carboxylate group and two or more active hydrogens, (d ) Preferably, it is an aqueous polyurethane resin having a carboxy group and/or a carboxylate group, which is obtained by carrying out a chain extension reaction using a chain extender.

In addition, such a second self-emulsifying water-based polyurethane resin (component (B)) is not particularly limited, but it has a structural unit derived from an organic polyisocyanate (component (a) above). It is preferable that the structural unit contains a structural unit derived from an aromatic polyisocyanate compound. As described above, when the second self-emulsifying water-based polyurethane resin contains a structural unit derived from an aromatic polyisocyanate compound, the strength (material fracture strength) tends to be further improved.

Furthermore, such a second self-emulsifying water-based polyurethane resin (component (B)) has a structural unit derived from an organic polyisocyanate (component (a) above), and has a structural unit derived from the organic polyisocyanate. It is more preferable that 5 to 70 mol% (more preferably 20 to 60 mol%, particularly preferably 40 to 60 mol%) of the total amount of structural units derived from the aromatic polyisocyanate compound. If the content of the structural unit derived from such an aromatic polyisocyanate compound is less than the above-mentioned lower limit, it is difficult to obtain a sufficient effect (further improvement in strength (material fracture strength)) by using the structural unit. On the other hand, if the above upper limit is exceeded, the emulsifying property of the polyurethane resin in water tends to decrease, and various physical properties tend to decrease accordingly. Hereinafter, such an organic polyisocyanate (the above-mentioned component (a)) and the above-mentioned components (b), (d) and (e) will be explained separately.

(a) Organic polyisocyanate The organic polyisocyanate (component (a) above) used as a raw material for such a water-based polyurethane resin is not particularly limited, and the first self-emulsifying water-based polyurethane resin (component (A)) is not particularly limited. ) can be suitably used as the raw materials described above, such as the aforementioned aliphatic polyisocyanate having two or more isocyanate groups, the aforementioned aliphatic polyisocyanate having two or more isocyanate groups, Polyisocyanates and the aforementioned aromatic polyisocyanates having two or more isocyanate groups can be used as appropriate. Such organic polyisocyanates (component (a)) may be used alone or in combination of two or more.

In addition, when producing the second self-emulsifying water-based polyurethane resin (component (B)), among such organic polyisocyanates (component (a) above), from the viewpoint of material fracture strength of the film formed Therefore, it is preferable to use an aromatic polyisocyanate compound together with at least one of an aliphatic polyisocyanate compound and an alicyclic polyisocyanate compound. As such an aromatic polyisocyanate compound, diphenylmethane diisocyanate is preferable. Further, as the aliphatic polyisocyanate compound and the alicyclic polyisocyanate compound, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexylmethane diisocyanate, norbornane diisocyanate, and 1,3-bis(isocyanatomethyl)cyclohexane are more preferred. preferable.

Further, when an aromatic polyisocyanate compound and at least one of an aliphatic polyisocyanate compound and an alicyclic polyisocyanate compound are used together as the organic polyisocyanate (component (a) above), the aromatic polyisocyanate The content ratio of the compound is preferably 5 to 70 mol%, more preferably 20 to 60 mol%, and 40 to 60 mol% based on the total amount of the organic polyisocyanate (component (a) above). It is particularly preferable that there be. If the content ratio of the aromatic polyisocyanate compound exceeds the above upper limit (70 mol%), the emulsifying property of the finally obtained component (B) in water tends to decrease; on the other hand, if it is less than the above lower limit, , it tends to be difficult to obtain sufficient effects (further improvement in strength (material fracture strength)) by using aromatic polyisocyanate compounds.

(b) Polyol The polyol (component (b) described above) used as a raw material for such a water-based polyurethane resin is not particularly limited as long as it has two or more hydroxyl groups, and the polyol used as a raw material for such a water-based polyurethane resin is not particularly limited as long as it has two or more hydroxyl groups. The same materials as those described above as raw materials for the aqueous polyurethane resin (component (A)) can be suitably used. In addition, when the component (e) has two or more hydroxyl groups, the polyol used as the component (b) is a polyol that is different from the component (e) (for example, one that has a carboxy group and a carboxylate group). It is preferable to utilize polyols that do not contain polyols.

As such a polyol (the above-mentioned component (b)), any known polyol that can be used as a raw material for polyurethane resin can be used as appropriate, such as the above-mentioned polyester polyol, the above-mentioned polycarbonate polyol, the above-mentioned polyol, etc. Ether polyols, the aforementioned polyether ester polyols having an ether bond and an ester bond, and the like can be used as appropriate. Such polyols (component (b) above) may be used alone or in combination of two or more.

In addition, when producing the second self-emulsifying water-based polyurethane resin (component (B)), such a polyol (component (b) above) has a weight average molecular weight of 500 to 5000 (more preferably 500 to 5000) during production. It is preferable to use both a high molecular weight diol having a molecular weight of 1000 to 3000) and a low molecular weight diol having a molecular weight of 400 or less. In addition, as such "weight average molecular weight", the weight average molecular weight determined by gel permeation chromatography method is adopted, GPC (HLC-8220GPC, manufactured by Tosoh Corporation) is used, and mobile phase: tetrahydrofuran (THF). , Detector: RI, UV (254 nm), Flow rate: 0.25 ml/min, Column: Tsk-gel SuperHZ2000 x 25cm x 2/SuperHZ4000 x 15cm x 1, Temperature control: Column oven (40°C)/Inlet oven (40°C) / RI detector (35°C), sample concentration: 0.2% THF solution, sample injection volume: 5 μl, based on the measurement results of a standard substance (polyethylene glycol) with a known weight average molecular weight. A value obtained by conversion using the obtained calibration curve can be employed.

Such high molecular weight diols having a weight average molecular weight of 500 to 5000 are not particularly limited as long as they have two hydroxyl groups, and include polyester diols, polycarbonate diols, polyether diols, as well as ether bonds and ester bonds. Polyether ester diols, silicone diols, and fluorine diols having the following can also be used. These high molecular weight diols may be used alone or in combination of two or more.

Further, such polyester diols include, for example, polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyhexamethylene isophthalate adipate diol, polyethylene succinate diol, polybutylene succinate diol, polyethylene sebacate diol, 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 and adipine Examples include copolycondensates of acids and dimer acids, polycondensates of nonanediol and dimer acids, and copolycondensates of ethylene glycol, adipic acid, and dimer acids. The polycarbonate diol is preferably one produced using a diol and a carbonic acid diester as raw materials and using a transesterification catalyst, and the diol includes a diol having 1 to 20 carbon atoms that may contain a hetero atom. . Examples of carbonic acid diesters include alkyl carbonates, aryl carbonates, and alkylene carbonates. Further, as the polyether diol, for example, a diol that is a homoaddition polymer or coaddition polymer of alkylene oxide having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, trimethylene oxide, and tetramethylene oxide. can be mentioned.

Furthermore, examples of the silicone diol include those in which two hydroxy groups and/or hydroxy group-containing organic groups are introduced into the terminal and/or side chain of dimethylpolysiloxane, such as carbinol-modified silicone oil, polysiloxane, etc. Examples include ether-modified silicone oil and silanol-terminated silicone oil. Further, as the fluorine diol, for example, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, 2,2,3,3,4,4,5, Examples include 5,6,6,7,7-dodecafluoro-1,8-octanediol.

Examples of the low molecular weight diols having a molecular weight of 400 or less include ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, bisphenol A, and bisphenol A alkylene oxide adducts. Can be mentioned. These low molecular weight diols may be used alone or in combination of two or more.

Among these low molecular weight diols having a molecular weight of 400 or less, from the viewpoint of mechanical strength of the formed film, low molecular weight diols having a molecular weight of 300 or less are more preferable, such as ethylene glycol, bisphenol A, bisphenol A alkylene oxide. More preferred is the adduct, 1,4-butanediol. The alkylene group in the bisphenol A alkylene oxide adduct is preferably an ethylene group, and the average number of moles added is preferably 1 to 3 moles relative to bisphenol A.

Such low molecular weight diols should not contain carboxy groups and/or carboxylate groups when reacting with component (a), from the viewpoint of mechanical strength of the film formed and water resistance when formed into a film. It is preferable to react simultaneously with a compound (component (e)) having two or more active hydrogens (component (e) in combination with a low molecular weight diol). In this case, from the viewpoint of the mechanical strength of the formed film, the amount of the low molecular weight diol used is preferably 3 to 40 mol% based on the total amount of the low molecular weight diol and component (e).

(d) Chain extender The chain extender (component (d)) used as a raw material for such a water-based polyurethane resin is not particularly limited, and includes the above-mentioned first self-emulsifying water-based polyurethane resin (component (A)). The same materials as those described above (for example, the above-mentioned polyamine compound having two or more amino groups and/or imino groups) can be suitably used. Further, such chain extenders may be used alone or in combination of two or more.

(e) A compound having a carboxy group and/or a carboxylate group and two or more active hydrogens A compound having a carboxy group and/or a carboxylate group and two or more active hydrogens (component (e) above) Examples include dihydroxycarboxylic acids such as 2,2-dimethylollactic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid. Such component (e) can be used alone or in combination of two or more.

<About the preparation method of the second self-emulsifying water-based polyurethane resin>
The second self-emulsifying water-based polyurethane resin (component (B): hereinafter referred to as "self-emulsifying water-based polyurethane resin having a carboxy group and/or carboxylate group") is the component (a), the above-mentioned (b) Component and the above (e) component are reacted to prepare a neutralized prepolymer with carboxy group and/or carboxylate group-containing isocyanate group terminals, and after self-emulsification in water, (d) chain extender It is possible to suitably utilize the product obtained by carrying out a chain elongation reaction using.

In this way, a self-emulsifying water-based polyurethane resin having a carboxy group and/or a carboxylate group is a neutralized product of an isocyanate group-terminated prepolymer having a carboxylate group (hereinafter referred to as "neutralized CA isocyanate group-terminated prepolymer"). According to such a preparation method, such a polyurethane resin can be obtained by self-emulsifying an emulsified dispersion of a polyurethane resin (hereinafter referred to as a water dispersion (referred to as a water dispersion)). It can be obtained as II). Note that such a self-emulsifying water-based polyurethane resin may be used by extracting only the resin component from the emulsified dispersion, but since it is easier to prepare the composition, it is possible to use the emulsified dispersion of the polyurethane resin. It is preferable to use it in the preparation of compositions in this state.

The CA isocyanate group-terminated prepolymer neutralized product is a carboxylate group in which a carboxy group derived from a compound having a carboxy group and/or a carboxylate group and two or more active hydrogens (component (e) above) is neutralized. (-COO ^- ) is an isocyanate group-terminated prepolymer neutralized product having the above (a) organic polyisocyanate, the above (b) polyol, and (e) a carboxy group and/or carboxylate group and two or more active hydrogen atoms. It is obtained by reacting a compound having The specific method for obtaining such a CA isocyanate group-terminated prepolymer neutralization product is not particularly limited, and for example, a conventionally known one-stage so-called one-shot method, a multi-stage isocyanate polyaddition reaction method, etc. can be manufactured. The reaction temperature at this time is preferably 40 to 150°C.

Further, when preparing such a neutralized product of CA isocyanate group-terminated prepolymer, a low molecular weight chain extender having two or more active hydrogen atoms can be used as necessary. The low molecular weight chain extender preferably has a molecular weight of 400 or less, particularly preferably 300 or less. In addition, examples of the low molecular weight chain extender include low molecular weight chain extenders such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, and sorbitol. Hydrolic alcohol; low molecular weight polyamines such as ethylenediamine, propylene diamine, hexamethylene diamine, diaminocyclohexylmethane, piperazine, 2-methylpiperazine, isophorone diamine, diethylene triamine, triethylene tetramine and the like. 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, when preparing a neutralized product of CA isocyanate group-terminated prepolymer, dibutyltin dilaurate, stannath octoate, dibutyltin-2-ethylhexanoate, triethylamine, triethylenediamine, N-methyl A reaction catalyst such as morpholine can be added. Furthermore, an organic solvent that does not react with isocyanate groups can be added during or after the reaction. Examples of the organic solvent include acetone, methyl ethyl ketone, toluene, tetrahydrofuran, dioxane, dimethylformamide, N-methylpyrrolidone, ethyl acetate, and methyl isobutyl ketone.

The above (e) neutralization of the carboxy group derived from the compound having a carboxy group and two or more active hydrogens may be performed simultaneously with the preparation of the isocyanate group-terminated prepolymer, or may be performed before or after the preparation. It may be. Such neutralization can be carried out using a known method as appropriate, and the compounds used for such neutralization are not particularly limited, and examples include trimethylamine, triethylamine, tri-n-propylamine, and tributylamine. , N-methyl-diethanolamine, N,N-dimethylmonoethanolamine, N,N-diethylmonoethanolamine, triethanolamine; potassium hydroxide; sodium hydroxide; ammonia, and the like. Among these, tertiary amines such as trimethylamine, triethylamine, tri-n-propylamine, and tributylamine are particularly preferred.

There is no particular restriction on the method for emulsifying and dispersing the CA isocyanate group-terminated prepolymer neutralized product in water, and examples thereof include methods using emulsifying equipment such as a homomixer, a homogenizer, and a disper. In addition, when emulsifying and dispersing the CA isocyanate group-terminated prepolymer neutralized product in water, the prepolymer neutralized product is emulsified in water by self-emulsification at a temperature range of room temperature to 40°C without using an emulsifier. It is preferable to disperse the isocyanate groups to suppress the reaction between the isocyanate groups and water as much as possible. Furthermore, when emulsifying and dispersing in this way, a reaction inhibitor such as phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, para-toluenesulfonic acid, adipic acid, benzoyl chloride, etc. is added as necessary. be able to.

In addition, when preparing the second self-emulsifying water-based polyurethane resin, it is preferable to adopt a multistage isocyanate polyaddition reaction method to prepare a neutralized product of the CA isocyanate group-terminated prepolymer, and among them, the following step (A )～(D):
[Step (A)]
A step of reacting the organic polyisocyanate as the component (a) with the high molecular weight diol having a weight average molecular weight of 500 to 5,000 as the component (b) to obtain an isocyanate group-terminated prepolymer (S1);
[Process (B)]
The isocyanate group-terminated prepolymer (S1), the low molecular weight diol having a molecular weight of 400 or less as the component (b), the carboxy group and/or carboxylate group as the component (e), and two or more active hydrogen atoms. A step of reacting with a compound having the following to obtain a CA hydroxyl group-terminated prepolymer (S2);
[Step (C)]
A step of reacting the CA hydroxyl group-terminated prepolymer (S2) with the organic polyisocyanate that is component (a) to obtain a CA isocyanate group-terminated prepolymer (S3);
[Step (D)]
Neutralizing the CA isocyanate group-terminated prepolymer (S3) to obtain a neutralized CA isocyanate group-terminated prepolymer;
Method (X) comprising; or the following steps (i) to (iv):
[Step (i)]
The organic polyisocyanate as the component (a), the low molecular weight diol with a molecular weight of 400 or less as the component (b), the carboxy group and/or carboxylate group as the component (e), and two or more active groups. A step of reacting with a compound having hydrogen to obtain a CA isocyanate group-terminated prepolymer (S11);
[Step (ii)]
A step of reacting the CA isocyanate group-terminated prepolymer (S11) with the high molecular weight diol having a weight average molecular weight of 500 to 5,000 as the component (b) to obtain a CA hydroxyl group-terminated prepolymer (S12);
[Step (iii)]
A step of reacting the CA hydroxyl group-terminated prepolymer (S12) with the organic polyisocyanate that is component (a) to obtain a CA isocyanate group-terminated prepolymer (S13);
[Step (iv)]
Neutralizing the CA isocyanate group-terminated prepolymer (S13) to obtain a neutralized CA isocyanate group-terminated prepolymer;
It is preferable to use method (Y) comprising:

When such method (X) is adopted, it is preferable that the types of organic polyisocyanates (component (a)) used in step (A) and step (C) are different; ) and step (C), an aromatic polyisocyanate compound is used, and in the other step, an aliphatic polyisocyanate compound (at least an aliphatic polyisocyanate compound and an alicyclic polyisocyanate compound) is used. As a result, it is more preferable to use an aromatic polyisocyanate compound and an aliphatic polyisocyanate compound together as component (a). Furthermore, when the types of organic polyisocyanates (component (a)) used in step (A) and step (C) are different, an aromatic polyisocyanate compound is used in step (A), and the type of organic polyisocyanate used in step (C) is different. ) preferably uses an aliphatic polyisocyanate compound. Similarly, even when method (Y) is adopted, it is preferable that the types of organic polyisocyanates (component (a)) used in step (i) and step (iii) are different; An aromatic polyisocyanate compound is used in one step of i) and step (iii), and an aliphatic polyisocyanate compound (among an aliphatic polyisocyanate compound and an alicyclic polyisocyanate compound) is used in the other step. As a result, it is more preferable to use an aromatic polyisocyanate compound and an aliphatic polyisocyanate compound together as component (a). Furthermore, when the types of organic polyisocyanates (component (a)) used in step (i) and step (iii) are different, an aromatic polyisocyanate compound is used in step (i), and an aromatic polyisocyanate compound is used in step (iii). ) preferably uses an aliphatic polyisocyanate compound.

When an aromatic polyisocyanate compound and an aliphatic polyisocyanate compound are used together in this way, the molar ratio ([aromatic The ratio of polyisocyanate compound]:[aliphatic polyisocyanate compound] is preferably 5:95 to 70:30, more preferably 40:60 to 60:40. If the usage ratio of the aromatic polyisocyanate compound is less than the above-mentioned lower limit, it tends to be difficult to sufficiently obtain the effect (further improvement of strength (material fracture strength)) by using the aromatic polyisocyanate compound, On the other hand, if the above upper limit is exceeded, the emulsifying property of the polyurethane resin finally obtained in water tends to decrease, and various physical properties tend to decrease accordingly. In this way, when an aromatic polyisocyanate compound and an aliphatic polyisocyanate compound (at least one of an aliphatic polyisocyanate compound and an alicyclic polyisocyanate compound) are used together, the final It is also possible to introduce a repeating unit derived from an aromatic polyisocyanate compound into the (B) component obtained, and the finally obtained component (B) can be in the above-mentioned preferred form. It becomes possible.

In addition, as a method for obtaining a neutralized product of the CA isocyanate group-terminated prepolymer, it is easy to prepare the second self-emulsifying water-based polyurethane resin and an aqueous dispersion of the resin, and the resulting leather material has a more sufficient effect. Among them, it is more preferable to employ the method (X) from the viewpoint of being able to impart a comfortable texture and material fracture strength. Therefore, the neutralized product of the CA isocyanate group-terminated prepolymer is preferably a neutralized product of the CA isocyanate group-terminated prepolymer (S3) obtained by method (X) (here, the CA isocyanate group-terminated prepolymer (S3) is a reaction product of a CA hydroxy group-terminated prepolymer (S2) and an organic polyisocyanate (component (a)), and the CA hydroxy group-terminated prepolymer (S2) is a reaction product of the isocyanate group-terminated prepolymer (S1) and the organic polyisocyanate (component (a)). A reaction product of a low molecular weight diol having a molecular weight of 400 or less (component (b)) and a compound having the carboxy group and/or carboxylate group and two or more active hydrogens (component (e)), and the isocyanate The group-terminated prepolymer (S1) is a reaction product of the organic polyisocyanate and the high molecular weight diol (one of the components (b)) having a weight average molecular weight of 500 to 5,000.

Further, after obtaining the neutralized product of the CA isocyanate group-terminated prepolymer, a chain extension reaction is performed using the chain extension agent (d) as described above. Such a chain elongation reaction of the neutralized prepolymer terminated with a CA isocyanate group is performed by adding the chain extender (d) (having two or more amino groups and/or imino groups) to the neutralized prepolymer terminated with a CA isocyanate group. or by adding the CA isocyanate group-terminated prepolymer neutralized product to the (d) chain extender (polyamine compound having two or more amino groups and/or imino groups). It can be carried out. Such 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 such a method for preparing an aqueous polyurethane resin having a carboxy group and/or a carboxylate group, the emulsification dispersion and the chain extension reaction may be performed simultaneously, and the CA isocyanate group-terminated prepolymer neutralization The chain extension reaction may be carried out after the substance is emulsified and dispersed, or the substance may be emulsified and dispersed after the chain extension reaction is carried out. In addition, when the above-mentioned organic solvent is used when producing the CA isocyanate group-terminated prepolymer neutralized product, it is preferable to remove the organic solvent by vacuum distillation or the like after the chain extension reaction or emulsification dispersion. Furthermore, although the polyurethane resin can be obtained as an emulsified dispersion of a polyurethane resin by such a preparation method, such an emulsified dispersion may further contain an emulsifier. As such an emulsifier, any known emulsifier that can be used when emulsifying a polyurethane resin can be appropriately used, and among them, it is preferable to use a nonionic surfactant. In addition, such nonionic surfactants include polyoxyethylene distyrylphenyl ether type nonionic surfactants, polyoxyethylene propylene distyrylphenyl ether type nonionic surfactants, and polyoxyethylene tristyrylphenyl ether type nonionic surfactants. Particularly preferred are nonionic surfactants, polyoxyethylene propylene tristyrylphenyl ether type nonionic surfactants, and pluronic type nonionic surfactants.

<(C) Crosslinking agent>
The crosslinking agent used as component (C) in the present invention is not particularly limited, and any known crosslinking agent capable of crosslinking polyurethane resins can be used as appropriate, such as isocyanate crosslinking agents, oxazoline crosslinking agents, Epoxy crosslinking agents, aziridine crosslinking agents, carbodiimide crosslinking agents, formaldehyde resins, melamine resins, and glyoxal resins can be used.

Among these crosslinking agents (component (C)), isocyanate-based crosslinking agents are more preferred from the viewpoint of further improving peel strength. As such an isocyanate crosslinking agent, aliphatic, alicyclic or aromatic polyisocyanates can be used. Examples of such isocyanate-based crosslinking agents include tolylene diisocyanate, diphenylmethane diisocyanate (MDI), liquid MDI such as polyphenylpolymethylpolyisocyanate, crude MDI, hexamethylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, Hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, trimers of these isocyanurate rings, trimethylolpropane adducts, etc., compounds obtained by treating these with a blocking agent (compounds in which the isocyanate group is protected with a blocking agent) etc.

Further, such blocking agents include phenol, ε-caprolactam, 2-butanone oxime, hydrogen sulfite, bisulfite, dimethyl pyrazole, etc. Among them, dimethyl pyrazole, which has a relatively low thermal dissociation temperature, is more preferable. . As such an isocyanate-based crosslinking agent, a self-emulsifying polyisocyanate having a hydrophilic functional group in its structure can also be used.

Moreover, as such an isocyanate-based crosslinking agent, aliphatic or alicyclic polyisocyanate is particularly preferable from the viewpoint of light resistance. Note that as such aliphatic or alicyclic polyisocyanate, commercially available products may be used as appropriate, such as Baihydur 3100 (manufactured by Sumika Covestro Urethane), Aquanate 110, 210 (manufactured by Nippon Polyurethane), NK Assist IS-100N, NY-27, NY-30, NY-50 (manufactured by NICCA CHEMICAL), TRIXENE AQUA BI220 (manufactured by BAXENDEN), etc. can be used as appropriate.

In addition, such a crosslinking agent (component (C)) can be diluted when preparing the composition from the viewpoint of shortening the drying time and suppressing shrinkage of the foam during drying to a higher degree. It is preferable to add it as is without adding it.

<(D) Foaming agent>
The foaming agent contained as component (D) in the present invention is not particularly limited, and any known foaming agent that can be used to foam a polyurethane resin can be used as appropriate. As such a foaming agent (component (D)), for example, an anionic surfactant can be used.

Examples of anionic surfactants that can be used as such a foaming agent (component (D)) include sulfate-based anionic surfactants, amino acid-based anionic surfactants, and phosphate-based anionic surfactants. surfactants, carboxylic acid-based anionic surfactants, and sulfonic acid-based anionic surfactants. In addition, from the viewpoint of further improving the stability of the foam-forming composition and making it possible to form a foam having a fine cell structure, such anionic surfactants include neutralizing surfactants. More preferably, it is in the form of a salt.

Examples of such sulfate ester-based anionic surfactants include alkyl sulfates, polyoxyalkylene alkyl ether sulfates, and polyoxyalkylene alkyl monoalkylolamide sulfates. Furthermore, such amino acid-based anionic surfactants include acylglycinate, acylsarcosinate, acylalaninate, acylalkylalaninate, acyltaurate, acylalkyltaurate, and acylglutamate. Further, examples of the phosphate-based anionic surfactant include alkyl phosphate ester salts, polyoxyalkylene alkyl ether phosphate ester salts, and the like. Further, examples of the carboxylic acid-based anionic surfactant include higher fatty acid salts, polyoxyethylene alkyl ether carboxylates, and the like. Furthermore, the sulfonic acid-based anionic surfactants include olefin (C14-16) sulfonate, alkyl sulfosuccinate, polyoxyethylene sulfosuccinate alkyl salt, alkyl ethyl ester sulfonate, sulfosuccinate alkyl amide, alkyl Examples include diphenyl ether disulfonate. As such foaming agents, one type may be used alone, or two or more types may be used in any combination. Therefore, as the foaming agent, one type of anionic surfactant may be used alone, or two or more types may be used in any combination.

In addition, as the foaming agent (component (D)) according to the present invention, the following compounds (D1) to (D3) can be used, from the viewpoint of making it possible to more efficiently form a foam having a fine cell structure. :
[Compound (D1)]
General formula (1) below:
R ¹ COOX...(1)
(In the formula, 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) X is 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 ammonium ion which may have a substituent. Either one.)
A compound (D1) represented by
[Compound (D2)]
General formula (2) below:

(In the formula, each of the two A is independently selected from the group consisting of groups represented by the formula: R ² O-, R ² N(H)-, (R ² ) ₂ N- and XO- and at least one of the two A is selected from the group consisting of a group 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. is any group selected from the group consisting of alkynyl groups having 8 to 30 carbon atoms, which may have one selected from the group).
A compound (D2) represented by
[Compound (D3)]
General formula (3) below:
^R3 - _OSO3X ...(3)
(R ³ is any one selected from the group consisting of an alkyl group having 6 to 30 carbon atoms, an alkenyl group having 6 to 30 carbon atoms, and an alkynyl group having 6 to 30 carbon atoms, and X is H, Na, K, and (Any one selected from the group consisting of ammonium ions that may have a substituent.)
It is preferable to utilize any one of these compounds.

Regarding the compound (D1) represented by the above general formula (1), R ¹ in formula (1) has a C11-29 alkyl group 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, which may have a hydroxyl group, and an alkynyl group having 11 to 29 carbon atoms, which may have a hydroxyl group. The alkyl group, alkenyl group, and alkynyl group that can be used as R ¹ in formula (1) all have 11 to 29 carbon atoms. ^R1 in the formula (1) is such that the stability of the foam-forming composition is further improved, that a foam having a fine cell structure can be formed, and that the texture and strength are improved. From the viewpoint of making it possible to form a foam with higher performance, a group that does not have a hydroxyl group is preferable, and among these, an alkyl group having 13 to 23 carbon atoms is preferable, and an alkyl group having 15 to 19 carbon atoms is preferable. A group is more preferred, an alkyl group having 16 to 18 carbon atoms is even more preferred, and an alkyl group having 17 carbon atoms is particularly preferred.

Moreover, X in such formula (1) is one selected from the group consisting of H, Na, K, and ammonium ion which may have a substituent. Examples of the substituent in the ammonium ion which may have such a substituent include a hydroxyethyl group, a methyl group, and an ethyl group. Such X is that the stability of the foam-forming composition is further improved, that it is possible to form a foam having a fine cell structure, and that it is possible to form a foam that has higher texture and strength. From the viewpoint of being possible, Na, K, or ammonium ions which may have a substituent are preferable, and ammonium ions (NH ₄ ⁺ ) are particularly preferable.

Examples of the compound (D1) represented by the general formula (1) include ammonium stearate, ammonium palmitate, ammonium oleate, etc., but the stability of the foam-forming composition is further improved. Ammonium stearate is particularly preferable from the viewpoints of making it possible to form a foam having a fine cell structure, and making it possible to form a foam with higher texture and strength. Note that such compounds (D1) may be used alone or in combination of two or more.

Regarding the compound (D2) represented by the above general formula (2), two A's in formula (2) each independently represent the formula: R ² O-, R ² N(H)-, (R ² ) ₂ Any one selected from the group consisting of groups represented by N- and XO-. In addition, in such a compound (D2), at least one of the two A is a group consisting of 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 one of the following is selected.

The two A's in formula (2) are that the stability of the foam-forming composition is further improved, that it is possible to form a foam with a fine cell structure, and that the texture and strength are improved. It is preferable that at least one of A is a group represented by the formula: R ² N(H)-, and at least one of the two It is more preferable that one 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 formula (2), R ² is an alkyl group having 8 to 30 carbon atoms which may have a hydroxyl group, or an alkyl group having 8 to 30 carbon atoms which may have a hydroxyl group. It is any group selected from the group consisting of an alkenyl group and an alkynyl group having 8 to 30 carbon atoms which may have a hydroxyl group. The alkyl group, alkenyl group, and alkynyl group that can be used as R ² all have 8 to 30 carbon atoms. Such ^R2 includes further improving the stability of the foam-forming composition, making it possible to form a foam with a fine cell structure, and forming a foam with higher texture and strength. From the viewpoint of being able to Particularly preferred are alkyl groups of number 12 to 18. In addition, when A in such formula (2) is a group represented by the formula: Either one is selected. Such A as X in the group represented by the formula: Na is more preferable from the viewpoint of making it possible to form a foam with higher texture and strength (i.e., when A is a group represented by the formula: XO-, the formula: (More preferably, it is a group represented by NaO-).

In addition, in such formula (2), X in the moiety represented by the formula: -SO ₃ That's it. From the same viewpoint as the preferable one for R ² , such X is preferably Na, K or an ammonium ion which may have a substituent, more preferably Na or K, and Na is more preferable. It is particularly preferable.

Examples of the compound (D2) represented by the general formula (2) include sulfosuccinic acid monoalkylamide sodium salt (here, the alkyl group has 8 to 30 carbon atoms, and 12 to 18 carbon atoms). sulfosuccinic acid monoalkylamide potassium salts (herein, the alkyl group has 8 to 30 carbon atoms, preferably 12 to 18 carbon atoms), and among them, foam-forming compositions Monoalkyl sulfosuccinates have been developed from the viewpoints of improving the stability of sulfosuccinates, making it possible to form foams with a fine cell structure, and making it possible to form foams with higher texture and strength. More preferred is the amide sodium salt. Note that such compounds (D2) may be used alone or in combination of two or more.

Regarding the compound (D3) represented by the above general formula (3), R ³ in formula (3) is an alkyl group having 6 to 30 carbon atoms, an alkenyl group having 6 to 30 carbon atoms, and an alkynyl group having 6 to 30 carbon atoms. Any group selected from the group consisting of groups. The alkyl group, alkenyl group, and alkynyl group that can be used as R ³ all have 6 to 30 carbon atoms. Such ^R3 includes further improving the stability of the foam-forming composition, making it possible to form a foam with a fine cell structure, and forming a foam with higher texture and strength. From the viewpoint of being able to perform the following, an alkyl group having 6 to 30 carbon atoms is particularly preferred, an alkyl group having 6 to 12 carbon atoms is more preferred, and an alkyl group having 8 to 10 carbon atoms is even more preferred.

Moreover, X in formula (3) is any one selected from the group consisting of H, Na, K, and ammonium ion which may have a substituent. From the same viewpoint, X is preferably Na, K, or an ammonium ion which may have a substituent.

As the compound (D3) represented by the general formula (3), for example, an alkyl sulfate having 6 to 12 carbon atoms can be mentioned as a preferable compound, and among them, from the viewpoint of foamability and strength of the foam, From these, alkyl sulfates having 8 to 10 carbon atoms are more preferred. Examples of such a compound (D3) include commercially available products (for example, Pearlcrete (Daiichi Kasei Sangyo Co., Ltd.), which is a commercial product of an alkyl sulfate having 8 carbon atoms). ) may be used alone or in combination of two or more.

In addition, the foaming agent (component (D)) according to the present invention further improves the stability of the composition for forming a foam, enables the formation of a foam having a fine cell structure, and improves texture. From the viewpoint of making it possible to form a foam with higher strength and strength, compound (D1) and compound (D2) are used in combination (including compound (D1) and compound (D2)). ) is more preferable. Further, in the present invention, when the foaming agent (component (D)) contains compound (D1) and compound (D2), in addition to compound (D1) and compound (D2), the above compound (D3) Those containing are more preferred. Thus, the foaming agent (component (D)) is more preferably one containing compound (D1), compound (D2) and compound (D3).

In addition, when the foaming agent (component (D)) contains compound (D1) and compound (D2) (component (D) includes at least one of compound (D1) and at least one of compound (D2)). When using one type in combination), the content ratio of compound (D1) and compound (D2) is 1:20 to 20: by mass ratio ([compound (D1)]:[compound (D2)]). The ratio is preferably 1, and more preferably 1:9 to 9:1.

In addition, when such a foaming agent (component (D)) contains compound (D1), compound (D2), and compound (D3) (as component (D), at least one of compound (D1) and at least one of compound (D2) and at least one of compound (D3)), containing compound (D1), compound (D2), and compound (D3) The ratio is preferably 45:45:10 to 10:45:45 in mass ratio ([compound (D1)]: [compound (D2)]: [compound (D3)]), and is preferably 10:50: More preferably, the ratio is 40 to 30:40:30.

<(E) Polysaccharide thickener>
The polysaccharide thickener contained as component (E) in the present invention is a thickener made of polysaccharide. The "polysaccharide" mentioned here may be any sugar composed of many monosaccharides (e.g., glucose, mannose, etc.) linked together through glycosidic bonds (a sugar formed by polymerizing many monosaccharides through glycosidic bonds). , any known polysaccharide that satisfies such conditions can be used as appropriate.

Examples of such polysaccharide thickeners include cellulose derivatives such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylhydroxypropylcellulose, and carboxymethylcellulose; starches such as soluble starch, carboxymethylstarch, and methylstarch; Alginic acid-based polysaccharides such as sodium alginate and propylene glycol alginate ester; guar gum, tamarind seed gum, carrageenan, galactan, gum arabic, locust Bingham, quince seed, gum tragacanth, pectin, mannan, starch, xanthan gum, dextran, saccharide Natural polysaccharide-based polysaccharides such as sinoglucan and salts thereof; mixtures thereof; etc. can be suitably used. As such polysaccharide thickeners, one type may be used alone, or two or more types may be used in any combination.

Further, the structure of the polysaccharide used as such a polysaccharide thickener includes, for example, linear, side chain, branched, and spherical forms. As such polysaccharide-based thickeners (component (E)), from the viewpoint of further improving peel strength, polysaccharides consisting of polysaccharides with side chain, linear, or branched structures are recommended. It is more preferable to use a thickener. Examples of polysaccharides having such side chain, linear, or branched structures include guar gum, tamarind seed gum, xanthan gum, carboxymethyl cellulose, and carrageenan. Thus, as the polysaccharide thickener (component (E)), guar gum, tamarind seed gum, xanthan gum, carboxymethylcellulose, and carrageenan are more preferable from the viewpoint of further improving peel strength.

Moreover, as such a polysaccharide-based thickener, commercially available products may be used as appropriate. Commercial products of such polysaccharide thickeners include HEC AX-15 (manufactured by Sumitomo Seika Co., Ltd., hydroxyethyl cellulose), KELZAN (manufactured by Sansho Co., Ltd., xanthan gum), and SUPERGEL 200 (manufactured by Sansho Co., Ltd., guar gum). ), GENUVISCO CSW-2 (manufactured by Sansho Co., Ltd., carrageenan), and the like.

<(F) Water>
In the present invention, water is contained as component (F). Thus, the foam-forming composition of the present invention is a liquid composition containing water as the component (F). The water contained as such component (F) is not particularly limited, and ion-exchanged water or distilled water can be suitably used. Note that such water (component (F)) may be, for example, an emulsified dispersion obtained by emulsifying and dispersing the first self-emulsifying aqueous polyurethane resin (component (A)) in water, and/or a second emulsifying dispersion in water. A foam-forming composition is prepared by mixing each of the components (A) to (D) in water using an emulsified dispersion in which a self-emulsifying aqueous polyurethane resin (component (B)) is emulsified and dispersed; Thereafter, by using the water as it is without distilling off the water in the emulsified dispersion, the water may be used as the component (F) in the foam-forming composition.

<About the composition>
The foam-forming composition of the present invention contains the above-mentioned components (A) to (F). As described above, the foam-forming composition of the present invention contains the first self-emulsifying aqueous polyurethane resin (component (A)) and the second self-emulsifying aqueous polyurethane resin ((B) as the polyurethane resin components. ) component).

In such a foam-forming composition of the present invention, the total amount of the first self-emulsifying water-based polyurethane resin (component (A)) and the second self-emulsifying water-based polyurethane resin (component (B)) [Total amount of polyurethane resin component consisting of component (A) and component (B)] is preferably 30 to 60% by mass, more preferably 35 to 55% by mass. If the content of such a polyurethane resin component (total amount of the above-mentioned (A) component and above-mentioned (B) component) is less than the above-mentioned lower limit, the thickness, texture, and strength of the foamed cured product obtained using the foam-forming composition will deteriorate. On the other hand, if the above upper limit is exceeded, the viscosity of the foam-forming composition tends to increase, making it difficult to handle.

In addition, in the polyurethane resin component consisting of the first self-emulsifying water-based polyurethane resin (component (A)) and the second self-emulsifying water-based polyurethane resin (component (B)), component (A) and The content ratio of component (B) is determined based on the viewpoint that it is possible to foam at a higher expansion ratio during the production of the foam and to obtain a foam with higher peel strength, and the resulting foam From the viewpoints of improving the water resistance of the foam, preventing migration during foam production, and imparting a better texture to the foam, the mass ratio ([component (A)]: [component (B)) of component]), preferably 90:10 to 50:50, more preferably 80:20 to 60:40, particularly preferably 80:20 to 70:30.

In addition, in the foam-forming composition of the present invention, the content of the crosslinking agent (component (C)) is determined from the content of the first self-emulsifying water-based polyurethane resin (component (A)) from the viewpoint of improving peel strength. and 0.5 to 30 parts by mass per 100 parts by mass of the second self-emulsifying water-based polyurethane resin (component (B)) (hereinafter, in some cases, simply referred to as "total amount of polyurethane resin components"). parts (more preferably 1 to 25 parts by mass). If the content of such a crosslinking agent is less than the lower limit, the peel strength tends to decrease; on the other hand, if it exceeds the upper limit, there is little further improvement in performance, and the performance is insufficient to justify the amount of crosslinking agent used and the cost. There is a tendency for no improvement to be achieved.

Furthermore, in the composition for forming a foam of the present invention, the content of the foaming agent (component (D)) is such that it exhibits high material breaking strength even at a high expansion ratio, has a good texture, and has a thick leather material ( From the viewpoint of making it possible to obtain a leather-like laminate), the first self-emulsifying water-based polyurethane resin (component (A)) and the second self-emulsifying water-based polyurethane resin (component (B)) The amount is preferably 0.2 to 40 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the total amount (total amount of polyurethane resin components). Further, when using the compounds (D1) to (D3) as the foaming agent (component (D)), from the same viewpoint, the content of the compounds (D1) to (D3) should be in the following range. is preferred. That is, the content of the compound (D1) is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, based on 100 parts by mass of the total amount of the polyurethane resin component. , more preferably 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, based on 100 parts by mass of the total amount of the polyurethane resin component. More preferably, the amount 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, based on 100 parts by mass of the total amount of the polyurethane resin component. More preferably, the amount is .1 to 5 parts by mass.

Furthermore, in the composition for forming a foam of the present invention, the content of the polysaccharide thickener (component (E)) is such that the thickness of the foam after drying can be more fully maintained. From this point of view, the amount is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the total amount of the polyurethane resin component. In addition, if the content of the polysaccharide thickener is less than the above-mentioned lower limit, it tends to be difficult to maintain sufficient thickness of the foam after drying, while on the other hand, if it exceeds the above-mentioned upper limit, the strength of the foam decreases. or water resistance tends to decrease. In addition, the content of the polysaccharide-based thickener is determined from the viewpoints of shortening the time required for foaming to reach a predetermined foaming ratio, and making it possible to impart better texture and material breaking strength. is particularly preferably 0.1 to 5 parts by mass.

Further, in the foam-forming composition of the present invention, the content of water (component (F)) is preferably 25 to 60% by mass, more preferably 30 to 55% by mass. If the water content exceeds the above upper limit, the thickness, texture, and strength of the foamed cured product obtained using the foam-forming composition tend to decrease, while if it is below the lower limit, the foam formation tends to decrease. The viscosity of the composition for use tends to increase, making it difficult to handle.

In addition, the foam-forming composition of the present invention may contain other components (preferably conventionally used known additive components such as the following) as necessary, within a range that does not affect the effects of the present invention. May be used together. Such additive components include, for example, various surfactants such as fluorine-based and acetylene glycol-based surfactants, n-methylpyrrolidone, Anti-repellent agents for solvents such as propylene glycol monomethyl ether acetate, tackifiers such as rosin resin, rosin ester resin, terpene resin, terpene phenol resin, coumaron resin, antioxidants, light stabilizers, ultraviolet absorbers, etc. Antifoaming agents, mineral oil-based or silicone-based antifoaming agents, plasticizers, coloring agents such as pigments, and urethane reaction catalysts may be used in combination.

Furthermore, the foam-forming composition of the present invention may contain other resin components other than the above-mentioned components (A) and (B), as appropriate, within a range that does not impair the effects of the present invention. In order to contain such other resin components, when preparing the composition, an aqueous dispersion of the resin component (for example, vinyl acetate-based, ethylene-vinyl acetate-based, acrylic-based emulsion, etc.; styrene-butadiene-based emulsion) is added. , acrylonitrile-butadiene-based latexes; polyethylene-based, polyolefin-based ionomers, polyesters, polyamides, epoxy-based resins, etc.) may be used as appropriate. Here, the acrylic emulsion refers to a polymer obtained by radical polymerization of an acrylic acid monomer and a nonionic monomer, or a polymer obtained by radical polymerization of an acrylic acid monomer, a sulfonic acid monomer, and a nonionic monomer. It is a polymer obtained by emulsifying and dispersing a polymer in which the content of acrylic acid monomer and sulfonic acid monomer in the monomer mixture is less than 30% by mass in water in the presence of a surfactant. . Such an acrylic emulsion may be obtained by emulsifying and dispersing a produced polymer in water in the presence of a surfactant, or by emulsifying and dispersing a monomer in water in the presence of a surfactant. , or an emulsion obtained by emulsion polymerization.

Further, in the present invention, the (A) first self-emulsifying aqueous polyurethane resin, the (B) second self-emulsifying aqueous polyurethane resin, the (C) crosslinking agent, the (D) foaming agent, the (E) A method for producing a foam-forming composition containing a polysaccharide thickener and (F) water is not particularly limited, and known methods can be used as appropriate. . Note that the above (A) component and the above (B) component are usually obtained as emulsified dispersions of resins (water emulsified dispersions: aqueous dispersions of aqueous polyurethane resins), and aqueous polyurethane resins are generally obtained as emulsified dispersions of resins. (Aqueous emulsified dispersion: an aqueous dispersion of an aqueous polyurethane resin) is distributed on the market, so when producing the foam-forming composition of the present invention, from the viewpoint of production efficiency, the above-mentioned ( Component A) and component (B) are each used as an emulsified dispersion (aqueous emulsified dispersion: an aqueous dispersion of an aqueous polyurethane resin), and are combined with the crosslinking agent (C), the foaming agent (D), And, by mixing the polysaccharide thickener (E), the (A) first self-emulsifying aqueous polyurethane resin, the (B) second self-emulsifying aqueous polyurethane resin, and the (C) It is preferable to prepare a foam-forming composition containing a crosslinking agent, the foaming agent (D), the polysaccharide thickener (E), and the water (F).

In addition, since it is easier to obtain a sufficient texture and strength in the foam-forming composition of the present invention, it is preferable to use water-based polyurethane resin containing 50 to 70% by mass of the component (A). Dispersion (I), an aqueous dispersion (II) of an aqueous polyurethane resin in which the content of the (B) component is 30 to 70% by mass, the (C) component, the (D) component, and the (E) component. It is preferable that it be obtained by mixing. In the foam-forming composition obtained in this way, the aqueous polyurethane resins can be used and mixed in a state where they are each emulsified and dispersed in water, and the polyurethane resin components are added to the foam-forming composition obtained ( By using the aqueous dispersion (I) and the aqueous dispersion (II), the aqueous polyurethane resin component ((A It is also possible to efficiently produce a foam-forming composition (liquid composition) in which the concentrations of component ) and component (B) are high (preferably 40% by mass or more).

Such an aqueous dispersion (I) is an aqueous dispersion in which the content of the first self-emulsifying aqueous polyurethane resin, which is the component (A), is 50 to 70% by mass (more preferably 50 to 65% by mass). (Emulsified dispersion) is preferable. By using such aqueous dispersion (I), the foam-forming composition of the present invention can be used to form a foam having the desired properties (sufficient texture and strength). It becomes possible to manufacture more efficiently. If the content of the first self-emulsifying water-based polyurethane resin is less than the lower limit, even if the resulting foam-forming composition is used to form a foam, it is difficult to obtain a foam with sufficient strength. On the other hand, if the above upper limit is exceeded, the texture of the resulting foam tends to deteriorate. Such an aqueous dispersion (I) can be obtained by self-emulsifying the SU isocyanate group-terminated prepolymer neutralized product into water when the above-mentioned preparation method is adopted as the first self-emulsifying aqueous polyurethane resin preparation method. The above-mentioned emulsified dispersion of polyurethane resin, which can be obtained by emulsifying dispersion and chain extension reaction, can be used as is. Although the aqueous dispersion (I) contains the first self-emulsifying aqueous polyurethane resin, it may contain an emulsifier as appropriate.

In addition, such aqueous dispersion (II) contains water in which the content of the second self-emulsifying aqueous polyurethane resin, which is the component (B), is 30 to 70% by mass (more preferably 30 to 60% by mass). A dispersion liquid (emulsified dispersion liquid) is preferable. By using such aqueous dispersion (II), it becomes possible to form the desired foam more efficiently. If the content of such a second self-emulsifying water-based polyurethane resin is less than the above-mentioned lower limit, the texture of the foam obtained using it tends to deteriorate; on the other hand, if it exceeds the above-mentioned upper limit, the foam-forming composition It is becoming increasingly difficult to manufacture products efficiently. Such an aqueous dispersion (II) is obtained by self-emulsifying the CA isocyanate group-terminated prepolymer neutralized product into water when the above-mentioned preparation method is adopted as the second self-emulsifying aqueous polyurethane resin preparation method. The above-mentioned emulsified dispersion of polyurethane resin, which can be obtained by emulsifying dispersion and chain extension reaction, can be used as is. Although the aqueous dispersion (II) contains the second self-emulsifying aqueous polyurethane resin, it may contain an emulsifier as appropriate.

In addition, such aqueous dispersions (I) and (II) are suitable for the purpose of achieving higher peel strength while making it possible to foam at a higher expansion ratio, and the composition for forming a foam of the present invention. The first self-emulsifying water-based polyurethane resin ((A ) component) and the second self-emulsifying aqueous polyurethane resin (component (B)), the total amount (total amount) is 30 to 60% by mass (more preferably 35 to 55% by mass) based on the total amount of the foam-forming composition. It is preferable to use the aqueous dispersions (I) and (II) in such a manner that the dispersions (wt%)

Further, such a composition for forming a foam may be prepared by gently stirring the above-mentioned components to prevent foaming during preparation, or the composition may be foamed after the composition for forming a foam is prepared. If the composition is to be used immediately for the preparation of a foam, the components are mixed (stirred) so as to foam at the time of preparation, and the foamed composition (foamed foam) is foamed while preparing the foam-forming composition. A foam-forming composition may be prepared as a foam-forming composition (foam-forming composition). Note that such a foaming composition may be manufactured by preparing a foam-forming composition in advance, which is a mixture of each component, and mixing the compositions so as to mechanically foam them. In this manner, the foam-forming composition of the present invention may be prepared as a foam composition containing foamed foam.

Further, the foam-forming composition of the present invention (which may be in the form of the foamed composition described above) has a viscosity of 500 to 100,000 mPa·s (more preferably 1,000 to 50,000 mPa·s). s) is preferred. If the viscosity is less than the lower limit, it tends to be difficult to sufficiently suppress the foam from disappearing during foaming, and as a result, it tends to be difficult to foam at a sufficiently high expansion ratio. If the above upper limit is exceeded, handling tends to become difficult, and foaming tends to become difficult. In addition, as such a viscosity, a value measured by a method of measuring under a temperature condition of 20° C. using a BM type viscometer, No. 4 rotor, 60 rpm or 6 rpm is adopted.

The foam-forming composition of the present invention has been described above, and the method for producing a foam and the foam of the present invention will be described below.

[Method for producing foam and foam]
The method for producing a foam of the present invention includes the steps of obtaining a foam composition by foaming the composition for forming a foam of the present invention, and applying the foam composition to a base material, drying and curing it, and applying the foam composition to a base material. This method is characterized in that it includes the steps of: obtaining a foam in which a foamed resin layer made of a foamed and cured product of the foam-forming composition is formed. Further, the foam of the present invention is characterized by comprising a base material and a foamed resin layer laminated on the base material and made of a foamed and cured product of the foam-forming composition of the present invention. It is. It is preferable that such a foam is obtained by the above-described method for producing a foam of the present invention. Hereinafter, the method for manufacturing the foam of the present invention will be explained separately for each step.

(Process of obtaining foamed composition)
The step of obtaining such a foaming composition includes the step of obtaining a foaming composition obtained by foaming the foam-forming composition of the present invention (the step of obtaining a foaming composition that is a foam-forming composition in a foamed state). ). Such a step may be a step (I) in which the foam-forming composition of the present invention is prepared in advance in an unfoamed state and is stirred and mechanically foamed to obtain a foamed composition; , each component to be included in the foam-forming composition of the present invention ((A) the first self-emulsifying aqueous polyurethane resin, (B) the second self-emulsifying aqueous polyurethane resin, the (C) ) A crosslinking agent, (D) a foaming agent, (E) a polysaccharide thickener, and (F) water) are prepared and mixed and stirred to form a foam made of a mixture of each component. A foaming composition that is foamed while preparing a foam-forming composition and contains foamed foam in the composition (foamed foam-forming composition: one form of a foam-forming composition (foamed foam)) This may also be the step (II) for obtaining the form).

In such a step, the foam-forming composition includes the aqueous dispersion (I), the aqueous dispersion (II), the (C) component, the (D) component, and the (E) component. (Note that the water of component (F) is contained in the resulting composition by the water in the aqueous dispersion (I) and the aqueous dispersion (II).) ) is preferred.

In addition, a method for foaming a foam-forming composition (an aqueous dispersion of the components (A) to (E) above: a liquid composition) as described above (in the case of foaming while preparing the composition in step (II)) (including foaming methods), for example, by mechanically stirring the cream while drawing in air to a predetermined foaming ratio using a normal batch-type stirrer, such as a Hobart mixer, whipper, or disper. A method of obtaining a foamed dispersion can be adopted. 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 using an oak mixer, a pin mixer, or the like.

When foaming in this way, the foam forming composition is applied at a foaming ratio of 1.5 to 5 times (more preferably 1.5 to 4.5 times, even more preferably 1.5 to 4 times). Foaming is preferred. If the expansion ratio is less than the lower limit, it tends to be difficult to form a foam with a sufficiently high texture, while if it exceeds the upper limit, the strength of the resulting foam tends to decrease. It is in. For such a foaming ratio, a value calculated based on the volume of the composition before and after foaming ([volume after foaming]/[volume before foaming]) is used.

Such a foaming composition (liquid foam) preferably has a viscosity of 3,000 to 100,000 mPa·s (more preferably 5,000 to 80,000 mPa·s). If the viscosity is less than the lower limit, it will be difficult to sufficiently suppress bubble breakage during foaming (it will be difficult to sufficiently suppress bubbles from disappearing), and it will be difficult to foam at a sufficient expansion ratio. On the other hand, if the upper limit is exceeded, handling tends to become difficult and coating tends to become difficult. In addition, as such a viscosity, a value measured by a method of measuring at a temperature of 20° C. using a BM type viscometer, No. 4 rotor, and 6 rpm is adopted.

(Process of obtaining foam)
In the present invention, the step of obtaining a foam includes applying the foaming composition obtained in the above step to a base material, drying and curing it, and applying a foamed resin comprising a foamed and cured product of the foam-forming composition to the base material. This is the process of obtaining a foam with layers formed thereon.

Such base materials are not particularly limited, and include release paper, skin layer materials, fiber base materials, etc., and appropriate ones should be selected and used from among known base materials depending on the purpose. Bye. In addition, as such materials for the skin layer, fiber base materials, etc., materials similar to those described below in connection with leather materials may be appropriately used.

Furthermore, the method for applying the foamed composition to the base material is not particularly limited, and any known application method can be used as appropriate, such as roll coating, gravure coating, knife coating, reverse coating, kiss coating. method, comma coating method, lip coating method, etc.

Although the conditions for applying the foam composition to the substrate are not particularly limited, the average thickness after drying is It is preferable to apply the coating so that the thickness is 0.1 to 3.0 mm. In addition, such an average value of the thickness can be determined by observing the cross section using an electron microscope, and measuring the thickness at any plurality of measurement points (preferably 3 or more points) based on the electron micrograph of the cross section. It can be determined by calculating the average value.

Furthermore, the method of drying and curing after applying the foaming composition (for example, a composition comprising the foam-forming composition in the form of a mechanically foamed dispersion) is not particularly limited; for example, hot air drying A method of curing can be appropriately employed by drying in a conventionally known dryer such as a dryer, an infrared irradiation dryer, a microwave irradiation dryer, or a moist heat dryer. The drying conditions in such a drying and curing step may be changed as appropriate depending on the heat resistance temperature of the base material, and are not particularly limited, but it is preferable that the temperature is 80 to 120°C.

In addition, in the present invention, since the foam-forming composition is used to prepare the foam, shrinkage of the foam composition can be sufficiently suppressed in the drying and curing step, and the foaming after curing can be suppressed. It is possible to make the layer thickness sufficient, and since the foaming property of the foam-forming composition is sufficiently high, the foam can be made sufficiently thick from the viewpoint of the flexibility and impact resilience of the resulting foam. It is also possible to have a texture.

In this way, the foam composition is applied to a base material and dried and cured to obtain a foam in which a foam resin layer made of a foamed cured product of the foam-forming composition is formed on the base material. be able to. That is, the foam obtained in this way comprises a base material and a foamed resin layer laminated on the base material, which is made of a foamed and cured product of the foam-forming composition of the present invention. . The thickness of such a foamed resin layer is not particularly limited, but the average value of the thickness is 0.1 to 3.0 mm (more preferably 0.1 to 3.0 mm), since the texture and strength of the resulting foam will be higher. .1 to 2.0 mm). Such a foam can be suitably used as a material for leather (leather agent: leather-like laminate). The leather material of the present invention will be explained below.

[Leather materials]
The leather material of the present invention is characterized by comprising the foam of the present invention described above. As described above, since the leather material of the present invention includes at least the foam, it has a laminate 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 may have the same structure as known leather materials containing foams. Such a structure of the leather material of the present invention includes, for example, a skin layer material (for example, a skin layer formed on release paper (release paper is peeled off to leave only the skin layer) as the base material of the foam. ), etc.), the fiber base material is attached to the surface of the foam on the side opposite to the skin layer (base material) side (on the surface of the foam layer) via an adhesive layer. A stacked structure may also be used. Examples of such fiber base materials include nonwoven fabrics and fabrics.

The method for forming such a leather material is not particularly limited, and any known method can be used as appropriate. For example, the composition for forming a skin layer is coated on a release paper and dried. A skin layer (base material) is formed on the skin layer (base material), and a foam composition obtained by mechanically foaming the foam-forming composition is applied onto the skin layer (base material), and a foam is formed by drying and curing. Furthermore, a composition for forming an adhesive layer is applied on the surface of the foam layer (foamed resin layer) of the foam, and a fiber base material (for example, nonwoven fabric, cloth, etc.) is directly bonded to the surface and dried to form a laminate. A release paper transfer method such as a wet lamination method to form a leather material made of a laminate, or a dry lamination method to form a leather material made of a laminate by first drying the composition for forming an adhesive layer and then laminating it together; A composition for forming a skin layer is applied to the surface and dried to form a material for a skin layer, and a foamed resin layer is separately formed on the fiber base material (base material) using a fiber base material as a base material. Thermal transfer method in which a leather material consisting of a laminate is formed by forming the foam of the present invention and bonding the skin layer material with the foam using heat; After forming the foam of the present invention in which a foamed resin layer is formed on a material (base material), a method of directly applying a composition for forming a skin layer on the foam and drying it can be mentioned. .

When adopting such a method for forming a leather material, the composition for forming the skin layer is not particularly limited, and may be any known composition that can be used to form the skin layer of artificial leather or synthetic leather. Any resin composition can be used as appropriate, and for example, an aqueous polyurethane resin composition described in JP-A No. 2008-248174 and the like can be suitably used. In addition, the method for applying the skin layer forming composition onto the release paper or foam is not particularly limited, but includes spray method, roll coating method, gravure coating method, knife coating method, reverse coating method, kiss coating method. , a direct coating method using a comma coating method, a lip coating method, and the like.

Furthermore, when applying the composition for forming a skin layer, it is preferable to adjust the viscosity of the composition for forming a skin layer in order to improve suitability for processing. It is more preferable to adjust to 2500 to 15000 mPa·s (BM type viscosity type, No. 4 rotor, 6 rpm). The thickener used to adjust the viscosity of such a composition for forming a skin layer is not particularly limited, and any known thickener that can be used in a composition for forming a skin layer can be used as appropriate. Further, the method for drying such a composition for forming a skin layer after application is not particularly limited, and for example, it may be dried in a conventionally known drying machine such as a hot air dryer, an infrared ray irradiation dryer, a microwave irradiation dryer, or a moist heat dryer. It is sufficient to dry the film at a temperature of about 70 to 130°C for 10 seconds to 3 minutes.

Among the methods for forming such leather materials (leather-like laminates), from the viewpoint of improving the quality and physical properties of the obtained leather-like laminates and the physical properties of the obtained skin layer, release paper transfer is recommended. Among such release paper transfer methods, it is more preferable to employ a dry lamination method.

Here, the dry lamination method will be explained in more detail. Such a composition for forming an adhesive layer is not particularly limited, and any known composition capable of forming an adhesive layer can be used as appropriate. In such a dry lamination method, for example, a thickener is mixed into the adhesive layer forming composition to make the viscosity 2500 to 15000 mPa·s (BM type viscosity type No. 4 rotor, 6 rpm), and then The composition for forming an adhesive layer is coated on the surface of the foamed resin layer of the foam, dried in a dryer at 70 to 130°C for 10 seconds to 3 minutes, and then the surface coated with the composition for forming an adhesive layer and the fibers are coated. A method of laminating by laminating the base material with a nip roll at 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 to stabilize adhesion. may be adopted. Thereby, a laminated leather material (leather-like laminate) can be obtained.

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

Furthermore, the thickness and shape of the fibers included in such a fiber base material are not particularly limited. Furthermore, it is also possible to use ultrafine fibers as such fibers, and for example, any of sea-island type, split or peel type, direct spun type, and orange peel type fibers may be used when forming ultrafine fibers. When using sea-island fibers, ultra-fine methods include dissolving and extracting the sea component or island component by treating with organic solvents such as toluene, decomposition-extracting method with alkali etc., water jet method using high-pressure water stream, etc. The method is not particularly limited.

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

EXAMPLES Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

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

(Preparation Example 1: Preparation of material for forming epidermal layer)
<Preparation process of water-based polyurethane resin composition for forming skin layer>
First, each component is mixed and prepared in the following composition to obtain a liquid composition, and then the liquid composition is left to stand for one day (24 hours) at a temperature of 25°C to form an epidermal layer. A water-based 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 water-based polyurethane resin composition for forming skin layer (amount used of each component)]
Evafanol HA-107C (manufactured by NICCA CHEMICAL CO., LTD., aqueous dispersion of aqueous polyurethane resin) 100g
Neo Sticker N (manufactured by NICCA CHEMICAL CO., LTD., associative thickener) 3g
NXH-6022 (manufactured by NICCA CHEMICAL CO., LTD., antifoaming agent) 0.1 g.

<Preparation process of material for forming the epidermal layer (preparation process of the epidermal layer)>
Next, the aqueous polyurethane resin composition for forming a skin layer obtained as described above was placed on release paper (Asahi Roll Co., Ltd., Asahi Release AR-148) so that the film thickness after drying would be 30 μm. After coating and drying using a pin tenter at a temperature of 80°C for 2 minutes, further drying at a temperature of 120°C for 1 minute to form a skin layer on the release paper, thereby forming a skin layer forming material. Obtained.

(Preparation Example 2: Preparation of self-emulsifying water-based polyurethane resin (component (A)) having sulfonate groups)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, a polycarbonate diol made from 1,6-hexanediol (product name: "ETERNACOLL UH-100" manufactured by Ube Industries, Ltd.), weight After 213.8 parts by mass (average molecular weight 1,000), 0.002 parts by mass of dibutyltin dilaurate, and 75 parts by mass of acetone were mixed uniformly, 73.0 parts by mass of isophorone diisocyanate was added and reacted at 80°C for 90 minutes. An acetone solution of an isocyanate group-terminated prebolimer having a content of free isocyanate groups of 2.7% by mass was obtained.

After cooling the solution to below 50°C, 625.0 parts by mass of acetone was added to the solution, and then further cooling to below 30°C, and sodium 2-(2-aminoethylamino)-ethanesulfonate was added. Add an aqueous solution (45% by mass aqueous solution) containing sodium 2-(2-aminoethylamino)-ethanesulfonate so that the amount added is 10.2 parts by mass, and immediately add water while stirring using a disper blade. 425.7 parts by mass was gradually added to obtain an emulsified dispersion in which an isocyanate group-terminated prepolymer having a sulfonate group was emulsified and dispersed. Then, 33 parts by mass of an aqueous polyamine solution in which ethylenediamine was dissolved in water (concentration of ethylenediamine: 20% by mass, 6.6 parts by mass of ethylenediamine and 26.4 parts by mass of water) was added to the emulsified dispersion, and the mixture was heated at 35°C. After a chain elongation reaction for 60 minutes, the solvent was removed (deacetone) at 35°C under reduced pressure (95 KPa) so that the amount of nonvolatile matter was 60.0% by mass, and self-emulsification with sulfonate groups was carried out. An emulsified dispersion (aqueous dispersion) of aqueous polyurethane resin (polycarbonate-based aqueous urethane resin: first self-emulsifying aqueous polyurethane resin) was obtained. The emulsified dispersion thus obtained has a content of the first self-emulsifying 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 sulfonate groups was 400 nm. Moreover, the obtained polyurethane resin had 8.1 milliequivalents (calculated value) of SO ₃ per 100 g. A part of the obtained emulsified dispersion (aqueous dispersion) was used to prepare an emulsified dispersion (solvent: water) with a concentration of 40% by mass, and the emulsified dispersion was left to stand at 20°C for 12 hours. No separation or sedimentation was observed in the emulsified dispersion, confirming that the obtained polyurethane resin was an aqueous resin. Furthermore, since the obtained aqueous polyurethane resin was dispersed in water without using a surfactant, it was found that it was a self-emulsifying type aqueous polyurethane resin.

(Preparation Example 3: Preparation of self-emulsifying water-based polyurethane resin having carboxylate groups (component (B)))
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, polycarbonate diol (trade name "Duranol T5652" manufactured by Asahi Kasei Corporation, hydroxyl value 56.1 mgKOH/g, number average molecular weight: 2000) was placed. After adding 282.1 g of ethylene glycol, 1.8 g of dicyclohexylmethane diisocyanate, 55.5 g of diphenylmethane diisocyanate, and 16.8 g of 2,2-dimethylolpropionic acid, 157.0 g of methyl ethyl ketone as a solvent and amine type 11.3 g of a 1% by mass methyl ethyl ketone solution of a catalyst (product name "U-CAT SA-603" manufactured by San-Apro Co., Ltd.) was added and reacted at 80°C for 3 hours until the content of free isocyanate groups was 1. A methyl ethyl ketone solution of an isocyanate group-terminated prepolymer having 10% by mass of carboxy groups was obtained.

Next, after cooling the solution to 50° C. or lower, 12.7 g of triethylamine was added and a neutralization reaction was carried out at 40° C. for 30 minutes to neutralize the carboxy groups. After neutralizing the carboxy groups, the solution was cooled to below 30°C, and then 633.8 g of water was gradually added using a disperser blade to dissolve the isocyanate group-terminated prepolymer having carboxylate groups. The neutralized product was emulsified and dispersed to obtain an emulsified dispersion. Then, an aqueous polyamine solution in which 9.3 g of piperazine dihydrate was dissolved in 23.1 g of water was added to the emulsified dispersion, and after a chain elongation reaction at 40° C. for 60 minutes, the amount of nonvolatile matter was 40.0 mass. % of the self-emulsifying water-based polyurethane resin (second self-emulsifying water-based polyurethane resin) by removing the solvent (removing methyl ethyl ketone) under reduced pressure (95 KPa) at 35°C. An emulsified dispersion (aqueous dispersion) was obtained. The emulsified dispersion thus obtained has a second self-emulsifying aqueous polyurethane resin content of 40% by mass, a viscosity of 100 mPa·s (BM viscometer, No. 2 rotor, 60 rpm), and a carboxylic The average particle diameter of the polyurethane resin having a rate group was 110 nm. Further, the obtained polyurethane resin had a COO of 31 milliequivalents (calculated value) per 100 g. In addition, when a part of the obtained emulsified dispersion (aqueous dispersion) was used and left to stand at 20°C for 12 hours, no separation or sedimentation was observed in the emulsified dispersion, and the obtained polyurethane resin was water-based. It was confirmed that the resin was Furthermore, since the obtained aqueous polyurethane resin was dispersed in water without using a surfactant, it was found that it was a self-emulsifying type aqueous polyurethane resin.

(Preparation Example 4: Preparation of self-emulsifying water-based polyurethane resin having carboxylate groups (component (B)))
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, polycarbonate diol (trade name "Duranol T5652" manufactured by Asahi Kasei Corporation, hydroxyl value 56.1 mg KOH/g, number average molecular weight: 2000) was added. ) and 110.0 g of methyl ethyl ketone were charged and mixed uniformly to obtain a mixed solution. 55.5 g of diphenylmethane diisocyanate (MDI) was added to the mixed solution and reacted at 60° C. for 120 minutes. A methyl ethyl ketone solution (isocyanate group-terminated prepolymer solution) of an isocyanate group-terminated prepolymer having a content of free isocyanate groups of 0.5% by mass was obtained (first reaction step).

Next, after cooling the isocyanate group-terminated prepolymer solution to 40°C or lower, 1.8 g of ethylene glycol, 16.8 g of 2,2-dimethylolpropionic acid, and an amine catalyst (trade name manufactured by San-Apro Co., Ltd.) were added. Add 11.3 g of a 1% by mass methyl ethyl ketone solution of "U-CAT SA-603"), raise the temperature to 60 °C, and react at 60 °C for 120 minutes to create a methyl ethyl ketone solution of a hydroxyl-terminated prepolymer having a carboxy group. was obtained (second reaction step). At this time, no free isocyanate groups were observed.

Next, 38.8 g of dicyclohexylmethane diisocyanate (H12MDI) and 10 masses of a bismuth catalyst (trade name "Neostane U-600" manufactured by Nitto Kasei Co., Ltd.) were added to the methyl ethyl ketone solution of the hydroxyl-terminated prepolymer having a carboxy group. Add 1.1 g of % methyl ethyl ketone solution, raise the temperature to 80 ° C., and react at 80 ° C. for 180 minutes to obtain a methyl ethyl ketone solution of an isocyanate group-terminated prepolymer having a carboxy group with a free isocyanate group content of 1.10 mass %. (third reaction step).

Thereafter, 12.7 g of triethylamine was added to the methyl ethyl ketone solution of the isocyanate group-terminated prepolymer, and a neutralization reaction was carried out at 30°C for 60 minutes to neutralize the carboxy groups, followed by 633.8 g of ion-exchanged water with strong stirring. was gradually added to emulsify and disperse the neutralized isocyanate group-terminated prepolymer having carboxylate groups to obtain an emulsified dispersion. Next, 9.3 g of piperazine dihydrate dissolved in 23.1 g of water was added to the emulsified dispersion, and a chain elongation reaction was carried out at 40° C. for 60 minutes. %, the solvent was removed (methyl ethyl ketone removed) under reduced pressure (95 KPa) at 35 to 45°C, and a self-emulsifying water-based polyurethane resin having carboxylate groups (second self-emulsifying water-based polyurethane resin) was obtained. ) was obtained (fourth reaction step).

The emulsified dispersion thus obtained has a content of the second self-emulsifying aqueous polyurethane resin of 40% by mass, a viscosity of 93 mPa·s (BM viscometer, No. 2 rotor, 60 rpm), and a carboxylic acid dispersion. The average particle diameter of the polyurethane resin having a rate group was 103 nm. It had a COO of 31 mmol equivalent (calculated value) per 100 g of the obtained polyurethane resin. The obtained polyurethane resin had a molar ratio (MDI:H12MDI) of diphenylmethane diisocyanate (MDI) and dicyclohexylmethane diisocyanate (H12MDI) of 60:40. Furthermore, the obtained water emulsified dispersion of polyurethane resin having a carboxylate group did not gel even when heated to 90° C., and had no heat-sensitive coagulation property. In addition, when a part of the obtained emulsified dispersion (aqueous dispersion) was used and left to stand at 20°C for 12 hours, no separation or sedimentation was observed in the emulsified dispersion, and the obtained polyurethane resin was water-based. It was confirmed that the resin was Furthermore, since the obtained aqueous polyurethane resin was dispersed in water without using a surfactant, it was found that it was a self-emulsifying type aqueous polyurethane resin.

(Preparation Example 5: Preparation of self-emulsifying water-based polyurethane resin having carboxylate groups (component (B)))
The amount of MDI used was changed to 4.6 g so that the molar ratio of diphenylmethane diisocyanate (MDI) and dicyclohexylmethane diisocyanate (H12MDI) (MDI:H12MDI) was 60:40 to 5:95, and the amount of H12MDI used was changed. An emulsified dispersion of a self-emulsifying aqueous polyurethane resin having a carboxylate group (second self-emulsifying aqueous polyurethane resin) was prepared in the same manner as in Preparation Example 4, except that the amount was changed to 91.5 g. Aqueous dispersion) was obtained.

The emulsified dispersion thus obtained had a content of the second self-emulsifying aqueous polyurethane resin of 40% by mass and a viscosity of 100 mPa·s (BM viscometer, No. 2 rotor, 60 rpm). When the mixture was allowed to stand at 20° C. for 12 hours, no separation or sedimentation was observed in the emulsified dispersion, confirming that the obtained polyurethane resin was an aqueous resin. Furthermore, since the obtained aqueous polyurethane resin was dispersed in water without using a surfactant, it was found that it was a self-emulsifying type aqueous polyurethane resin.

(Preparation Example 6: Preparation of self-emulsifying water-based polyurethane resin having carboxylate groups (component (B)))
The amount of MDI used was changed to 9.2 g so that the molar ratio of diphenylmethane diisocyanate (MDI) and dicyclohexylmethane diisocyanate (H12MDI) (MDI:H12MDI) was 60:40 to 10:90, and the amount of H12MDI used was changed. An emulsified dispersion of a self-emulsifying aqueous polyurethane resin having a carboxylate group (second self-emulsifying aqueous polyurethane resin) was prepared by employing the same method as in Preparation Example 4, except that the amount was changed to 86.8 g. Aqueous dispersion) was obtained.

The emulsified dispersion thus obtained had a content of the second self-emulsifying aqueous polyurethane resin of 40% by mass and a viscosity of 98 mPa·s (BM viscometer, No. 2 rotor, 60 rpm). When the mixture was allowed to stand at 20° C. for 12 hours, no separation or sedimentation was observed in the emulsified dispersion, confirming that the obtained polyurethane resin was an aqueous resin. Furthermore, since the obtained aqueous polyurethane resin was dispersed in water without using a surfactant, it was found that it was a self-emulsifying type aqueous polyurethane resin.

(Preparation Example 7: Preparation of self-emulsifying water-based polyurethane resin having carboxylate groups (component (B)))
The amount of MDI used was changed to 27.6 g so that the molar ratio of diphenylmethane diisocyanate (MDI) and dicyclohexylmethane diisocyanate (H12MDI) (MDI:H12MDI) was 60:40 to 30:70, and the amount of H12MDI used was changed. An emulsified dispersion of a self-emulsifying aqueous polyurethane resin having a carboxylate group (second self-emulsifying aqueous polyurethane resin) was prepared in the same manner as in Preparation Example 4, except that 67.6 g was changed. Aqueous dispersion) was obtained.

The emulsified dispersion thus obtained had a content of the second self-emulsifying aqueous polyurethane resin of 40% by mass and a viscosity of 110 mPa·s (BM viscometer, No. 2 rotor, 60 rpm). When the mixture was allowed to stand at 20° C. for 12 hours, no separation or sedimentation was observed in the emulsified dispersion, confirming that the obtained polyurethane resin was an aqueous resin. Furthermore, since the obtained aqueous polyurethane resin was dispersed in water without using a surfactant, it was found that it was a self-emulsifying type aqueous polyurethane resin.

(Preparation Example 8: Preparation of self-emulsifying water-based polyurethane resin having carboxylate groups (component (B)))
The amount of MDI used was changed to 46.2 g so that the molar ratio of diphenylmethane diisocyanate (MDI) and dicyclohexylmethane diisocyanate (H12MDI) (MDI:H12MDI) was 60:40 to 50:50, and the amount of H12MDI used was changed to 46.2 g. An emulsified dispersion of a self-emulsifying aqueous polyurethane resin having a carboxylate group (second self-emulsifying aqueous polyurethane resin) was prepared in the same manner as in Preparation Example 4, except that the amount was changed to 48.4 g. Aqueous dispersion) was obtained.

The emulsified dispersion thus obtained had a content of the second self-emulsifying aqueous polyurethane resin of 40% by mass and a viscosity of 180 mPa·s (BM viscometer, No. 2 rotor, 60 rpm). When the mixture was allowed to stand at 20° C. for 12 hours, no separation or sedimentation was observed in the emulsified dispersion, confirming that the obtained polyurethane resin was an aqueous resin. Furthermore, since the obtained aqueous polyurethane resin was dispersed in water without using a surfactant, it was found that it was a self-emulsifying type aqueous polyurethane resin.

Here, regarding the self-emulsifying aqueous polyurethane resins having carboxylate groups obtained in Preparation Examples 3 to 8, Table 1 shows the proportions (mole ratio) of the raw materials (monomers) used in the production of each resin.

(Preparation Example 9: Preparation of forced emulsification type water-based polyurethane resin ((B') component))
Into a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 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 (manufactured by ADEKA Co., Ltd., product name: After adding 6.0 parts by mass of "ADEKA Polyether PR-3007", number average molecular weight: 3,000, oxyethylene group content: 70 mass%) and 49.2 parts by mass of methyl ethyl ketone as a solvent and mixing uniformly, Furthermore, 34.6 parts by mass of dicyclohexylmethane diisocyanate, which is an organic polyisocyanate, and 0.02 parts by mass of bismuth tris(2-ethylhexanoate) as a catalyst were added, and the temperature was adjusted to 80±5°C. The reaction was carried out for a minute to obtain a methyl ethyl ketone solution of a urethane prepolymer containing terminal isocyanate groups in which the content of free isocyanate groups in the urethane prepolymer was 1.34%. Next, 1.0 parts by mass of sodium dihydrogen phosphate as a reaction inhibitor and a polyoxyethylene tristyrylphenyl ether type nonionic surfactant (20 moles of ethylene oxide adduct of tristyrenated phenol) as an emulsifier were added to the methyl ethyl ketone solution. After adding 0.9 parts by mass and mixing uniformly, 290 parts by mass of water was gradually added and stirred to emulsify and disperse the terminal isocyanate group-containing urethane prepolymer. To the emulsified 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 3 parts of a 20% aqueous solution of diethylenetriamine After adding .75 parts by mass (0.75 parts by mass as diethylenetriamine) and stirring for 90 minutes while keeping the temperature at 40 ± 5°C, reduce the pressure so that the amount of non-volatile content was 47.0% by mass. Solvent removal (methyl ethyl ketone removal) was performed at 40° C. (95 KPa) to obtain an emulsified dispersion (aqueous dispersion) of a forced emulsification type aqueous polyurethane resin (forced emulsification type polycarbonate-based aqueous urethane resin). The emulsified dispersion thus obtained had a nonvolatile content of 47.0% by mass, a forced emulsification type aqueous polyurethane resin content of 45.0% by mass, and an emulsifier (20 mol of ethylene oxide of tristyrenated phenol). The content of adduct) was 2.0% by mass, the viscosity (at 20° C.) was 40 mPa·s, and the average particle diameter of the polyurethane resin was 0.3 μm. The polyurethane resin thus obtained has hydrophilic functional groups such as sulfo groups, sulfonate groups, carboxy groups, carboxylate groups, and quaternary ammonium groups, as is clear from the types of monomers. It was found that it was a forced emulsification type polyurethane resin (forced emulsification type polyurethane resin) because it required a surfactant to disperse in water. Further, using a part of the obtained emulsified dispersion (aqueous dispersion), an emulsified dispersion having a concentration of 40% by mass (solvent: water, containing the above emulsifier) was prepared, and the emulsified dispersion was When the emulsified dispersion was allowed to stand for 12 hours, no separation or sedimentation was observed in the emulsified dispersion, confirming that the obtained polyurethane resin was an aqueous resin.

(Preparation Example 10: Preparation of sulfosuccinic acid monoalkylamide sodium salt)
After reacting 1 mol of maleic anhydride with 1 mol of Firmin CS (manufactured by Kao Corporation) according to a conventional method, caustic soda (1.1 mol) and water were added to neutralize the mixture to obtain a reaction solution. Thereafter, anhydrous sodium bisulfite (1.2 mol) was added to the obtained reaction solution for further reaction to obtain a 35% by mass aqueous solution of sulfosuccinic acid monoalkylamide sodium salt.

(Regarding the emulsified dispersion liquid etc. used in each example etc.)
Hereinafter, the types of emulsified dispersions used in each example etc. will be explained.

<i> Regarding the emulsified dispersion liquid used to introduce component (A) (first self-emulsifying aqueous polyurethane resin) into the composition [component for introducing component (A)] Sulfonate obtained in Preparation Example 2 emulsified dispersion of a self-emulsifying aqueous polyurethane resin having a group (aqueous dispersion: content of component (A) (self-emulsifying aqueous polyurethane resin obtained in Preparation Example 2): 60% by mass, solvent (water) content 40% by mass).

<ii> Regarding the emulsified dispersion [component for introducing component (B)] used to introduce component (B) (second self-emulsifying aqueous polyurethane resin) into the composition obtained in Preparation Examples 3 to 8 Emulsified dispersion of a self-emulsifying aqueous polyurethane resin having carboxyl groups (aqueous dispersion: content of component (B) (second self-emulsifying polyurethane resin obtained in Preparation Examples 3 to 8): 40% by mass , a solvent (water) content of 60% by mass).
(In Comparative Examples 3 to 6, in order to introduce component (B') (forced emulsification type aqueous polyurethane resin) into the composition, the "component for introducing component (B')" obtained in Preparation Example 9 was used. (Using an emulsified dispersion (aqueous dispersion) of forced emulsification type water-based polyurethane resin).

<iii> Regarding the components used to introduce component (C) (crosslinking agent) into the composition [components for introducing component (C)] Baihydur 3100 (polyether-modified aliphatic polyisocyanate (component (C)), Content of polyether-modified aliphatic polyisocyanate (solid content) 100% by mass, manufactured by Sumika Covestro Urethane).

<iv> Regarding the component used to introduce component (D) (foaming agent) into the composition [component for introducing component (D)] Aqueous solution of ammonium stearate (content of ammonium stearate (solid content) 30% by mass, solvent (water) 70% by mass: hereinafter, "ammonium stearate" is sometimes referred to as "compound (D1)")
Aqueous solution of sulfosuccinic acid monoalkylamide sodium salt obtained in Preparation Example 10 (content (solid content) of sulfosuccinic acid monoalkylamide sodium salt 35% by mass, solvent (water) 65% by mass: hereinafter, in some cases, "sulfosuccinic acid (referred to as "compound (D2)")
Pearlcrete (C8 alkyl sulfate monoethanolamine salt, C8 alkyl sulfate monoethanolamine salt content (solid content) 24% by mass, solvent (water) 76% by mass, manufactured by Daiichi Kasei Sangyo Co., Ltd.: The following may be used depending on the case. "C8 alkyl sulfate monoethanolamine salt" is referred to as "compound (D3)").

<v> Regarding the components used to introduce component (E) (polysaccharide thickener) into the composition [components for introducing component (E)] The following (E1) to (E3):
(E1) KELZAN (xanthan gum, manufactured by Sansho Co., Ltd., xanthan gum content (solid content) 100% by mass: hereinafter, "xanthan gum" is sometimes referred to as "polysaccharide thickener (E1)".)
(E2) SUPERGEL200 (guar gum, manufactured by Sansho Co., Ltd., guar gum content (solid content 100% by mass: hereinafter, "guar gum" is sometimes referred to as "polysaccharide thickener (E2)".)
(E3) GENUVISCO CSW-2 (carrageenan, manufactured by Sansho Co., Ltd., carrageenan content (solid content 100% by mass: hereinafter, "carrageenan" in some cases is referred to as "polysaccharide thickener (E3)".)
Any one of these.
(In addition, in Reference Examples 1 and 2, instead of containing component (E) (polysaccharide thickener) in the composition, a nonionic polymer (hereinafter, nonionic polymer) was used as a reference component of the thickener. In some cases, the composition may be simply referred to as "component (E')"), and when producing the composition, the component for introducing component (E') is used instead of the component for introducing component (E). In addition, the "component for introducing component (E')" was "Vislyser AP-2 (nonionic polymer (associative ether thickener), manufactured by Sanyo Chemical Industries, Ltd., containing nonionic polymer. (solid content: 30% by mass, solvent (water): 70% by mass).

(Example 1)
First, as a component for introducing component (A), an emulsified dispersion of a self-emulsifying water-based polyurethane resin having a sulfonate group obtained in Preparation Example 2 (content of the first self-emulsifying water-based polyurethane resin is 60% by mass). and an emulsified dispersion of the self-emulsifying aqueous polyurethane resin having a carboxyl group obtained in Preparation Example 3 as a component for introducing component (B) (content of the second self-emulsifying polyurethane resin). 40% by mass) was used in a proportion of 30 parts by mass, and the mixed solution was stirred with a disper to obtain an emulsified dispersion of an aqueous polyurethane resin.

Next, 0.2 parts by mass of (E1) KELZAN (xanthan gum content (solid content) 100% by mass) was added as a component for introducing component (E) to the emulsified dispersion of the aqueous polyurethane resin, and then A mixed solution was obtained by stirring with a disper so that component (E) (xanthan gum) was uniformly dissolved in the emulsified dispersion.

Next, 2 parts by mass of an aqueous solution of ammonium stearate (ammonium stearate content (solid content) 30% by mass) was added as a component for introducing component (D) to the obtained mixed solution in Preparation Example 10. 4 parts by mass of the obtained aqueous solution of sulfosuccinic acid monoalkylamide sodium salt (content (solid content) of sulfosuccinic acid monoalkylamide sodium salt 35% by mass), Pearlcrete (content of C8 alkyl sulfuric acid monoethanolamine salt ( After adding 4 parts by mass of (solid content) 24% by mass), 10 parts by mass of Byhydur 3100 (content (solid content) of polyether-modified aliphatic polyisocyanate 100% by mass) was added as a component for introducing component (C). Then, the mixture was stirred using a disper at a rotational speed of 1,000 RPM for 10 minutes to obtain a foam-forming composition (unfoamed composition). Next, the obtained foam-forming composition (unfoamed composition) was further stirred with a tabletop whipper at a rotation speed of 950 RPM so that the foaming ratio was 3 times, and the viscosity was 30. , 000 mPas, a cream-like mechanically foamed dispersion (foaming ratio 3 times) [foaming composition (composition for forming a foamed body), solvent: water, component (A) in the dispersion and ( B) Total amount of component: 45% by mass] was obtained. The foaming ratio was determined based on the volume of the unfoamed foam-forming composition (unfoamed composition) before mechanical foaming with a tabletop whipper and the volume of the composition after foaming. The value is ([volume of foamed composition]/[volume of unfoamed composition]). The composition of the foam-forming composition obtained as described above (total amount: 120.2 parts by mass) is as follows: (A) component: 42 parts by mass, (B) component: 12 parts by mass, (C) Component: 10 parts by mass, component (D): 2.96 parts by mass (compound (D1): 0.6 parts by mass, compound (D2): 1.4 parts by mass, compound (D3): 0.96 parts by mass) , component (E): 0.2 parts by mass, and component (F) (water): 53.04 parts by mass.

Next, the obtained dispersion (foamed composition) was applied onto the skin layer of the skin layer forming material obtained in Preparation Example 1 by a knife coating method using a doctor knife until the thickness of the coating film was 1.8 mm. (Hereinafter, the set value of the coating film thickness will be regarded as the average value of the coating film thickness (application thickness). The foamed resin layer is laminated on the skin layer by applying the foam to a thickness of 5 minutes and drying it using a hot air dryer at a temperature of 120°C for 5 minutes to harden the coating. A foam was obtained. In addition, when the vertical cross section of the foam thus obtained was measured using an electron microscope, it was confirmed that the thickness (average thickness) of the foamed resin layer after drying was 1.75 mm. It was confirmed that the foamed resin layer was a porous structure having a fine and uniform cell structure.

Next, an adhesive having the following composition was applied onto the foam formed on the skin layer so that the average thickness after drying would be 50 μm, and dried using a pin tenter at a temperature of 80° C. for 1 minute. After drying in this way, it is immediately laminated with a polyester knit (trade name "Polyester Double Pique" manufactured by Shirozome Co., Ltd., weight: 241 g/m ² ), and further using a calendar at a temperature of 150°C and a pressure of 30 kg/cm ² Lamination was carried out under these conditions. Thereafter, it was aged for 2 days in a constant temperature and humidity chamber adjusted to a temperature of 45° C. and a humidity of 40% RH, and the release paper was peeled off to obtain a material for leather (leather-like laminate).
[Adhesive composition (amount of each component used)]
Evafanol HO-38 (manufactured by NICCA CHEMICAL CO., LTD., main ingredient of two-component water-based polyurethane resin adhesive): 100g
Bayhidur 3100: 10g
Neo Sticker N (Nicca Chemical Co., Ltd., associative thickener): 1 g.

(Comparative Examples 1 to 5 and Reference Example 1)
The same operations as in Example 1 were carried out, except that the types and amounts of ingredients used in the production of the composition were changed to those shown in Table 2, respectively, to prepare a leather material (leather-like laminated layer). body) were obtained. Note that the symbol "-" in Table 2 indicates that the component is not contained (the content of the component is 0).

[About the characteristics of the leather materials (leather-like laminates) obtained in Example 1, Comparative Examples 1 to 5, and Reference Example 1]
The properties of the leather materials (leather-like laminates) obtained in Example 1, Comparative Examples 1 to 5, and Reference Example 1 were evaluated as follows. The evaluation results are shown in Table 3.

<Evaluation of texture>
The texture of the leather materials (leather-like laminates) obtained in each Example and each Comparative Example was evaluated by touch according to the following criteria. Regarding the "texture" evaluated here, if it is grade 3 or higher, it can be judged that it is of a sufficiently high level, and the material for leather (leather-like laminate) with a texture of grade 3 or higher is It can be said that it has a good texture.
[Texture evaluation criteria]
Grade 5: Extremely soft and resilient to the touch, excellent texture Grade 4: Flexible and highly resilient to the touch, excellent texture Grade 3: Flexible and resilient to the touch, satisfactory Texture 2nd grade: Slightly rough, hard and paper-like (paper-like) feel, slightly unsatisfactory texture.1st grade: Rough, hard and paper-like (paper-like) touch, unsatisfactory texture.

<Measurement of foam layer thickness after drying>
Using the foams obtained in the preparation of leather materials (leather-like laminates) in each Example and Comparative Example, the vertical cross section of the foams was observed with an electron microscope, and the foamed The average thickness of the foamed resin layer in the body was calculated. This value is referred to as the "thickness of the foamed layer after drying." Further, when measuring the average thickness of the foamed resin layer, the thickness was measured at three arbitrary measurement points in the cross section, and the average value was determined. In addition, when the cross-sections of the foamed resin layers formed in each example were observed using an electron microscope, the surfaces of all of them were sufficiently smooth and the thickness of each foamed resin layer was sufficiently uniform. Therefore, in this measurement, the average thickness of the foamed resin layer formed in each example and each comparative example (thickness of the foamed layer after drying) is the average thickness of any three measurement points. The value was adopted. Here, if the thickness of the foam layer after drying (average thickness of the foam resin layer) is 50% or more of the thickness of the foam layer before drying, it is a good foam with sufficient thickness. It can be evaluated as such. In other words, if the "foam layer thickness retention rate (hereinafter simply referred to as "foam layer thickness retention rate" in some cases) obtained by calculating formula (I) below is 50% or more, In some cases, it can be evaluated as a good foam with sufficient thickness.
[Calculation formula (I)]
[R]={[T _A ]/[T _B ]}×100
(In the formula, R indicates the retention rate of the foam layer thickness (foam layer thickness retention rate, unit: %), T _A indicates the thickness of the foam layer after drying, and T _B indicates the thickness of the foam layer before drying. ).

<Measurement of material fracture strength>
JIS K6854-3:1999 (Adhesives - Peel adhesion strength test method - Part 3: T-shaped peel) for the leather materials (leather-like laminates) obtained in each example and each comparative example. A test similar to that described in was conducted to measure the material breaking strength of a leather material (leather-like laminate). In addition, for the test, a test piece with a width of 2 cm was prepared using a material for leather (leather-like laminate). Further, if the material breaking strength is 4.0 N/cm or more, it can be said that the material for leather (leather-like laminate) has a sufficiently high level of material breaking strength, and furthermore, if the material breaking strength is 4.0 N/cm or more, it can be said that the material for leather (leather-like laminate) has a sufficiently high level of material breaking strength. cm or more, it can be evaluated as a very good leather material (leather-like laminate) having a very high material breaking strength.

<Evaluation of foamability of foam-forming composition>
In each Example and each Comparative Example, when obtaining a creamy mechanically foamed dispersion (foaming composition) from the unfoamed foam-forming composition (unfoamed composition) In addition, the time required for the foaming ratio to increase to 3 times from an unfoamed state (unfoamed composition) is shown in Table 3 as "time required for 3 times foaming."

Note that Table 3 also shows the composition of the foam-forming composition. Furthermore, in Table 3, component (A) represents the self-emulsifying water-based polyurethane resin obtained in Preparation Example 2, and component (B) represents the self-emulsifying water-based polyurethane resin having a carboxyl group obtained in Preparation Example 3. Component (B') represents the forced emulsification type aqueous polyurethane resin obtained in Preparation Example 9, Component (C) represents the polyether-modified aliphatic polyisocyanate, and Component (D) represents the compounds (D1) to Indicates a mixture of compound (D3), (E) component indicates polysaccharide thickener (E1) (KELZAN), (E') component indicates nonionic polymer (reference component of thickener), ( Component F) indicates water (however, the numerical value of component (F) in Comparative Examples 3 to 5 is not the numerical value of only water, but the numerical value of component (F) contained in water and the emulsified dispersion of the forced emulsification type aqueous polyurethane resin used. The content of emulsifier in component (F) of Comparative Examples 3 to 5 is 2 parts by mass (Comparative Example 3), 0.6 parts by mass (Comparative Example 4), and 0.6 parts by mass (Comparative Example 4), respectively. 0.6 parts by mass (Comparative Example 5)). Furthermore, the symbol "-" in Table 3 indicates that the component is not contained (the content of the component is 0).

As is clear from the results shown in Table 3, when the foam-forming composition of the present invention was used (Example 1), the time (minutes) required to foam 3 times was 3 minutes; It was confirmed that the foaming property of the composition was sufficiently high and that it was possible to foam efficiently since the time required for foaming to a high magnification such as 2.5 times was sufficiently short.

Further, when the composition for forming a foam of the present invention was used (Example 1), the average value of the thickness of the foamed resin layer after drying was the average value of the thickness of the coating film before drying (1.8 mm). Since the foam layer thickness retention rate was 97%, it was confirmed that a good foam with sufficient thickness could be obtained. Furthermore, when the composition for forming a foam of the present invention was used (Example 1), the resulting leather material (material for leather) had an extremely excellent texture. Furthermore, when the foam-forming composition of the present invention was used (Example 1), the material breaking strength of the resulting leather material (leather material) was 6.5 N/cm, and the material breaking strength was 6.5 N/cm. was confirmed to be extremely high.

On the other hand, when the foam forming compositions obtained in Comparative Examples 1 to 3 were used, the foam layer thickness retention rate was less than 50%, resulting in good foaming with sufficient thickness. Couldn't get the body. Furthermore, when the foam-forming composition obtained in Comparative Example 4 was used, the material breaking strength was 3.5 N/cm, which is a sufficiently high level of material breaking strength of 4.0 N/cm or more. It was not possible to obtain the breaking strength.

In addition, when the composition for forming a foam obtained in Comparative Example 5 is used, the average value of the thickness of the foamed resin layer after drying is the average value of the thickness of the coating film before drying (1.8 mm). Since the foam layer thickness retention rate was 97%, it was confirmed that a good foam with sufficient thickness could be obtained. Furthermore, when the foam-forming composition obtained in Comparative Example 5 was used, the resulting leather material (leather material) had an extremely excellent texture. Further, when the composition for forming a foam obtained in Comparative Example 5 was used, the material fracture strength was 5.0 N/cm, which was a sufficiently high level of material fracture strength. Here, the foam-forming composition obtained in Comparative Example 5 and the foam-forming composition obtained in Example 1, which have almost the same composition except for the type of polyurethane resin component, were compared. In comparison, Example 1, which uses components (A) and (B) as polyurethane resin components, is better than Comparative Example 5, which uses components (A) and (B') as polyurethane resin components. It was found that even higher material fracture strength (6.5 N/cm) was obtained than that of the above. From these results, it was found that according to the foam-forming composition of the present invention, it is possible to obtain a leather material (leather material) having even more excellent properties in terms of material breaking strength. .

Furthermore, when the composition for forming a foam obtained in Reference Example 1 was used, the average value of the thickness of the foamed resin layer after drying was the average value of the thickness of the coating film before drying (1.8 mm). The foam layer thickness retention rate was 94%, confirming that a good foam with sufficient thickness could be obtained. Furthermore, when the foam-forming composition obtained in Reference Example 1 was used, the resulting leather material (leather material) had an extremely excellent texture. Further, when the composition for forming a foam obtained in Reference Example 1 was used, the material fracture strength was 6.0 N/cm, which was a sufficiently high level of material fracture strength. From these results, it was confirmed that even when the composition of Reference Example 1 was used, a leather material (material for leather) having sufficiently excellent physical properties could be formed. In addition, when comparing the foam-forming composition obtained in Example 1 and the foam-forming composition obtained in Reference Example 1, which differ only in the type of thickener, it is found that the polysaccharide-based thickener was not used. It was found that the foam-forming composition used in Example 1 had higher material fracture strength. From these results, it was found that according to the foam-forming composition of the present invention, it is possible to obtain a leather material (leather material) having even more excellent properties in terms of material breaking strength. .

(Examples 2 to 9)
The same operations as in Example 1 were carried out, except that the types and amounts of the components used in the production of the composition were changed to those shown in Table 4, respectively, to prepare a leather material (leather-like laminated layer). body) were obtained. Note that the symbol "-" in Table 4 indicates that the component is not contained (the content of the component is 0). For reference, Table 4 also shows the types and amounts of components used in the production of the composition for Example 1 as well.

[About the characteristics of the leather materials (leather-like laminates) obtained in Examples 2 to 9]
Using the same method as the evaluation method for the characteristics of the leather material (leather-like laminate) obtained in Example 1, Comparative Examples 1 to 5, and Reference Example 1, the texture and thickness of the foam after drying were evaluated. , material breaking strength, and foaming property (time required until the foaming ratio increased to 3 times) were evaluated. The results obtained are shown in Table 5. For reference, the results of Example 1 are also shown in Table 5. Table 5 also shows the compositions of the foam-forming compositions obtained in each example. In Table 5, component (A) represents the self-emulsifying water-based polyurethane resin obtained in Preparation Example 2, and component (B) represents the self-emulsifying water-based polyurethane resin having carboxyl groups obtained in Preparation Examples 3 to 8. Component (C) represents a polyether-modified aliphatic polyisocyanate, and component (D) represents a mixture of compounds (D1) to (D3) (Examples 1 to 6 and 8 to 9). Component (E) represents a polysaccharide thickener (E1), Component (F) represents water.

As is clear from the descriptions in Tables 4 and 5, the components for introducing component (A) (the sulfonate group-containing type self-emulsifying water-based polyurethane obtained in Preparation Example 2 (the first self-emulsifying water-based polyurethane resin) : Emulsified dispersion of component (A)) and component (B) for introducing component (carboxylate group-containing self-emulsifying aqueous polyurethane resin (second self-emulsifying aqueous polyurethane resin: component (B)). Comparison of Examples 1 to 6 in which the amount (mass ratio) of emulsified dispersion) was 70:30, and only the type of component (B) was different as the composition of the foam-forming composition. , when component (B) is obtained in a multi-stage reaction format (Preparation Examples 4 to 8), when component (B) is obtained in a so-called one-shot reaction format (preparation examples 4 to 8), The material breaking strength is higher than that in Example 3), and when the second self-emulsifying water-based polyurethane resin obtained in Preparation Examples 4 to 8 is used as component (B), the material It was found that it is possible to increase the breaking strength. From the results shown in Table 5, Examples 2 to 6 have better results than Example 1 in terms of material fracture strength, and other evaluation items (3 times It was found that the same results as in Example 1 were obtained regarding the time (minutes) required for foaming, the average thickness of the foamed resin layer after drying, and the texture. Therefore, when component (B) is obtained in a multi-stage reaction format (Preparation Examples 4 to 8), when component (B) is obtained in a so-called one-shot reaction format ( It was found that a leather material having better properties than Preparation Example 3) could be produced.

Furthermore, as is clear from the descriptions in Tables 4 and 5, in the composition of the foam-forming composition, in addition to the amount of water (component (F)), "compound (D3)" is used as component (D). Comparison of Examples 6 and 7, which differ only in whether or not they contain a compound (D3 ) (when compound (D3) is further used in addition to compound (D1) and compound (D2): Example 6), the material fracture strength is higher and the texture is also higher. It was found that the time required for foaming to be 3 times as large can be shortened.

Furthermore, as is clear from the descriptions in Tables 4 and 5, when the composition of the foam-forming composition has the same type of component (B), except for the amount of water (component (F)), (A) Example 6, which differs only in the content of the component and the component (B) (content of the component (A): 42 parts by mass, content of the component (B): 12 parts by mass, mass ratio ([component (A)] : [(B) component]) is 78:22), Example 8 ((A) component content: 30 parts by mass, (B) component content: 20 parts by mass, mass ratio ([(A) component]) ]: [component (B)]) is 60:40), Example 9 (content of component (A): 36 parts by mass, content of component (B): 16 parts by mass, mass ratio ([(A) component]: [component (B)]) was 69:31). When checking the evaluation results, it was found that 7.0 N was obtained when using any of the foam forming compositions obtained in Examples 6 and 8 to 9. It was confirmed that a sufficiently high material fracture strength of /cm was achieved. Furthermore, among the foam-forming compositions obtained in Examples 6 and 8 to 9 having such excellent properties, when further compared, the total amount of component (A) and component (B) was On the other hand, by using the foam-forming composition obtained in Example 6 in which the content of component (A) is 70% by mass or more, it is possible to achieve an even higher level of material fracture strength, and also to achieve a foamed layer film. It has been found that the thickness retention rate can also be made higher.

(Examples 10-11, Comparative Example 6 and Reference Example 2)
The same operations as in Example 8 were carried out, except that the types and amounts of the components used in the production of the composition were changed to those shown in Table 6, respectively, to obtain a leather material (leather-like laminated layer). body) were obtained. Note that the symbol "-" in Table 6 indicates that the component is not contained (the content of the component is 0). For reference, Table 6 also shows the composition of Examples 10 to 11 and Example 8, which uses the same ingredients in the same amounts, except for the type and amount of the component for introducing component (E). It also shows the types and amounts of ingredients used in the manufacture of the product.

[About the characteristics of the leather materials (leather-like laminates) obtained in Examples 10 to 11, Comparative Example 6, and Reference Example 2]
Using the same method as the evaluation method for the characteristics of the leather material (leather-like laminate) obtained in Example 1, Comparative Examples 1 to 5, and Reference Example 1, the texture and thickness of the foam after drying were evaluated. , material breaking strength, and foaming property (time required until the foaming ratio increased to 3 times) were evaluated. The results obtained are shown in Table 7. For reference, the results of Example 8 are also shown in Table 7. Table 7 also shows the compositions of the foam-forming compositions obtained in each example. Furthermore, in Table 7, component (A) represents the self-emulsifying water-based polyurethane resin obtained in Preparation Example 2, and component (B) represents the self-emulsifying water-based polyurethane resin having a carboxyl group obtained in Preparation Example 3. Component (B') represents the forced emulsification type aqueous polyurethane resin obtained in Preparation Example 9, Component (C) represents the polyether-modified aliphatic polyisocyanate, and Component (D) represents the compound (D1). - Indicates a mixture of compound (D3), component (E) indicates any of the polysaccharide thickeners (E1) to (E3), and component (E') indicates a nonionic polymer (reference component of thickener). ), and component (F) represents water.

As is clear from the descriptions in Tables 6 and 7, when the foam-forming composition of the present invention was used (Example 8 and Examples 10 to 11), the time (minutes) required to foam three times ) was 3 minutes, which is a sufficiently short time for foaming to a high magnification of 3 times, confirming that the foaming properties of the composition are sufficiently high and that it is possible to foam efficiently. . In addition, when the composition for forming a foam of the present invention was used (Example 8 and Examples 10 to 11), the average value of the thickness of the foamed resin layer after drying was the average value of the thickness of the coating film before drying. The size (1.6 mm) is almost the same as the value (1.8 mm), and the foam layer thickness retention rate is 89%, so a good foam with sufficient thickness can be obtained. was confirmed. Furthermore, when the foam-forming composition of the present invention is used (Example 8 and Examples 10 to 11), the resulting leather material (material for leather) has an extremely excellent texture. In addition, the material breaking strength of the obtained leather materials (materials for leather) was all 6.2 N/cm or more, and it was confirmed that the material breaking strength was extremely high. By comparing the results of Example 8 and Examples 10 to 11, which have the same composition except for the type and amount of component (E) used, it was found that polysaccharide was used as component (E) (polysaccharide thickener). Among the thickeners (E1) to (E3), it was found that it was possible to further increase the material breaking strength when using the polysaccharide thickener (E1) (xanthan gum). .

Further, when the composition for forming a foam obtained in Reference Example 2 was used, the average value of the thickness of the foamed resin layer after drying was 1.50 mm, and the foamed layer thickness retention rate was 83. %, it was confirmed that a good foam with sufficient thickness could be obtained. Furthermore, when the foam-forming composition obtained in Reference Example 2 was used, the resulting leather material (leather material) had an extremely excellent texture. Further, when the composition for forming a foam obtained in Reference Example 2 was used, the material fracture strength was 5.5 N/cm, which was a sufficiently high level of material fracture strength. From these results, it was confirmed that even when the composition of Reference Example 2 was used, a leather material (material for leather) having sufficiently excellent physical properties could be formed. In addition, when comparing the foam-forming compositions obtained in Example 8 and Examples 10 to 11, which differ only in the type of thickener, and the foam-forming composition obtained in Reference Example 2, it is found that It was found that the foam-forming compositions (the present invention) obtained in Example 8 and Examples 10 to 11 that utilized a sugar-based thickener had higher material breaking strength. Ta. From these results, it was found that according to the foam-forming composition of the present invention, it is possible to obtain a leather material (leather material) having even more excellent properties in terms of material breaking strength. .

Furthermore, when the foam-forming composition obtained in Comparative Example 6 was used, the average thickness of the foamed resin layer after drying was 1.50 mm, and the foamed layer thickness retention rate was 83. %, it was confirmed that a good foam with sufficient thickness could be obtained. Furthermore, when the foam-forming composition obtained in Comparative Example 6 was used, the resulting leather material (leather material) had an extremely excellent texture. Further, when the composition for forming a foam obtained in Comparative Example 6 was used, the material fracture strength was 4.8 N/cm, which was a sufficiently high level of material fracture strength. Here, the foam-forming composition obtained in Comparative Example 6 and the foam-forming composition obtained in Example 8 have almost the same composition except for the type of polyurethane resin component. From the comparison, it was found that the foam-forming composition (invention) obtained in Example 8 had even higher material fracture strength. From these results, it was found that according to the foam-forming composition of the present invention, it is possible to obtain a leather material (leather material) having even more excellent properties in terms of material breaking strength. .

(Examples 12 to 15)
The content ratio (parts by mass) of component (E) in the composition ranges from 0.2 parts by mass (Example 8) to 0.15 parts by mass (Example 12) and 0.08 parts by mass (Example 13), respectively. , 0.5 parts by mass (Example 14), and 1.8 parts by mass (Example 15), except that the amount (mass ratio) of the component for introducing component (E) was changed. The same operations as in Example 8 were performed to obtain leather materials (leather-like laminates).

(Comparative example 7)
Leather materials (leather-like laminates) were obtained by carrying out the same operations as in Example 8, except that the component for introducing component (E) was not used.

[About the characteristics of the leather materials (leather-like laminates) obtained in Examples 12 to 15 and Comparative Example 7]
Using the same method as the evaluation method for the characteristics of the leather material (leather-like laminate) obtained in Example 1, Comparative Examples 1 to 5, and Reference Example 1, the texture and thickness of the foam after drying were evaluated. , material breaking strength, and foaming property (time required until the foaming ratio increased to 3 times) were evaluated. The results obtained are shown in Table 8. Further, the results of Example 8 are also shown in Table 8. Furthermore, the compositions of the foam-forming compositions obtained in Example 8, Examples 12 to 15, and Comparative Example 7 and the composition of the foam-forming composition obtained in Example 8 are also shown in Table 8. . The symbol "-" in Table 8 indicates that the component is not contained (the content of the component is 0). Furthermore, in Table 8, component (A) represents the self-emulsifying water-based polyurethane resin obtained in Preparation Example 2, and component (B) represents the self-emulsifying water-based polyurethane resin having a carboxyl group obtained in Preparation Example 3. component (C) represents a polyether-modified aliphatic polyisocyanate, component (D) represents a mixture of compounds (D1) to (D3), and component (E) represents a polysaccharide-based polyisocyanate. The thickener (E1) is shown, and the (F) component is water. Note that the foam-forming compositions obtained in Examples 12 to 15 and Comparative Example 7 are different from the foam-forming composition obtained in Example 8, as is clear from the above-mentioned manufacturing method. The compositions have basically the same composition except for the content of component (E).

As is clear from the results shown in Table 8, when the foam-forming composition of the present invention was used (Example 8 and Examples 12 to 15), the time (minutes) required for foaming to triple was Since the time was sufficiently short at 3.0 minutes or 3.5 minutes, it was confirmed that the foaming properties of the composition were sufficiently high and that it was possible to foam efficiently. Furthermore, when the composition for forming a foam of the present invention was used (Example 8 and Examples 12 to 15), the average thickness of the foamed resin layer after drying was 1.55 mm or more. Since the foam layer thickness retention rate was 86% or more, it was confirmed that a good foam with sufficient thickness could be obtained. In addition, when the foam-forming composition of the present invention was used (Example 8 and Examples 12 to 15), the obtained leather materials (materials for leather) were all at a sufficiently high level of grade 4 or higher. It was confirmed that the texture was as follows. Furthermore, when the foam-forming composition of the present invention was used (Example 8 and Examples 12 to 15), the material breaking strength of the resulting leather material (leather material) was 5.0 N/ cm or more, and it was confirmed that the material fracture strength was extremely high.

On the other hand, the foam-forming composition obtained in Comparative Example 7, which did not use the component (E), had a foam layer thickness retention rate of 50% or less, resulting in a foam with sufficient thickness. Couldn't get the body. In addition, when the foam-forming composition obtained in Comparative Example 7 was used, the resulting leather material (leather material) could not have a sufficient texture, and furthermore, material damage occurred. It was also not possible to achieve a sufficient level of strength.

From the results of the foam-forming compositions obtained in Example 8 and Examples 12 to 15 and the foam-forming composition obtained in Comparative Example 7 (results shown in Table 8), (E) When checking the case where the usage amount (mass ratio) of the component is changed in the range of 0.08 to 1.8, it is found that when the usage amount of component (E) is 0.15 to 0.5, the texture and material damage are It was confirmed that the strength of It was found that the value of the material fracture strength was the highest when the amount was 0.4 parts by mass.

(Examples 16 to 18)
The resulting dispersion (foamed composition) was applied onto the skin layer of the skin layer forming material obtained in Preparation Example 1 using a knife coating method using a doctor knife, so that the thickness of the coating film was set to 1.8 mm. In the process of coating so that the thickness of the coating film becomes the same, the set value of the coating film thickness (thickness of the foam layer before drying) is changed from 1.8 mm to 1.00 mm (Example 16) and 0.50 mm (Example 17), respectively. , 0.30 mm (Example 18), the same operations as in Example 8 were performed to obtain leather materials (leather-like laminates). Thus, in Examples 16 to 18, leather materials (leather-like laminates) were obtained in the same manner as in Example 8, except that the thickness of the foam layer before drying was changed.

[About the characteristics of the leather materials (leather-like laminates) obtained in Examples 16 to 18]
Using the same method as the evaluation method for the characteristics of the leather material (leather-like laminate) obtained in Example 1, Comparative Examples 1 to 5, and Reference Example 1, the texture and thickness of the foam after drying were evaluated. , material breaking strength, and foaming property (time required until the foaming ratio increased to 3 times) were evaluated. The results obtained are shown in Table 9. The results of Example 8 are also shown in Table 9. Table 9 also shows the compositions of the foam-forming compositions obtained in each example. Here, in Table 9, component (A) represents the self-emulsifying water-based polyurethane resin obtained in Preparation Example 2, and component (B) represents the self-emulsifying water-based polyurethane resin having carboxyl groups obtained in Preparation Example 3. Component (C) represents a polyether-modified aliphatic polyisocyanate, component (D) represents a mixture of compounds (D1) to (D3), and component (E) represents a polysaccharide thickener ( E1), and the component (F) represents water. Note that the foam-forming compositions obtained in Examples 16 to 18 were the same compositions as the foam-forming composition obtained in Example 8, as is clear from the above-mentioned manufacturing method. It is.

As is clear from the results shown in Table 9, the same foam-forming composition was used in Example 8 and Examples 16 to 18, and the time (minutes) required for the composition to foam three times was Since the time was sufficiently short at 3 minutes, it was confirmed that the compositions used in Example 8 and Examples 16 to 18 had sufficiently high foaming properties and could be foamed efficiently. It was done.

Furthermore, from the results shown in Table 9, when using the composition for forming a foam of the present invention, when the thickness of the foam layer before drying was 1.0 mm or more (Examples 8 and 16), the foam layer film thickness It is possible to achieve a retention rate of 80% or more, and the foam layer thickness retention rate can be maintained at a sufficiently high value, making it possible to produce a good foam with sufficient thickness. It was confirmed that there is. Furthermore, when using the composition for forming a foam of the present invention, even when the thickness of the foam layer before drying is as thin as 0.5 mm or less (Examples 17 and 18), the foam layer film thickness It is possible to achieve a retention rate of 60% or more, and even when the thickness of the foam layer before drying is reduced to 0.5 mm or less, the retention rate of the foam layer thickness can be sufficiently maintained and a sufficient thickness can be achieved. It was confirmed that it is possible to produce a good foam with a As described above, when the foam-forming composition of the present invention was used (Example 8 and Examples 16 to 18), the thickness of the foam layer before drying (set value of coating film thickness) was 0. It was found that even if the thickness was varied from 3 mm to 1.8 mm, the foam layer thickness retention rate could be maintained at a sufficiently high value, and it was possible to produce a good foam with sufficient thickness. Ta.

In addition, from the results shown in Table 9, when the composition for forming a foam of the present invention was used (Example 8 and Examples 16 to 18), the thickness of the foam layer before drying (the setting of the thickness of the coating film) Even if the value) is changed from 0.3 mm to 1.8 mm, the texture of the resulting leather material (leather material) remains at grade 5, and when the thickness of the foam layer before drying is reduced (e.g. It was found that even when the thickness is reduced to 0.5 mm or less, it has the same texture as when the thickness is 1.8 mm, resulting in a leather material (leather material) with an extremely excellent texture. . Furthermore, when using the foam-forming composition of the present invention (Example 8 and Examples 16 to 18), even if the thickness of the foam layer before drying was varied from 0.3 mm to 1.8 mm, When the material breaking strength of the obtained leather material (leather material) is 5.0 N/cm or more, and the thickness of the foam layer before drying is reduced (for example, when the thickness is reduced to 0.5 mm or less) It has been found that it is possible to obtain leather materials (materials for leather) having sufficiently high material breaking strength even in the case of As described above, when the composition for forming a foam of the present invention is used (Example 8 and Examples 16 to 18), when the thickness of the foam layer before drying is reduced (for example, to 0.5 mm or less), It was confirmed that it is possible to obtain leather materials (materials for leather) with sufficiently high levels of texture and material breaking strength even in cases where the That is, when the composition for forming a foam of the present invention was used (Example 8 and Examples 16 to 18), the texture was not affected by the thickness of the foam layer (foamed resin layer), and the texture and material It was found that properties such as breaking strength can be maintained at a sufficiently high level regardless of thickness. These results show that the foam-forming composition of the present invention is highly versatile as a material for forming leather materials.

(Examples 19-23)
Instead of performing the step of further stirring the foam-forming composition so that the foaming ratio becomes 3 times, the foam-forming composition was stirred at a foaming ratio of 1.5 times (Example 19) shown in Table 10. ), 2 times (Example 20), 2.5 times (Example 21), 4 times (Example 22), or 5 times (Example 23)). The same operations as in Example 8 were performed to obtain leather materials (leather-like laminates). Thus, in Examples 19 to 23, leather materials (leather-like laminates) were obtained in the same manner as in Example 8, except that the expansion ratio was changed.

[About the characteristics of the leather materials (leather-like laminates) obtained in Examples 19 to 23]
Using the same method as the evaluation method for the characteristics of the leather material (leather-like laminate) obtained in Example 1, Comparative Examples 1 to 5, and Reference Example 1, the texture and thickness of the foam after drying were evaluated. , the material fracture strength was evaluated. The results obtained are shown in Table 10. Note that the results of Example 8 are also shown in Table 10. Table 10 also shows the composition of the foam-forming composition used in each example. Here, in Table 10, component (A) represents the self-emulsifying water-based polyurethane resin obtained in Preparation Example 2, and component (B) represents the self-emulsifying water-based polyurethane resin having carboxyl groups obtained in Preparation Example 3. Component (C) represents a polyether-modified aliphatic polyisocyanate, Component (D) represents a mixture of compounds (D1) to (D3), and Component (E) represents a polysaccharide thickener. (E1) is shown, and the (F) component is water. Note that the foam-forming compositions obtained in Examples 19 to 23 are the same compositions as the foam-forming composition obtained in Example 8 from the above-mentioned manufacturing method.

As is clear from the description in Table 10, the foam-forming compositions of the same composition were used in Example 8 and Examples 19 to 23, and the foam-forming composition used in Example 8 had a higher expansion ratio. Since it takes 3.0 minutes to triple the size, all of the foam-forming compositions used in Examples 19 to 23 have sufficiently high foaming properties and can be efficiently It is clear that foaming is possible. Furthermore, when using the composition for forming a foam of the present invention (Example 8 and Examples 19 to 23), even if the foaming ratio was changed from 1.5 to 5 times, the foam layer thickness was maintained. The ratio was 88% or more in all cases, and it was confirmed that it was possible to produce a good foam with sufficient thickness. Furthermore, when using the foam-forming composition of the present invention (Examples 8 to 19 to 23), even when the foaming ratio was changed from 1.5 to 5 times, the resulting leather material The texture of (material for leather) was grade 3 or higher (grade 3 to grade 5), and it was confirmed that the texture was of a sufficient level. Furthermore, when using the foam-forming composition of the present invention (Examples 8 to 19 to 23), even when the foaming ratio was changed from 1.5 to 5 times, the resulting leather material The material breaking strength of all of the materials (materials for leather) was 5.0 N/cm or more, confirming that it is possible to obtain leather materials (materials for leather) with extremely high material breaking strength. .

As explained above, when the foam forming compositions obtained in Examples 1 to 23 were used, it was confirmed that the foaming properties were sufficiently high and it was possible to foam efficiently. It was also confirmed that the foamed layer after drying had a sufficient thickness, and that the foamed resin layer could have a sufficient thickness. Furthermore, in all cases where the foam-forming compositions obtained in Examples 1 to 23 were used, the resulting leather material (leather material) had a sufficiently good texture of grade 3 or higher, It was confirmed that the material fracture strength was also very high, 5.0 N/cm or more. From these results, the foam-forming compositions of the present invention (Examples 1 to 23) impart sufficient texture and a higher level of material breaking strength to leather materials obtained using the compositions. It turns out that it is possible.

According to the present invention, although it is a foam-forming composition containing an aqueous polyurethane resin, it has sufficiently high foaming properties and can be foamed efficiently, and can also be foamed from a foamed and cured product of the composition. It is possible to make the resin layer sufficiently thick, and when a leather material is manufactured using the composition, the resulting leather material has a sufficient texture and a higher level of material breaking strength. A foam-forming composition capable of providing a foam-forming 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; ; and a leather material comprising the foam. Such a composition for forming a foam of the present invention can be used, for example, as a material for pseudo-leather-like materials (artificial leather or synthetic leather) used in vehicles, furniture, clothing, shoes, bags, bags, sandals, miscellaneous goods, etc. It is particularly useful as a

Claims (10)

(A) a first 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 first self-emulsifying aqueous polyurethane resin selected from the group consisting of a carboxy group and a carboxylate group; (C) a crosslinking agent, (D) a foaming agent, (E) a polysaccharide thickener, and (F) water. A composition for forming a foam, comprising: The foamed foam according to claim 1, wherein the component (B) has a structural unit derived from an organic polyisocyanate, and the structural unit includes a structural unit derived from an aromatic polyisocyanate compound. Composition for body formation. The component (B) has a structural unit derived from an organic polyisocyanate, and 5 to 60 mol% of the total amount of structural units derived from the organic polyisocyanate is a structural unit derived from an aromatic polyisocyanate compound. The composition for forming a foam according to claim 1 or 2, characterized in that: The composition for forming a foam according to any one of claims 1 to 3, wherein the component (D) contains the following compound (D1) and the following compound (D2);
[Compound (D1)]
General formula (1) below:
R ¹ COOX...(1)
(In the formula, 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) X is 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 ammonium ion which may have a substituent. Either one.)
A compound represented by;
[Compound (D2)]
General formula (2) below:
(In the formula, each of the two A is independently selected from the group consisting of groups represented by the formula: R ² O-, R ² N(H)-, (R ² ) ₂ N- and XO- and at least one of the two A is selected from the group consisting of a group 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. is any group selected from the group consisting of alkynyl groups having 8 to 30 carbon atoms, which may have one selected from the group).
A compound represented by The composition for forming a foam according to claim 4, wherein the component (D) further contains the following compound (D3);
[Compound (D3)]
General formula (3) below:
^R3 - _OSO3X ...(3)
(R ³ is any one selected from the group consisting of an alkyl group having 6 to 30 carbon atoms, an alkenyl group having 6 to 30 carbon atoms, and an alkynyl group having 6 to 30 carbon atoms, and X is H, Na, K, and (Any one selected from the group consisting of ammonium ions that may have a substituent.)
A compound represented by Any one of claims 1 to 5, wherein the component (E) consists of at least one polysaccharide selected from the group consisting of guar gum, tamarind seed gum, xanthan gum, carboxymethyl cellulose, and carrageenan. The composition for forming a foam according to item (1). A step of obtaining a foaming composition by foaming the composition for forming a foam according to any one of claims 1 to 6, and applying the foaming composition to a substrate and drying and curing it to form a substrate. A method for producing a foam, the method comprising: obtaining a foam on which a foamed resin layer made of a foamed cured product of the foam-forming composition is formed. 8. The method for producing a foam according to claim 7, 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. base material and
A foamed resin layer comprising a foamed cured product of the foam-forming composition according to any one of claims 1 to 6, laminated on the base material;
A foam comprising: A leather material comprising the foam according to claim 9.