JP2000355885A - Production of leather-mode sheetlike material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a sheetlike material for leather having flexibility and sense of fulfillment, closely similar to a natural leather by impregnating a specific dry heat gelling composite resin emulsion into a base composed of an extrafine fiber forming fiber, thermally coagulating the emulsion and subjecting the fiber to extrafine treatment. SOLUTION: A base composed of an extrafine fiber forming fiber is impregnated with a dry heat gelling composite resin emulsion which is a composite resin emulsion obtained by subjecting (B) an ethylenic unsaturated monomer such as (meth)acrylic acid (derivative), etc., to emulsion polymerization in the presence of (A) a polyurethane-based emulsion formed by using an aromatic polyisocyanate compound in the weight ratio of the polyurethane in the component A to the component B of 70:30 to 10:90 and having 0.1-50 mmol tertiary amino group based on 100 g of the composite resin and has <=5×108 dyn/cm2 and >=5×106 dyn/cm2 modulus of elasticity at 90 deg.C and 160 deg.C of a film formed at 50 deg.C dry heat and having 100 μm thickness. The base is then subjected to heat coagulation treatment and the base constituent fiber is subjected to extrafine treatment to give a sheetlike material for a leather.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a leather-like sheet and a leather-like sheet obtained thereby. More specifically, the present invention provides a leather-like sheet by impregnating a specific composite resin emulsion into a fibrous base material made of ultrafine fiber-forming fibers and heat-coagulating the fibrous base material to convert the fibrous base material to ultrafine fibers. The present invention relates to a production method and a leather-like sheet obtained thereby. In the case of the present invention, it has flexibility and a sense of fulfillment, has a high-grade feel and touch with a luxurious feeling similar to natural leather, and furthermore, dyeability, dyeing fastness, light resistance, durability and the like. A high-quality leather-like sheet having excellent properties can be produced smoothly and with high productivity in a simple process without using an organic solvent for coagulating a resin.

[0002]

2. Description of the Related Art As a substitute for natural leather (artificial leather),
BACKGROUND ART A leather-like sheet in which a fibrous base material is impregnated with a resin binder such as polyurethane has been conventionally produced. Among them, the leather-like sheet material in which the fibrous base material is made of ultrafine fibers occupies an important position because it has a high-grade feel and touch similar to natural leather. As a typical method for producing a leather-like sheet material in which the fibrous base material is composed of ultrafine fibers, (i) impregnating and adhering a resin to the fibrous base material composed of ultrafine fiber-forming fibers, A method of dissolving and removing a part of a resin component constituting a fiber or causing separation and separation between resins to form an ultrafine fiber, and (ii) forming a fibrous base material comprising an ultrafine fiber in advance, A method of impregnating and adhering a resin to a fibrous base material may be used.

In view of the technique for producing a leather-like sheet from the viewpoint of the method of impregnating and adhering a resin to a fibrous base material, the method of impregnating and adhering a resin includes (a) a resin component such as polyurethane. A method in which a solution dissolved in an organic solvent such as dimethylformamide is impregnated into a fibrous base material and then coagulated with a non-solvent such as water (wet method) or (b) a solution in which a resin component is dissolved in an organic solvent or dispersed in water A method (dry method) of impregnating a fibrous base material with a dried emulsion and then drying or heating and coagulating it is generally adopted. Among these methods, when the wet method (a) is used, particularly when the resin impregnation / adhesion method by the wet method (a) is used in the method (i), the method (b) is used. Although a sheet-like material with a feeling closer to that of natural leather can be obtained as compared to the dry method, the disadvantage is that productivity is low and the use of an organic solvent such as dimethylformamide is indispensable to coagulate the resin. is there. On the other hand, among the dry methods of the above (b), those using an aqueous emulsion of a resin have the advantage that the impregnation and adhesion of the resin to the fibrous base material can be performed without using an organic solvent. (A)
No high-quality feeling comparable to that of the leather-like sheet obtained by the wet method has been developed yet. The reason is that, in the leather-like sheet obtained by the dry method of the above (b), in the drying process, the resin is entangled with the fibers and strongly restrained to give a hard feeling to the sheet, There is a case where a large number of large voids in which no resin is present are generated, and the sense of fulfillment is lost.

[0004] In particular, when the impregnation and adhesion of the resin by the method (i) is performed by the dry method (b), the ultrafine fiber forming fibers constituting the fibrous base material are converted into ultrafine fibers. During the processing process for heating and drying the impregnated resin after ultrafine fiber heating, the resin easily penetrates into the ultrafine fiberized fiber bundle and becomes a structure that strongly restrains the fiber, and the resulting leather-like In many cases, the feeling of the sheet-like material becomes hard. If the amount of resin adhered is reduced in order to prevent a hard texture, the texture will not be a leather-like texture but a fibrous substrate-like texture without a sense of fulfillment. Further, the conventional leather-like sheet obtained by impregnating and adhering a resin by the method of (b) by the dry method of (b) has sufficient dyeing properties, color fastness, and light fastness. Is not satisfactory.

As a specific example of the above-mentioned prior art, there is a method of producing a base fabric for synthetic leather by impregnating a fabric with a mixture of a polyurethane emulsion and a polyacrylate emulsion and then subjecting the fabric to hot water treatment (Japanese Patent Laid-Open No. 55-1
No. 28078), an emulsion obtained by dissolving and mixing inorganic salts in an aqueous polyurethane emulsion having an average particle size of 0.1 to 2.0 μm, including a fiber layer mainly composed of ultrafine fibers having a single fiber fineness of 0.5 denier or less. A method for producing artificial leather by impregnating a nonwoven fabric and drying by heating.
No. 316877) is known. However,
Artificial leather obtained by these methods is insufficient in flexibility, fullness and the like, and it is difficult to say that the feeling is sufficiently improved. As another method, after impregnating an aqueous emulsion of a polyurethane formed from aliphatic diisocyanate, polytetramethylene glycol and aliphatic diamine into a nonwoven fabric made of ultrafine fiber-forming fiber composed of two or more polymers, There has been proposed a method of producing artificial leather by converting ultrafine fiber forming fibers constituting a nonwoven fabric into ultrafine fibers using an aqueous solution or an organic solvent (Japanese Patent Application Laid-Open No. Hei 9-132876). However,
Artificial leather obtained by this method is not sufficiently improved in terms of flexibility and a sense of fulfillment.

[0006] Therefore, in the production of artificial leather,
Although the productivity is low and the organic solvent is indispensable for the coagulation of the resin, the resin impregnation / adhesion method (impregnation / coagulation method) by the above-mentioned wet method (a) provides high quality artificial leather. At present, it is used exclusively for industrial reasons. However, one of the dry methods (b) described above, which is a technique for producing a leather-like sheet that is heated and solidified after impregnating an aqueous emulsion of a resin into a fibrous base material, involves impregnation of the fibrous base material with the resin. There is no need to use an organic solvent when solidifying the impregnated resin, and it is extremely effective in terms of environmental compatibility, work environment safety, and simplification of the process. Technology for producing a high-quality leather-like sheet with excellent flexibility and fullness, and excellent dyeability, dyeing fastness, and light resistance by a dry method of impregnating a fibrous base material with heat and coagulating it. There is a strong need for development.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to employ a dry method in which an aqueous emulsion of a resin is impregnated into a fibrous base material and then heat-coagulated. Without using organic solvents that cause contamination, and with a simple process, it has flexibility and fullness, has a high-grade feel and touch similar to natural leather, and has dyeability. Another object of the present invention is to provide a method for producing a high-quality leather-like sheet having excellent properties such as dyeing fastness, light fastness and durability with high productivity, and a leather-like sheet obtained thereby.

[0008]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors to achieve the above object, a fibrous base made of ultrafine fiber-forming fibers was used as a fibrous base, and a polyurethane-based base was used. Impregnated with a specific composite resin emulsion obtained by polymerizing an ethylenically unsaturated monomer in the presence of an emulsion, having a thermosensitive gelling property, having a predetermined amount of tertiary amino groups, and capable of forming a film having predetermined physical properties. After heating and coagulation, the ultrafine fiber forming fibers forming the fibrous base material are converted into ultrafine fibers to give a soft and rich feeling and a high-grade feel and touch that is close to that of natural leather. A high-quality leather-like sheet that is comparable to the leather-like sheet obtained by the wet method, and has excellent properties such as dyeability, color fastness, light fastness, and durability. Composite tree for base material Without the use of organic solvents during solidification of the impregnation time and the emulsion of the emulsion it was found to be able to safely and manufactured with good productivity by a simple process. That is, when the fibrous base material is impregnated with a specific composite resin emulsion having a tertiary amino group having such a thermosensitive gelling property, and then the fibrous base material is made into a fine fiber, the composite resin becomes a fibrous base material. The ultrafine fibers that make up the base material are no longer strongly restrained, and are impregnated and coagulated in the fibrous base material while maintaining an appropriate fiber space, providing flexibility, a sense of fulfillment, dyeability, dyeing fastness, The inventors have found that a high-quality leather-like sheet having excellent light resistance and durability can be obtained, and completed the present invention.

That is, the present invention relates to (1) a method of forming a fibrous base material after impregnating a fibrous base material composed of ultrafine fiber-forming fibers with a composite resin emulsion satisfying the following requirements and heating and coagulating; A method for producing a leather-like sheet, characterized in that the ultrafine fiber forming fibers are converted to ultrafine fibers; a thermosensitive gelling composite resin emulsion; drying the composite resin emulsion at 50 ° C. The modulus of elasticity at 90 ° C. of a 100 μm thick film obtained by the above method is 5.0 × 10 ⁸ dyn / cm ² or less; 160 ° C. of a 100 μm thick film obtained by drying the composite resin emulsion at 50 ° C. Is not less than 5.0 × 10 ⁶ dyn / cm ² ; In the presence of the polyurethane-based emulsion (A), the ethylenically unsaturated monomer (B) is Weight ratio of polyurethane in emulsion (A)]: [ethylenically unsaturated monomer (B)] = 70:30 to 10:90
And the composite resin in the composite resin emulsion has tertiary amino groups at a ratio of 0.1 to 50 mmol per 100 g of the composite resin.

[0010] The present invention provides:
(1) The method for producing (1), which is an ultrafine fiber-forming fiber containing polyamide as one component; (3) The α-dispersion temperature of a 100 μm-thick film obtained by drying the composite resin emulsion at 50 ° C.
(4) The method according to (1) or (2), wherein the polyurethane emulsion (A) is a polyurethane emulsion formed using an aromatic polyisocyanate compound. (5) the ethylenically unsaturated monomer (B) is a monofunctional ethylenically unsaturated monomer (B1) consisting mainly of (meth) acrylic acid and / or a derivative thereof;
(1) comprising 9% by weight and 0.1 to 10% by weight of a polyfunctional ethylenically unsaturated monomer (B2) having 2 or more functional groups;
(6) The method according to any one of (1) to (5), wherein the ethylenically unsaturated monomer (B) contains a tertiary amino group-containing unsaturated monomer in an amount of 0.1 to 10% by weight. As a preferred embodiment.

The present invention also provides: (7) the ultrafine fiber forming fibers constituting the fibrous base material are sea-island mixed spun fibers and / or sea-island type composite spun fibers; (1) the method of any one of (1) to (6), wherein after impregnation and heat coagulation, the sea component in the ultrafine fiber-forming fibers constituting the fibrous base material is removed to produce ultrafine fibers; 8) The thermosensitive gelation temperature of the composite resin emulsion is 30
７０70 ° C., wherein the composite resin emulsion is impregnated into the fibrous base material, and then heated to a temperature higher than the thermosensitive gelling temperature by at least 10 ° C. to solidify the composite resin emulsion. As a preferred embodiment. Further, the present invention provides (9) a leather-like sheet obtained by the production method according to any one of (1) to (8).

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the present invention, a fibrous base material made of ultrafine fiber-forming fibers is used as a fibrous base material for impregnating the composite resin emulsion. As the ultrafine fiber forming fibers constituting the fibrous base material, the fibrous base material can be impregnated with a composite resin emulsion, coagulated by heating, then converted to ultrafine fibers, and the leather-like sheet material has an appropriate thickness and flexibility. Any material that can give a sense of fulfillment can be used, and any of the ultrafine fiber-forming fibers conventionally used for leather-like sheet materials can be used.

Among them, as the ultrafine fiber-forming fiber constituting the fibrous base material, an ultrafine fiber-forming mixed spun fiber and / or composite spun fiber composed of two or more polymers is preferably used. As the mixed spun fiber and the composite spun fiber, two or more kinds of polymers are mixed or spun in a form such as a sea-island type, a side-by-side type, a random type, or a multilayer lamination type. By dissolving and / or decomposing a part of the polymer forming the fiber, or by causing a separation (peeling) between the respective polymer phases forming the mixed spun fiber and the conjugate spun fiber. What is made into ultrafine fibers is used. Among them, in the present invention, the fact that the fibrous base material is formed from sea-island mixed spun fibers and / or sea-island composite spun fibers that can be converted to ultrafine fibers by removing sea components, It is preferable because it is easy to form ultrafine fibers of uniform fineness and shape, and the physical properties of the obtained leather-like sheet material are good. The proportion of the island component and the sea component in the sea-island mixed spun fiber and the sea-island composite spun fiber is not particularly limited, but the mixed spun fiber and the composite spun fiber are easily manufactured, the ultrafine fiber is easily formed, and the obtained leather-like sheet is obtained. In general, the weight ratio of the island component to the sea component is 15: 8 from the viewpoint of the physical properties of the state substance.
5:85:15, preferably 25: 75-7
More preferably, the weight ratio is 5:25. The number and size of the island components in the sea-island mixed spun fiber and the sea-island composite spun fiber are not particularly limited, and the dispersion state of the island components in the sea component is not particularly limited. Any method can be used as long as it can be easily performed.

Examples of the polymer constituting the ultrafine fiber forming fiber include polyamides such as 6-nylon, 6,12-nylon, 6,6-nylon and modified nylon, polyethylene terephthalate, polybutylene terephthalate and modified polyester. Polyolefins such as polyesters, polyethylene and polypropylene, polystyrene,
Examples include polymethacrylic acid esters, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyurethane elastomers, polyamide elastomers, polyester elastomers, and the like. Among these polymers, two polymers having different solubility in an organic solvent were used.
Separation / separation at the boundary between polymer phases by combining more than one kind, or by combining two or more kinds of polymers having different degradability (solubility) with a decomposing agent such as an aqueous alkali solution, or by applying external stress or heating By combining two or more kinds of the resulting polymers, an ultrafine fiber-forming fiber for forming a fibrous base material can be obtained.

Among them, in the present invention, the fibrous base material is formed from a mixed island-and-sea type spun fiber and / or a composite island-and-sea spun fiber having an island component mainly composed of polyamide and / or polyester, particularly polyamide. It is preferable that the fibrous base material in the finally obtained leather-like sheet is formed of polyamide and / or polyester, particularly ultrafine fibers derived from island components mainly composed of polyamide,
In that case, the leather-like sheet obtained is very flexible and tactile to that of natural leather, and the leather-like sheet has excellent dyeability, light-fastness, light-fastness, and durability. Becomes In particular, it is more preferable that 60% by weight or more of the island component in the sea-island type mixed spun fiber and the sea-island type composite spun fiber is made of polyamide, more preferably 70% by weight or more is made of polyamide, and 80% by weight or more is made of polyamide. More preferably, When dyeing a leather-like sheet, if the fibrous base material is formed of ultrafine fibers mainly composed of polyamide, both the fibrous base material and the composite resin impregnated and adhered to it are dyed simultaneously with an acid dye. it can. On the other hand, when the fibrous base material is formed of ultrafine fibers mainly composed of polyester, the fibrous base material is dyed with a disperse dye, and the composite resin impregnated and attached to the fibrous base material is dyed with an acid dye. A step dyeing method is generally employed. Therefore, in the present invention,
It is particularly preferable that the fibrous base material is formed from ultrafine fibers mainly composed of polyamide, from the viewpoint that dyeing can be performed in one step.

As a specific example of the sea-island mixed spun fiber and the sea-island composite spun fiber having polyamide as an island component, a sea-island mixed spun fiber and sea-island having an island component made of polyamide and a sea component made of polyethylene and / or polystyrene. Type composite spun fiber. When the fibrous base material is formed from such sea-island type mixed spun fiber and / or sea-island type composite spun fiber, after impregnating the fibrous base material with the composite resin emulsion and heat coagulating,
The sea component polyethylene and / or polystyrene is dissolved and removed using an organic solvent such as aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated hydrocarbons such as carbon tetrachloride and perchrene to remove island components. By leaving the eggplant polyamide in the form of ultrafine fibers,
The desired leather-like sheet material can be obtained. The leather-like sheet obtained thereby has excellent flexibility and a sense of fulfillment, has a very good feeling similar to natural leather, and can be suitably used as a material for artificial leather.

The fibrous base material used in the present invention may be any of a nonwoven fabric, a woven or knitted fabric, or a combination of a nonwoven fabric and a woven or knitted fabric (a laminate of a nonwoven fabric and a woven or knitted fabric). Among them, the fibrous base material is composed of only a nonwoven fabric, or a laminate of a nonwoven fabric having at least one nonwoven fabric layer and a woven fabric and / or a knitted fabric (for example, a laminate of a nonwoven fabric layer and a knitted woven fabric layer. Layer structure, a three-layer structure having a nonwoven fabric on the front and back surfaces and a woven and knitted fabric in the center).
The leather-like sheet material thus obtained is preferable because the feeling and feel of the leather-like sheet material are closer to those of natural leather. Examples of the type of nonwoven fabric preferably used as the fibrous base material include entangled nonwoven fabrics and wrap-type nonwoven fabrics. Among them, entangled nonwoven fabrics are preferred because a leather-like sheet-like material having an excellent feeling and touch is obtained. Used.

The fibrous base material (the fibrous base material before being converted into ultrafine fibers) used in the present invention may be any of the above-mentioned ultrafine fiber-forming materials as long as the feeling and touch of the obtained leather-like sheet material are not impaired. If necessary, other fiber materials may be used in combination with the fibers. Examples of other fiber materials include ordinary fibers, shrinkable fibers, latent spontaneously extensible shrinkable fibers, multilayer bonded latently splittable fibers, special porous fibers, and the like. The above can be used. Examples of these other fibers include polyamide fibers, polyester fibers, polyolefin fibers,
Synthetic fibers such as polyvinyl chloride fibers, polyvinylidene chloride fibers, and polyvinyl alcohol fibers, semi-synthetic fibers such as rayon, and natural fibers such as cotton, wool, and hemp. In the case where the fibrous base material is formed from ultrafine fiber-forming fibers and other fibers as described above, the ratio of the other fibers in the fibrous base material is the fibrous material before the ultrafine fibers are formed. Based on the weight of the base material, the content is preferably 30% by weight or less in order to obtain a leather-like sheet having excellent feeling and touch, and more preferably 15% by weight or less.

The monofilament fineness of the ultrafine fiber forming fibers constituting the fibrous base material after ultrafine fiber formation is such that a leather-like sheet having a natural leather-like feeling excellent in flexibility and fullness can be obtained. , Preferably 0.5 denier or less,
More preferably, it is 0.4 denier or less.

The thickness of the fibrous base material can be selected according to the intended use of the obtained leather-like sheet material, etc. Is preferably 0.3 to 3.0 mm,
More preferably, it is 0.6 to 2.5 mm.

The apparent density of the fibrous base material is determined by converting the ultrafine fiber forming fibers constituting the fibrous base material into ultrafine fibers in view of the resilience, stiffness, and flexibility of the obtained leather-like sheet. in state after, it is preferably 0.1 to 0.5 g / cm ^3, more preferably 0.15~0.45g / cm ^3. The apparent density of the fibrous base material is as described above.
If it is less than 1 g / cm ³ , the resulting leather-like sheet will have poor resilience and low back feeling, making it difficult to obtain a feeling similar to natural leather. On the other hand, if the apparent density of the fibrous base material is larger than the above-mentioned 0.5 g / cm ³ , the resulting leather-like sheet will not have a firm feeling,
It tends to have a bad rubbery feel.

In the present invention, in order to uniformly and rapidly impregnate the above-mentioned fibrous base material composed of ultrafine fiber-forming fibers with the composite resin emulsion, the fibrous base material is impregnated with the composite resin emulsion. Prior to this, a wet penetrant such as an aqueous solution of a surfactant or an aqueous emulsion may be applied to the fibrous base material, or a wet penetrant may be added to the composite resin emulsion. When a wet osmotic agent is previously applied to the fibrous base material, the fibrous base material to which the aqueous solution or the aqueous emulsion of the surfactant is applied is combined with the fibrous base material when the fibrous base material still retains moisture. The resin emulsion is preferably impregnated. Even when the surfactant is applied to the fibrous base material, the effect of promoting the penetration of the composite resin emulsion is hardly exhibited when the fibrous base material is in a dry state. The amount (in dry matter) of the surfactant previously applied to the fibrous base material or added to the composite resin emulsion is preferably 0.01 to 20% by weight based on the weight of the fibrous base material.

In the present invention, the above-mentioned fibrous base material composed of ultrafine fiber-forming fibers is impregnated with a thermogelling composite resin emulsion (composite resin emulsion satisfying the above-mentioned requirements) and coagulated by heating. Here, the “thermosensitive gelling emulsion” in the present invention refers to an emulsion that loses fluidity when heated and becomes a gel (solidifies). The heat-sensitive gelation temperature (temperature at which fluidity is lost by heating and gelation occurs) of the composite resin emulsion used in the present invention is preferably 30 to 70 ° C, and 40 to 7 ° C.
The temperature is more preferably 0 ° C. If the composite resin emulsion is not thermosensitive gelling, a migration phenomenon occurs in which the composite resin moves to the surface of the fibrous base material when the fibrous base material is impregnated with the composite resin emulsion and dried by heating.
The composite resin cannot be uniformly dispersed and adhered to the fibrous base material, and the resulting leather-like sheet-like material has poor physical properties such as high elongation and flexibility, and has a poor feel.

The heat-sensitive gelling composite resin emulsion may be a heat-sensitive gelling composite resin emulsion by itself or a heat-sensitive gelling composite resin obtained by adding a heat-sensitive gelling agent to a composite resin emulsion. Any of the emulsions can be used. Examples of the thermosensitive gelling agent for obtaining a thermogelling composite resin emulsion include, for example,
Inorganic salts, polyethylene glycol-type nonionic surfactants, polyvinyl methyl ether, polypropylene glycol, silicone polyether copolymer, polysiloxane, and the like can be used, and one or more of these can be used. .

Among them, as the heat-sensitive gelling agent, a combination of an inorganic salt and a polyethylene glycol-type nonionic surfactant because of exhibiting good heat-sensitive gelling property, good storage stability and low cost. Is preferably used. As the inorganic salt in that case, a metal salt capable of lowering the cloud point of the polyethylene glycol type nonionic surfactant is preferably used, for example, sodium carbonate, potassium carbonate, sodium sulfate, calcium sulfate, sodium chloride, chloride, and the like. Potassium, calcium chloride, zinc chloride, aluminum chloride, magnesium chloride,
Examples thereof include sodium nitrate and lead nitrate, and one or more of these can be used. Also,
Examples of the polyethylene glycol type nonionic surfactant include an ethylene oxide adduct of a higher alcohol, an ethylene oxide adduct of an alkyl phenol,
Ethylene oxide adducts of fatty acids, ethylene oxide adducts of fatty acid esters of polyhydric alcohols, ethylene oxide adducts of higher alkylamines, ethylene oxide adducts of polypropylene glycol, and the like. One or more of these may be mentioned. Can be used.

When a heat-sensitive gelling agent containing a heat-sensitive gelling agent is used as the heat-sensitive gelling compound resin emulsion, the content of the heat-sensitive gelling agent is 0.2 to 100 parts by weight of the composite resin in the composite resin emulsion. It is preferably about 20% by weight.

Further, the composite resin emulsion used in the present invention has a 100 μm-thick film obtained by drying the composite resin emulsion at 50 ° C. and having an elastic modulus at 90 ° C. of 5.0 × 10 ⁸ dyn / cm ² or less. (The above requirement), preferably 3.0 × 10 ⁸ dyn / cm ² or less, and 2.0 × 10 ⁸ dyn / cm ^2.
It is more preferred that: When a composite resin emulsion which gives the dry film having an elastic modulus at 90 ° C. of more than 5.0 × 10 ⁸ dyn / cm ² is used, the obtained leather-like sheet material has a poor hardness and lacks flexibility. become.

Further, the composite resin emulsion used in the present invention has a 100 μm-thick film obtained by drying the composite resin emulsion at 50 ° C. and having an elastic modulus at 160 ° C. of 5.0 × 10 ⁶ dyn / cm ² or more. It is necessary (the above-mentioned requirement), and it is preferably 8.0 × 10 ⁶ dyn / cm ² or more, and 1.0 × 10 ⁷ dyn / cm ^2.
More preferably, it is the above. When a composite resin which gives the dry film having an elastic modulus at 160 ° C. of less than 5.0 × 10 ⁶ dyn / cm ² is used, the ultrafine fiber forming fibers constituting the fibrous base material may be converted into an organic solvent or the like. When processing using squeezing rolls etc. to make ultra-fine fibers using squeezing, the so-called "sagging" that the thickness becomes thin due to the pressure of the squeezing rolls etc. occurs, and the obtained leather-like sheet-like material However, the feeling of flexibility, fulfillment and waist is lost, resulting in a poor texture. In addition, 9 of the said dry film in this invention
The method of measuring the elastic modulus at 0 ° C. and 160 ° C. is as described in the Examples section below.

The composite resin emulsion used in the present invention has a α-dispersion temperature (Tα) of a 100 μm-thick film obtained by drying the composite resin emulsion at 50 ° C.
The temperature is preferably 10 ° C, more preferably -20 ° C or less. By using a composite resin which gives the dry film having an α-dispersion temperature of −10 ° C. or less, the physical properties such as cold resistance and flex resistance of the obtained leather-like sheet material are further improved. . In the present invention, the α-dispersion temperature (T
The method for measuring α) is as described in the section of Examples below.

The composite resin emulsion used in the present invention is
In the presence of the polyurethane-based emulsion (A), the ethylenically unsaturated monomer (B) was mixed with the [polyurethane in the polyurethane-based emulsion (A)]: [ethylenically unsaturated monomer (B)] weight ratio = 70:30. It is a composite resin emulsion obtained by emulsion polymerization at a ratio of 10 to 90 (the above requirement). The weight ratio of the above-mentioned [polyurethane in the polyurethane-based emulsion (A)]: [ethylenically unsaturated monomer (B)] in the production of the composite resin emulsion is preferably 65:35 to 15:85, and 6
The ratio is more preferably 0:40 to 20:80. If the proportion of the polyurethane during the production of the composite resin emulsion is less than 10% by weight [the proportion of the ethylenically unsaturated monomer (B) exceeds 90% by weight], the solvent resistance of the obtained composite resin decreases, and the fiber When processing using ultra-fine fiber forming fibers that make up the porous base material with ultra-fine fibers using an organic solvent, etc., using a squeezing roll, the thickness is reduced due to the pressure of the squeezing roll. The resulting leather-like sheet-like material has a poor texture with a lack of flexibility, fullness, and waist. On the other hand, if the proportion of the polyurethane during the production of the composite resin emulsion exceeds 70% by weight [the proportion of the ethylenically unsaturated monomer (B) is less than 30% by weight], the weather resistance and hydrolysis resistance of the composite resin decrease. In addition, the cost is high, so that practical use is difficult.

Further, the composite resin emulsion used in the present invention contains 3 g per 100 g of the composite resin in the composite resin skeleton.
It is necessary to have a primary amino group in a ratio of 0.1 to 50 mmol (the above requirement). When the composite resin in the composite resin emulsion has the tertiary amino group in the above-described ratio, the dyeability of the leather-like sheet obtained in the present invention is improved, so that the leather-like sheet can be dyed sharply, and The leather-like sheet after dyeing has excellent dyeing fastness and is free from fading and discoloration. Since the composite resin in the composite resin emulsion has tertiary amino groups in the above ratio, the dyeability of the composite resin impregnated and adhered to the fibrous base material with the acid dye is improved, and at the same time, the color fastness Also improve. In particular, in a leather-like sheet material in which the ultrafine fibers constituting the fibrous base material are mainly composed of a polyamide resin, the composite resin impregnated and adhered to the fibrous base material has the tertiary amino group in the above ratio. With this method, both the fibrous base material and the composite resin can be simultaneously dyed with an acid dye, and a dyed product without dye spots can be easily obtained in a single dyeing process. In particular, it is excellent in light fastness to light. When the content of the tertiary amino group in the composite resin is less than 0.1 mmol, it is difficult to obtain the effect of improving the dyeability and the color fastness. On the other hand, when the content exceeds 50 mmol, the cost becomes high, and furthermore, The effect of improving the properties and color fastness cannot be obtained.

The polyurethane emulsion (A) for producing the composite resin emulsion used in the present invention may be any polyurethane emulsion in which a polyurethane polymer is stably emulsified and dispersed in an aqueous liquid. The type of polyurethane in the polyurethane emulsion, the method for producing the same, and the method for producing the polyurethane emulsion are not particularly limited. The polyurethane emulsion (A) is, for example, an emulsion of a self-emulsifiable polyurethane having a large number of hydrophilic groups for promoting emulsification in a polyurethane skeleton, or a polyurethane having a low emulsifiability using an emulsifier such as a surfactant. May be a polyurethane-based emulsion forcibly emulsified in an aqueous liquid.

The polyurethane in the polyurethane-based emulsion (A) can be generally produced by appropriately combining and reacting a polymer polyol, an organic polyisocyanate compound and a chain extender.

The above-mentioned high molecular polyol used in the production of polyurethane includes polyester polyol,
Polycarbonate polyol, polyester polycarbonate polyol, polyether polyol and the like can be mentioned, and polyurethane can be produced by using one or more of these.

Polyester polyols that can be used in the production of polyurethane are prepared by, for example, directly esterifying a polyol component with a polycarboxylic acid component such as a polycarboxylic acid, an ester thereof, or an ester-forming derivative such as an anhydride, according to a conventional method. Alternatively, it can be produced by a transesterification reaction. Further, the polyester polyol can also be produced by ring-opening polymerization of lactone.

Examples of the polycarboxylic acid component which is a raw material for producing a polyester polyol which can be used for producing a polyurethane include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecane diacid, and the like. 2-methylsuccinic acid, 2-methylglutaric acid, 3-methylglutaric acid, 2-methyladipic acid, 3
-Methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecandioic acid, 3,
Aliphatic dicarboxylic acids such as 7-dimethyldecandioic acid;
Alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, phthalic acid, and naphthalenedicarboxylic acid; tricarboxylic acids such as trimellitic acid and trimesic acid; Derivatives and the like can be mentioned, and the polyester polyol can be formed using one or more of the above-mentioned polycarboxylic acid components. Among them, the polyester polyol is mainly composed of an aliphatic dicarboxylic acid or an ester-forming derivative thereof as a polycarboxylic acid component, and optionally contains a small amount of a trifunctional or more polycarboxylic acid or an ester-forming derivative thereof. It is preferably manufactured.

As the polyol component which is a raw material for producing a polyester polyol which can be used for producing polyurethane, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl- 1,3-
Propanediol, 2,2-diethyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-
1,5-pentanediol, neopentyl glycol,
1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 3-methyl-1,8-
Aliphatic diols such as octanediol, 2,7-dimethyl-1,8-octanediol, 1,9-nonanediol, 2,8-dimethyl-1,9-nonanediol and 1,10-decanediol; cyclohexanedi Alicyclic diols such as methanol, 1,4-cyclohexanediol and dimethylcyclooctanedimethanol;
Aromatic diols such as bis (β-hydroxyethoxy) benzene; polyalkylene glycols; triols such as glycerin, trimethylolpropane, butanetriol, hexanetriol, trimethylolbutane, and trimethylolpentane; and tetraols such as pentaerythritol. And one or more of the above-mentioned polyol components can be used. Among them, it is preferable that the polyester polyol is produced using an aliphatic diol as a polyol component, and optionally using a polyol component containing a small amount of a trifunctional or higher functional polyol.

As a lactone which is a raw material for producing polyester polyol which can be used for producing polyurethane, ε-
Caprolactone, β-methyl-δ-valerolactone and the like can be mentioned.

The polycarbonate polyol which can be used for producing polyurethane is obtained, for example, by reacting the polyol with a carbonate compound such as dialkyl carbonate, alkylene carbonate and diaryl carbonate. As the polyol which is a raw material for producing a polycarbonate polyol, the above-mentioned polyols which are raw materials for producing a polyester polyol can be used. Examples of the dialkyl carbonate include dimethyl carbonate and diethyl carbonate, examples of the alkylene carbonate include ethylene carbonate, and examples of the diaryl carbonate include diphenyl carbonate.

Examples of the polyester polycarbonate polyols that can be used in the production of polyurethane include those obtained by simultaneously reacting a polyol, a polycarboxylic acid, and a carbonate compound, and those obtained by reacting a polyester polyol previously produced with a carbonate compound. Obtained products, those obtained by reacting a pre-produced polycarbonate polyol with a polyol and a polycarboxylic acid, those obtained by reacting a pre-produced polyester polyol with a polycarbonate polyol, and the like are exemplified. be able to.

Examples of the polyether polyols that can be used in the production of polyurethane include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly (methyltetramethylene glycol), and one or more of these. Can be used.

The number average molecular weight of the high molecular polyol used for producing the polyurethane is preferably from 500 to 10,000, more preferably from 700 to 5,000, even more preferably from 750 to 4,000. . In addition, the number average molecular weight of the high molecular polyol referred to in this specification refers to a number average molecular weight calculated based on a hydroxyl value measured according to JIS K1577.

The number of hydroxyl groups per molecule of the high molecular polyol used for producing the polyurethane may be larger than 2 as long as the production of the polyurethane emulsion (A) is not hindered. The polymer polyol having a number of hydroxyl groups per molecule larger than 2 is, for example, in the case of a polyester polyol, the above-mentioned trifunctional or higher functional polycarboxylic acid or polyol is used as a part of a raw material for producing the polyester polyol. Can be manufactured.

The kind of the organic polyisocyanate compound used for the production of the polyurethane is not particularly limited, and any of the known organic polyisocyanates conventionally used for the production of the polyurethane emulsion can be used. Examples of the organic polyisocyanate compound that can be used for producing polyurethane include, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-
Diphenylmethane diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 1,5
-Naphthylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-
Examples thereof include dicyclohexylmethane diisocyanate and norbornene diisocyanate, and one or more of these can be used.

Of the organic polyisocyanate compounds described above, aromatic polyisocyanate compounds such as tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate are preferably used because the resulting polyurethane has excellent solvent resistance. When using a composite resin emulsion containing a polyurethane obtained from an aromatic polyisocyanate compound, a fibrous base material composed of ultrafine fiber-forming fibers is impregnated with the composite resin emulsion, and then heat-coagulated to form a fibrous base material. When ultrafine fiber forming fibers to be converted into ultrafine fibers using an organic solvent (for example, when the sea component in sea-island mixed spun fibers and / or conjugate spun fibers is dissolved and removed with an organic solvent to form ultrafine fibers, etc.) ) Since the composite resin has excellent solvent resistance, a decrease in the physical properties of the composite resin due to the organic solvent is suppressed, and a leather-like sheet having excellent feeling and mechanical properties can be obtained.

As the chain extender used in the production of the polyurethane, any of the chain extenders conventionally used in the production of the polyurethane emulsion can be used. A low molecular compound having a molecular weight of 400 or less and having two or more of them is preferably used. Such chain extenders include
For example, hydrazine, ethylenediamine, propylenediamine, hexamethylenediamine, nonamethylenediamine, xylylenediamine, isophoronediamine, norbornenediamine, 4,4′-diaminodicyclohexylmethane, piperazine and derivatives thereof, phenylenediamine, tolylenediamine, xylenediamine , 4,4 '
-Diaminodiphenylmethane, adipic dihydrazide, isophthalic dihydrazide, N-methyl-3,3 '
Diamines such as iminobis (propylamine); triamines such as diethylenetriamine; tetraamines such as triethylenetetramine; ethylene glycol, propylene glycol, 1,4-butanediol,
1,6-hexanediol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-cyclohexanediol, bis (β-hydroxyethyl) terephthalate,
Diols such as xylylene glycol and N-methyldiethanolamine; triols such as trimethylolpropane; tetraols such as pentaerythritol; amino alcohols such as aminoethyl alcohol and aminopropyl alcohol;
One or more of these can be used. Among these, ethylene diamine, isophorone diamine, diethylene triamine, ethylene glycol and the like are preferably used.

In the production of the polyurethane, the molar ratio of the high molecular weight polyol to the organic polyisocyanate compound used in the synthesis of the prepolymer is preferably in the range of 1: 1.1 to 5.0, particularly preferably in the range of 1: 1.3 to 3: 1. 0.0 is preferred. When the prepolymer is chain-extended, the molar ratio of the prepolymer to the chain extender is 1: 0.5 to 2.0.
A range of 0 is preferable, and a range of 1: 0.7 to 1.5 is particularly preferable. Excess isocyanate groups and active hydrogen after the chain elongation reaction are consumed by the reaction with water and by the subsequent crosslinking reaction and the like.

Also, a polyurethane emulsion (A)
In view of the polymerization stability and the ease of imparting heat-sensitive gelling property when the ethylenically unsaturated monomer (B) is emulsion-polymerized in the presence of the polyurethane-based emulsion (A), the polyurethane skeleton contains 100 g of polyurethane per 100 g of polyurethane. 3 to 3
It preferably has 0 mmol of neutralized carboxyl and / or sulfonic acid groups. The introduction of neutralized carboxyl groups and / or sulfonic acid groups into the polyurethane skeleton is used as a raw material for producing polyurethane.
Polyurethane is produced by using in combination a compound having a carboxyl group, a sulfonic acid group and / or a base thereof and containing at least one isocyanate-reactive active hydrogen atom such as a hydroxyl group or an amino group. This is achieved by neutralization with a basic compound such as a tertiary amine or an alkali metal hydroxide. Such compounds include, for example, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxymethyl) butyric acid, 2,2
Carboxyl group-containing compounds such as 2-bis (hydroxymethyl) valeric acid and derivatives thereof; sulfonic acid groups such as 1,3-phenylenediamine-4,6-disulfonic acid and 2,4-diaminotoluene-5-sulfonic acid Compounds and derivatives thereof can be mentioned, and one or more of these can be used. Furthermore, it can be achieved by producing polyurethane using polyester polyol, polyester polycarbonate polyol, etc. obtained by copolymerizing the above-mentioned compounds. Among them, a polyurethane prepolymer is produced using 2,2-bis (hydroxymethyl) propionic acid and / or 2,2-bis (hydroxymethyl) butyric acid, and after completion of the prepolymer production reaction, triethylamine, trimethylamine, water A method of producing a polyurethane in which a basic substance such as sodium oxide or potassium hydroxide is added for neutralization, and the neutralized prepolymer is reacted with a chain extender to produce a polyurethane is preferably employed.

The polyurethane emulsion (A) used for producing the composite resin emulsion can be produced by the same method as that conventionally used for producing the polyurethane emulsion. For example, (1) a hydrophobic polyurethane prepolymer having a terminal isocyanate group obtained by reacting a polymer polyol and an organic polyisocyanate compound is forcibly forced into water by high mechanical shearing force in the presence of an emulsifier. A method of producing a polyurethane emulsion by reacting with a chain extender such as a polyamine at the same time as or after emulsifying and dispersing, thereby producing a polyurethane emulsion. A method in which a polyurethane prepolymer is self-emulsified in water, or at the same time or thereafter, is reacted with a chain extender such as a polyamine to increase the molecular weight, thereby producing a polyurethane emulsion. In order to facilitate the emulsification and dispersion of polyurethane in water, a polyurethane prepolymer having an isocyanate group at an end may be diluted with an organic solvent such as acetone, methyl ethyl ketone, toluene, ethyl acetate, tetrahydrofuran, and dimethylformamide. The organic solvent can be removed before or after emulsion polymerization. Further, part or all of the chain extender may be reacted before emulsification of the polyurethane.

The polyurethane-based emulsion (A) is described above in view of the polymerization stability at the time of emulsion polymerization of the ethylenically unsaturated monomer (B) and the ease of imparting a thermosensitive gelling property to the composite resin emulsion. The emulsifier in the method (1) preferably contains 0.5 to 10 g of a surfactant based on 100 g of the polyurethane in the polyurethane emulsion (A). Examples of the surfactant include anionic surfactants such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium polyoxyethylene tridecyl ether acetate, sodium dodecyl benzene sulfonate, sodium alkyl diphenyl ether disulfonate, and sodium di (2-ethylhexyl) sulfosuccinate. Surfactants: Nonionic surfactants such as polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene-polyoxypropylene block copolymer. And one or more of these can be used. Among them, anionic surfactants such as sodium lauryl sulfate, ammonium lauryl sulfate and sodium polyoxyethylene tridecyl ether acetate are preferred.

The composite resin emulsion used in the present invention is
It is produced by emulsion polymerization of an ethylenically unsaturated monomer (B) in the presence of a polyurethane emulsion (A). As the ethylenically unsaturated monomer (B), a monofunctional ethylenically unsaturated monomer (B1) mainly composed of (meth) acrylic acid and / or a derivative thereof is 90 to 9%.
The content of 9.9% by weight and 0.1 to 10% by weight of the bifunctional or higher-functional polyfunctional ethylenically unsaturated monomer (B2) makes the leather-like sheet obtained more excellent in feeling and weather resistance. From 9 to 99.8% by weight of a monofunctional ethylenically unsaturated monomer (B1) mainly composed of (meth) acrylic acid and / or a derivative thereof and a polyfunctional ethylenically unsaturated monomer (B2) having two or more functional groups. More preferably, it comprises 0.2 to 8% by weight.

The monofunctional ethylenically unsaturated monomer (B1) used for producing the composite resin emulsion includes:
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate , Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate,
(Meth) acrylic acid, glycidyl (meth) acrylate,
Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylic acid 2
(Meth) acrylic acid or (meth) acrylic acid derivatives such as -hydroxyethyl, 2-hydroxypropyl (meth) acrylate; styrene, α-methylstyrene, p-
Aromatic vinyl compounds such as methylstyrene; (meth) acrylamide, diacetone (meth) acrylamide,
Acrylamides such as N- [3- (dimethylamino) propyl] (meth) acrylamide; maleic acid, fumaric acid, itaconic acid or derivatives thereof; heterocyclic vinyl compounds such as vinylpyrrolidone; vinyl chloride, acrylonitrile, vinyl ether, Vinyl compounds such as vinyl ketone and vinyl amide; α-olefins such as ethylene and propylene; and one or more of these can be used. Among them, the monofunctional ethylenically unsaturated monomer (B1) is excellent in weather resistance, hydrolysis resistance and the like of the obtained composite resin. The proportion of the (meth) acrylic acid derivative is preferably at least 60% by weight, more preferably at least 70% by weight, even more preferably at least 80% by weight.

Bifunctional or higher functional polyfunctional ethylenically unsaturated monomer (B2) used for producing a composite resin emulsion
Specific examples of ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate,
Polyethylene glycol di (meth) acrylate, 1,
4-butanediol di (meth) acrylate, 1,6-
Di (e.g., hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, glycerin di (meth) acrylate, etc. (Meth) acrylates; tri (meth) acrylates such as trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate; tetra (meth) acrylates such as pentaerythritol tetra (meth) acrylate; divinylbenzene, trivinyl A polyfunctional aromatic vinyl compound such as vinylbenzene; a compound containing two or more different ethylenically unsaturated bonds such as allyl (meth) acrylate and vinyl (meth) acrylate;
Molecular weights such as a 2: 1 addition reaction product of 3-phenoxypropyl acrylate and hexamethylene diisocyanate, a 2: 1 addition reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate, and a 2: 1 addition reaction product of glycerin dimethacrylate and tolylene diisocyanate Of 1,500 or less, and one or more of these can be used.

In the production of the composite resin emulsion, the addition of the ethylenically unsaturated monomer (B) to the polyurethane emulsion (A) may be carried out by any of batch, divided or continuous methods. The polymerization may be performed by a multi-stage polymerization method in which the polymerization is changed for each polymerization step or a power feed method in which the polymerization is continuously changed. When the emulsion polymerization is carried out by the multi-stage polymerization method or the power feed method, the total amount of the bifunctional or higher polyfunctional ethylenically unsaturated monomer (B2) among the total ethylenically unsaturated monomers (B) used for the polymerization is 0.1%. Preferably it is 1 to 10% by weight. Further, an ethylenically unsaturated monomer (B)
An emulsifier such as a surfactant may be appropriately added at the time of polymerization.

Examples of the polymerization initiator which can be used for the emulsion polymerization of the ethylenically unsaturated monomer (B) include, for example, benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, di-t-butyl peroxide, cumene hydroperoxide. , T-butyl hydroperoxide, oil-soluble peroxides such as diisopropylbenzene hydroperoxide; 2,2′-azobisisobutyronitrile;
2'-azobis- (2,4-dimethylvaleronitrile)
Oil-soluble azo compounds such as hydrogen peroxide, potassium persulfate, sodium persulfate and ammonium persulfate; water-soluble peroxides; azobiscyanovaleric acid, 2,2′-azobis- (2-amidinopropane) dihydrochloride, etc. And a water-soluble azo compound, and one or more of them can be used. Among these, it is preferable to use an oil-soluble polymerization initiator such as an oil-soluble peroxide and / or an oil-soluble azo compound. Also,
A redox initiator system using a polymerization initiator together with a reducing agent and, if necessary, a chelating agent may be used. Examples of the reducing agent include formaldehyde alkali metal sulfoxylates such as Rongalit (formaldehyde sodium sulfoxylate); sulfites such as sodium sulfite and sodium bisulfite; pyrosulfites such as sodium pyrosulfite; sodium thiosulfate; Thiosulfates; phosphorous acid or salts thereof such as phosphorous acid and sodium phosphite; pyrophosphites such as sodium pyrophosphite; mercaptans; ascorbic acid such as ascorbic acid and sodium ascorbate or salts thereof Erythorbic acid and salts thereof such as erythorbic acid and sodium erysorbate; saccharides such as glucose and dextrose; metal salts such as ferrous sulfate and copper sulfate. Examples of the chelating agent include sodium pyrophosphate and ethylenediaminetetraacetate. These polymerization initiators, reducing agents and chelating agents are used in appropriate amounts depending on the combination of the respective polymerization initiator systems.

As described above, the composite resin in the composite resin emulsion used in the present invention has a tertiary amino group in the composite resin skeleton at a ratio of 0.1 to 50 mmol per 100 g of the composite resin (as described above). Requirements). Since the dyeability of the dye to the composite resin, particularly the acid dye, becomes better,
It is preferable that at least one of the three substituents of the tertiary amino group is an alkyl group having 4 or less carbon atoms. Methods for introducing such a tertiary amino group into the composite resin skeleton include, for example, (1) dimethylaminoethyl (meth) acrylate, (meth) acrylic acid as a part of the ethylenically unsaturated monomer (B). Diethylaminoethyl acid,
A method using a tertiary amino group-containing monomer such as N- [3- (dimethylaminopropyl)] (meth) acrylamide; (2) N-methyl-3, 3'-iminobis (propylamine), 3- (diethylamino)
Propylamine, N-methyldiethanolamine, N,
A method using a compound having one or more tertiary amino groups and an isocyanate-reactive functional group such as N-dimethylethanolamine and N, N-diethylethanolamine can be used. Among them, the method (1) is preferable because the introduction amount of the tertiary amino group is easily adjusted and the polymerization stability when the ethylenically unsaturated monomer (B) is emulsion-polymerized is excellent. When a tertiary amino group-containing monomer is used, the amount of the tertiary amino group-containing monomer is preferably 0.1 to 10% by weight based on the total amount of the ethylenically unsaturated monomer (B). It is preferable from the viewpoints that the polymerization stability of the saturated monomer (B) and the feeling of the obtained leather-like sheet material are further improved.

In the composite resin emulsion used in the present invention, a hindered amino group and / or an ultraviolet absorbing group having a light stabilizing effect are contained in the composite resin skeleton in order to further improve the light resistance of the obtained leather-like sheet. It is also possible to introduce. As a method for introducing a hindered amino group and / or an ultraviolet-absorbing group having a light stabilizing effect into the composite resin skeleton, for example, (1) as a part of the ethylenically unsaturated monomer (B), 4- ( (Meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,
6,6-pentamethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-1,2,2
An ethylenically unsaturated monomer having a hindered amino group such as 6,6-pentamethylpiperidine, or 2- [2 ′
-Hydroxy-5 '-(meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2-hydroxy-4- (meth) acryloyloxybenzophenone,
A method using an ethylenically unsaturated monomer having an ultraviolet absorbing group such as 2-hydroxy-4- (meth) acryloyloxyethylbenzophenone; (2) 4-hydroxy as a raw material for producing polyurethane in the polyurethane emulsion (A); -2,2,6,6-tetramethylpiperidine, 4-hydroxy-1,2,2,6,6-pentamethylpiperidine, 1- (2-hydroxyethyl)-
4-hydroxy-2,2,6,6-tetramethylpiperidine, 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine and polycondensate of succinic acid, 1- Examples thereof include a method using a hindered amine compound having a hydroxyl group such as a polycondensate of (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine and adipic acid. When hindered amino groups and / or ultraviolet absorbing groups are introduced into the composite resin skeleton in the composite resin emulsion, the amount of the hindered amino groups and ultraviolet absorbing groups (total of hindered amino groups and ultraviolet absorbing groups) is 0.1% per 100 g of the composite resin. It is preferable that the amount be from 50 to 50 mmol because the light stabilizing effect can be exhibited well.

The composite resin emulsion used in the present invention is:
Other polymers may be contained in the composite resin emulsion as long as the properties of the obtained leather-like sheet material are not impaired.
As such other polymers, for example, acrylonitrile-butadiene copolymer, polybutadiene, polyisoprene, polyacrylate, acrylic copolymer, olefin copolymer, silicone, other polyurethane, polyvinyl acetate, ethylene -A polymer having elasticity and / or flexibility such as a vinyl acetate copolymer, polyvinyl chloride, a polyester elastomer, and a polyamide elastomer can be used, and one or more of these can be contained.

The composite resin emulsion used in the present invention is
If necessary, further known additives, for example, light stabilizers, antioxidants, ultraviolet absorbers, surfactants such as penetrants, thickeners, fungicides, water solubility such as polyvinyl alcohol and carboxymethyl cellulose. Polymer compounds, dyes,
One or more of pigments, fillers, coagulation regulators and the like may be contained.

The method of impregnating the fibrous base material comprising the ultrafine fiber-forming fibers with the composite resin emulsion may be any method capable of uniformly impregnating the fibrous base material with the composite resin emulsion. Generally, a method of immersing a fibrous base material in a composite resin emulsion is preferably employed. Furthermore, after impregnating the fibrous base material with the composite resin emulsion, the impregnation amount of the composite resin emulsion can be adjusted to an appropriate amount using a press roll, a doctor knife or the like. The impregnation amount of the composite resin emulsion into the fibrous base material is determined by converting the ultrafine fiber-forming fibers constituting the fibrous base material into ultrafine fibers and finally obtaining the leather-like sheet-like material. Preferably, the amount of the composite resin adhered to the substrate is 5 to 150% by weight, more preferably 10 to 100% by weight, more preferably 20 to 80% by weight. More preferably, If the attached amount of the composite resin is less than 5% by weight, the obtained leather-like sheet-like material lacks a sense of fulfillment, and it becomes difficult to obtain a natural leather-like feeling, while 150% by weight is obtained.
When the ratio exceeds the above range, the obtained leather-like sheet material tends to be hard, so that it is difficult to obtain a natural leather-like feeling.

Next, the composite resin impregnated in the fibrous base material is solidified by heating. Examples of the method of heat coagulation of the composite resin emulsion include, for example, (1) a method in which a fibrous base material impregnated with the composite resin emulsion is immersed in a hot water bath at a temperature higher than the thermal gelation temperature of the composite resin emulsion and coagulated. 2) a method of spraying heated steam above the thermal gelation temperature of the composite resin emulsion onto the fibrous base material impregnated with the composite resin emulsion to coagulate it; Examples thereof include a method of directly introducing into a drying device having a temperature higher than the thermosensitive gelling temperature, coagulating by heating, and drying. Among them, the method (1) of heating and coagulating in a hot water bath or the method (2) of using heated steam is preferably employed from the viewpoint that a leather-like sheet having a feeling excellent in flexibility can be obtained. Is done. In the above methods (1) to (3), the coagulation temperature of the composite resin emulsion impregnated in the fibrous base material is reduced by rapidly completing the coagulation of the composite resin emulsion to reduce the uneven distribution of the composite resin in the fibrous base material. From the viewpoint of prevention, the temperature is preferably 10 ° C. or more higher than the thermal gelation temperature of the composite resin emulsion. Although it depends on the thermal gelation temperature of the composite resin emulsion, the above (1)
In the method (1), a hot water bath at 70 to 100 ° C is generally preferably used, and in the method (2), the temperature is generally 100 to 200 ° C.
Is preferably employed, and in the above method (3), generally, a drying temperature of 50 to 150 ° C. is preferably employed. When the coagulation method (1) or (2) is used, it is preferable to remove the water contained in the leather-like sheet by heating and coagulating the composite resin emulsion after heat coagulation.

After impregnating the fibrous base material with the composite resin emulsion and coagulating by heating, the fine fiber forming fibers constituting the fibrous base material are subjected to a treatment for converting the fibers into ultrafine fibers to form the leather-like sheet of the present invention. Manufacturing things. The method for forming ultrafine fibers at that time is performed according to the type of the ultrafine fiber forming fibers constituting the fibrous base material. For example, when the ultrafine fiber forming fiber is a sea-island mixed spun fiber or a composite spun fiber composed of two or more polymers having different solubility in an organic solvent or decomposability to a decomposing agent such as an alkaline aqueous solution, the sea-spun fiber may be used. The ultrafine fibers can be formed by dissolving and removing the polymer constituting the component with an organic solvent or by decomposing and removing the polymer with a decomposing agent to leave the island component. Further, the ultrafine fiber-forming fibers are easily separated (separated) from each other, for example, at the contact surface.
In the case of a mixed spun fiber or a composite spun fiber composed of at least one kind of polymer (particularly, a laminated type mixed spun fiber or a composite spun fiber), it is treated with a release agent (separating agent) to separate (separate) the polymer phases. ) To produce ultrafine fibers, a method of heating using the difference in heat shrinkage between polymers to cause separation (separation) between polymer phases to produce ultrafine fibers, and mechanical treatment from the outside (for example, (E.g., rubbing treatment) to cause separation (separation) between the polymer phases to form ultrafine fibers. Among them, as mentioned above,
In the present invention, the fibrous base material is preferably formed from sea-island mixed spun fibers or composite spun fibers composed of two or more polymers having different solubility in an organic solvent,
In this case, the above-described method of dissolving and removing sea components with an organic solvent to form ultrafine fibers is employed. In this case, the sea component in contact with the composite resin in the sea-island type mixed spun fiber and / or the composite spun fiber impregnated in the fibrous base material and confined by the heat-coagulated composite resin is removed, and the composite is removed. As a result of the island components not contacting the resin remaining as ultrafine fibers, the resultant leather-like sheet-like material is in a state where the constraint of the composite resin on the fibrous base material composed of ultrafine fibers is weakened, and has a sense of fulfillment. Thus, a leather-like sheet having excellent flexibility can be obtained.

The leather-like sheet material of the present invention obtained as described above is rich in flexibility, at the same time has a sense of fulfillment, and has a very good feeling and feel similar to natural leather.
There is no inferiority to the artificial leather obtained by the conventional wet coagulation method. As a result of the observation by the electron microscope of the present inventors, in the leather-like sheet-like material according to the present invention, the composite resin does not strongly restrain the fine fibers in the fibrous base material, while leaving a suitable space between the fine fibers. It was observed that the voids were filled and solidified. Therefore, in the leather-like sheet according to the present invention, a decrease in flexibility caused by binding of fibers and sagging of the leather-like sheet is prevented. Moreover, in the leather-like sheet according to the present invention, the filling amount of the apparent resin portion increases due to the fact that the composite resin fills the voids between the fibers while leaving a space between the fibers as described above. Compared to a leather-like sheet of a resin emulsion impregnated type, a leather-like sheet with excellent feeling and touch that is very close to natural leather with a sense of fulfillment while maintaining good flexibility. I have. In addition, the leather-like sheet of the present invention is excellent in properties such as dyeability, dyeing fastness (especially lightfastness to dyeing), lightfastness, and durability.

The leather-like sheet material of the present invention can be used, for example, in mattresses, bag lining materials, clothing interlinings, shoe interlinings, cushioning materials, automobiles, trains, aircrafts, etc. by utilizing the above-mentioned excellent properties. It can be effectively used for a wide range of applications such as interior materials, wall materials, carpets and the like. Further, by raising the leather-like sheet of the present invention, a suede-like leather-like sheet can be obtained, for example, clothing, lining materials for furniture such as chairs and sofas, automobiles, trains, aircrafts, and the like. It can be suitably used as an overlay, a wall material, gloves, etc. of the sheet. Further, by forming a polyurethane layer or the like on one side of the leather-like sheet material of the present invention by a known method, it is also suitably used as artificial leather with silver used for sports shoes, men's shoes, bags, handbags, school bags, and the like. can do.

[0065]

EXAMPLES The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited to the following examples. In the following examples, the thermal gelation temperature of the composite resin emulsion, the elastic modulus at 90 ° C. and 160 ° C. of the film obtained by drying the composite resin emulsion, the α dispersion temperature, the flexibility of the leather-like sheet, and the bending resistance The properties, hand, dyeability, and lightfastness of dyeing were measured or evaluated by the following methods.

[Thermal Gelation Temperature of Composite Resin Emulsion] 10 g of the composite resin emulsion was weighed into a test tube,
The temperature was raised while stirring in a constant temperature hot water bath at 0 ° C., and the temperature of the composite resin emulsion when the composite resin emulsion lost its fluidity and became a gel-like material was defined as the thermosensitive gelling temperature.

[Elastic Modulus and α at 90 ° C. and 160 ° C. of Film Obtained by Drying Composite Resin Emulsion
Dispersion Temperature] A 100 μm-thick film obtained by drying the composite resin emulsion at 50 ° C. is heat-treated at 130 ° C. for 10 minutes, and then a viscoelasticity measuring device “FT Rheospectral DVE-V4” manufactured by Rheology Co., Ltd. And the elastic modulus (E ′) and α-dispersion temperature (Tα) at 90 ° C. and 160 ° C. were determined.

[Flexibility (Bending Rigidity) of Leather-Like Sheet Material] A leather-like sheet material was cut into a size of 10 cm × 10 cm, and a pure bending tester (KATO TEKKO) was prepared at a room temperature of 20 ° C. and a humidity of 65%. KES-FB2-
L "), the flexural rigidity (gf) in the direction perpendicular to the winding direction of the nonwoven fabric used for producing the leather-like sheet material
cm ² / cm) as an index of flexibility.

[Bending Resistance of Leather-Like Sheet] The leather-like sheet was cut into a size of 7 cm × 4.5 cm, and was subjected to JI.
According to SK6545, a bending resistance tester (Ball
y "Flexometer") at a temperature of 20
A bending test was performed under the conditions of ° C and a humidity of 65%. Number of bending 1
The surface condition of the leather-like sheet was observed every 100,000 times, and the number of times until cracks and / or holes were formed was measured. When cracks and / or perforations did not occur even after 500,000 times, it was judged that the bending resistance was sufficiently good (○).

[Hand of Leather-Like Sheet] When the leather-like sheet is touched by hand, it is judged as good (O) when it has the same feel (flexibility and fullness) as natural leather. And
When it was harder than natural leather and lacked flexibility, and / or when it lacked a sense of fulfillment, it was determined to be poor (x).

[Dyeability of Leather-Like Sheet] After one side of the leather-like sheet was fluffed with emery paper, 100 parts by weight of the brush-treated leather-like sheet was used, and a dye containing gold (Ciba Geigy Co., Ltd.) was used. Company made Irgalan
Green GL ”) (acid dye)
Dyeing was carried out at a bath ratio of 1:40 at 90 ° C. for 1 hour. The surface of the leather-like sheet after dyeing is visually observed, and when the dye is uniformly dyed without color spots, the dyeability is judged to be good (O). The case where there was a spot was determined as poor staining (x).

[Light-fastness to Light Dyeing of Leather-Like Sheet Material] A leather-like sheet material dyed by the above method was subjected to a fade tester (“UV Long Life Fade Tester FAL-5H · B. BR ", ultraviolet carbon arc lamp, 63 ° C.) for 20 hours, and the leather-like sheet-like material has a gray scale of fading (JIS).
L 0804). Note that the smaller the value, the greater the degree of fading.

The abbreviations and contents of the polymer diols used in the following examples are as follows. ＰＭ PMPA2000 : Polyester diol having a number average molecular weight of 2,000 (produced by reacting 3-methyl-1,5-pentanediol with adipic acid) Ｐ PTMG1000 : Polytetramethylene glycol having a number average molecular weight of 1,000 Polyhexamethylene carbonate diol

Reference Example 1 [Fibrous base material (entangled nonwoven fabric)
Production of 60 parts by weight of 6-nylon and 40 parts by weight of highly flowable polyethylene, which are mixed and spun, stretched, and cut to obtain a sea-island type mixed spun fiber (single fiber fineness: 4 denier, fiber length: 51
mm, 6-nylon is island component, polyethylene is sea component,
Using the number of islands of 100 in the fiber cross section), an entangled nonwoven fabric having an apparent density of 0.16 g / cm ³ was produced through the steps of card, cross wrapper and needle punch.
The entangled non-woven fabric is heated to partially melt polyethylene as a sea component and heat-set between the fibers to obtain an apparent density of 0.2.
An entangled nonwoven fabric of 85 g / cm ³ with both surfaces smoothed was obtained.

Reference Example 2 [Production of Polyurethane Emulsion] In a three-necked flask, PMPA20 was added as a polymer diol.
300.0 g of 2,00.87 g of 2,4-tolylene diisocyanate and 7.85 g of 2,2-bis (hydroxymethyl) propionic acid were weighed, and the mixture was stirred at 90 ° C. for 2 hours under a dry nitrogen atmosphere. The hydroxyl groups in the reaction were quantitatively reacted to produce a polyurethane prepolymer having an isocyanate group end. To this, 195.4 g of 2-butanone
, And the mixture was stirred uniformly, then the temperature in the flask was lowered to 40 ° C., and 5.92 g of triethylamine was added, followed by stirring for 10 minutes. Next, an aqueous solution obtained by dissolving 7.83 g of sodium lauryl sulfate in 285.0 g of distilled water as an emulsifier was added to the polyurethane prepolymer, and the mixture was emulsified by stirring with a homomixer for 1 minute. An aqueous solution in which 70 g was dissolved in 496.4 g of distilled water was added, and the mixture was stirred with a homomixer for 1 minute to perform a chain extension reaction. Then 2
-Butanone was removed by a rotary evaporator to obtain a polyurethane emulsion having a solid content of 35% by weight (hereinafter referred to as "PU emulsion").

Reference Example 3 [Production of Polyurethane Emulsion] PTMG10 was used as a polymer diol in a three-necked flask.
00: 150.0 g, PHC2000: 150.0 g
g, 2,4-tolylene diisocyanate (74.45 g) and 2,2-bis (hydroxymethyl) propionic acid (9.05 g) were weighed and stirred at 90 ° C. for 2 hours in a dry nitrogen atmosphere to remove hydroxyl groups in the system. By reacting quantitatively, an isocyanate group-terminated polyurethane prepolymer was produced. After adding 202.9 g of 2-butanone to the mixture and uniformly stirring, the temperature in the flask was lowered to 40 ° C., and 6.83 g of triethylamine was added, followed by stirring for 10 minutes. Next, 6.10 g of sodium lauryl sulfate was used as an emulsifier.
And 6.10 g of ETC-3NEX (anionic emulsifier manufactured by Nippon Surfactant Industries, Ltd.) in distilled water 29
An aqueous solution dissolved in 6.6 g was added to the above polyurethane prepolymer, and the mixture was emulsified by stirring with a homomixer for 1 minute. The mixture was stirred for 1 minute with a homomixer to perform a chain extension reaction. Thereafter, 2-butanone was removed by a rotary evaporator to obtain a polyurethane emulsion having a solid content of 35% by weight (hereinafter referred to as “PU emulsion”).

Reference Example 4 [Production of Polyurethane Emulsion] In Reference Example 2, instead of isophoronediamine, N-
3. Methyl-3,3'-iminobis (propylamine)
A polyurethane emulsion having a solid content of 35% by weight (hereinafter referred to as "PU emulsion") was obtained in the same manner as in Reference Example 2 except that 87 g was used.

Example 1 [Production of leather-like sheet] (1) Production of composite resin emulsion: (i) P obtained in Reference Example 2 was placed in a flask equipped with a cooling tube.
240g of U emulsion, ferrous sulfate heptahydrate _{(FeSO 4 · 7H 2 O)} 0.020g, potassium pyrophosphate 0.294 g, Rongalite (dihydrate of sodium formaldehyde sulfoxylate) 0.451 g, ethylenediamine Tetraacetic acid disodium salt (EDTA ・ 2
Na) 0.020 g of distilled water and 246 g of distilled water
After the temperature was raised to 0 ° C., the inside of the system was sufficiently purged with nitrogen. (Ii) Then, 147.4 g of butyl acrylate, 4.70 g of diethylaminoethyl methacrylate, 3.14 g of 1,6-hexanediol diacrylate, 1.57 g of allyl methacrylate and the same anionicity as used in Reference Example 3 1.57 g of emulsifier ("ECT-3NEX")
(Monomer mixture), cumene hydroperoxide 0.314 g, ECT-3NEX 0.314 g
And an emulsion (initiator) consisting of 15.0 g of distilled water
Was dropped into the flask from separate dropping funnels over 4 hours, and after completion of the dropping, the mixture was kept at 40 ° C. for 30 minutes. (Iii) Then, 38.4 g of methyl methacrylate,
A mixture of 0.78 g of 1,6-hexanediol diacrylate and 0.392 g of ECT-3NEX (monomer mixture) and 0.078 of cumene hydroperoxide
2. 0.078 g of ECT-3NEX and distilled water.
0 g of an emulsion (initiator) was dropped into the flask from a separate dropping funnel over 1 hour and 30 minutes, and after completion of the dropping, the mixture was maintained at 50 ° C. for 60 minutes to complete the polymerization.
A composite resin emulsion having a solid content of 40% by weight was produced. (Iv) Emulgen 109P (manufactured by Kao Corporation, nonionic surfactant) (4 parts by weight) and calcium chloride (1 part by weight) were mixed with 100 parts by weight of the composite resin emulsion obtained in (iii) above, and heat-sensitive. A composite resin emulsion having gelling properties was obtained. The thermal gelation temperature of this composite resin emulsion, the elastic modulus (E ') at 90 ° C. and 160 ° C. and the α-dispersion temperature (Tα) at 90 ° C. and 160 ° C. of the film obtained by drying the composite resin emulsion are shown in Table 4 below. It was as follows.

(2) Production of leather-like sheet material: (i) The entangled nonwoven fabric obtained in Reference Example 1
Immersed in the bath of the thermogelling composite resin emulsion obtained in the above to impregnate the thermogelling composite resin emulsion, taken out of the bath, squeezed with a press roll, and then
The thermosensitive gelling composite resin emulsion was immersed in a hot water bath at 0 ° C. for 1 minute to coagulate, and then dried in a hot air drier at 130 ° C. for 30 minutes to produce a sheet. (Ii) The sheet-like material obtained in the above (i) is heated at a temperature of 90 ° C.
Immersed in toluene and squeezed five times with a ² kg / cm ² press roll during immersion to obtain a sea component (polyethylene) in the sea-island mixed spun fiber constituting the nonwoven fabric
Was dissolved and removed to produce a leather-like sheet in which an elastic polymer composed of a coagulated composite resin was impregnated and adhered to a 6-nylon ultrafine fiber bundle entangled nonwoven fabric. The attached weight of the composite resin in the leather-like sheet was 60% by weight based on the weight of the nonwoven fabric after the ultrafine fiber treatment. The flexural modulus, flex resistance, hand feeling, dyeability and light fastness to light of this leather-like sheet were measured or evaluated by the methods described above. The results are as shown in Table 4 below. It was a leather-like sheet having a very good feel and feel close to that of natural leather and having excellent durability, dyeability and light-fastness to light dyeing.

Example 2 [Production of leather-like sheet] (1) Production of composite resin emulsion: (1) of Example 1
In the same manner as described above, a composite resin emulsion having heat-sensitive gelling property was produced using the raw materials shown in Table 2 below.
The heat-sensitive gelation temperature of the obtained composite resin emulsion, 90% of the film obtained by drying the composite resin emulsion
The elastic modulus (E ') and α-dispersion temperature (Tα) at ° C and 160 ° C were as shown in Table 4 below. (2) Production of leather-like sheet material: (i) The entangled nonwoven fabric obtained in Reference Example 1 was subjected to the above (1)
Immersed in the bath of the thermogelling composite resin emulsion obtained in the above, and impregnated with the thermogelling composite resin emulsion, taken out of the bath, squeezed by a press roll, and then squeezed with a pressure of 1.5 kg / cm ² . Heated steam (temperature 112
° C) is sprayed on the whole to solidify the thermosensitive gelling composite resin emulsion, which is then dried in a hot air drier at 130 ° C for 30 minutes.
After drying for a minute, a sheet was produced. (Ii) The sheet-like material obtained in the above (i) is subjected to ultrafine fiber treatment in the same manner as in (2) of Example 1 (2) to form a 6-nylon ultrafine fiber bundle entangled nonwoven fabric. A leather-like sheet was impregnated with and adhered to an elastic polymer comprising a coagulated composite resin. The attached weight of the composite resin in the leather-like sheet was 59% by weight based on the weight of the nonwoven fabric after the ultrafine fiber treatment. The flexural modulus, flex resistance, hand feeling, dyeability and light fastness to light of this leather-like sheet were measured or evaluated by the methods described above. The results are as shown in Table 4 below. It was a leather-like sheet having a very good feel and feel close to that of natural leather and having excellent durability, dyeability and light-fastness to light dyeing.

<< Example 3 >> [Production of leather-like sheet-like material] (1) Production of composite resin emulsion: (1) of Example 1
In the same manner as described above, a composite resin emulsion having heat-sensitive gelling property was produced using the raw materials shown in Table 2 below.
The heat-sensitive gelation temperature of the obtained composite resin emulsion, 90% of the film obtained by drying the composite resin emulsion
The elastic modulus (E ') and α-dispersion temperature (Tα) at ° C and 160 ° C were as shown in Table 4 below. (2) Production of leather-like sheet material: (i) 100 parts by weight of the heat-sensitive gelling composite resin emulsion obtained in (1) above, a penetrating agent (substrate wetting agent “Polyflow KL260 manufactured by TCS”) )) After adding 0.5 parts by weight, the entangled nonwoven fabric obtained in Reference Example 1 was immersed in the bath to impregnate the heat-sensitive gelling composite resin emulsion, and then taken out of the bath and press rolled. And then heated in a hot air dryer at 130 ° C. for 30 minutes to coagulate and dry to produce a sheet-like material. (Ii) The sheet-like material obtained in the above (i) is subjected to ultrafine fiber treatment in the same manner as in (2) of Example 1 (2) to form a 6-nylon ultrafine fiber bundle entangled nonwoven fabric. A leather-like sheet was impregnated with and adhered to an elastic polymer comprising a coagulated composite resin. The attached weight of the composite resin in the leather-like sheet was 54% by weight based on the weight of the nonwoven fabric after the ultrafine fiber treatment. The flexural modulus, flex resistance, hand feeling, dyeability and light fastness to light of this leather-like sheet were measured or evaluated by the methods described above. The results are as shown in Table 4 below. It was a leather-like sheet having a very good feel and feel close to that of natural leather and having excellent durability, dyeability and light-fastness to light dyeing.

Example 4 [Production of leather-like sheet-like material] (1) Production of composite resin emulsion: (1) of Example 1
In the same manner as described above, a composite resin emulsion having heat-sensitive gelling property was produced using the raw materials shown in Table 2 below.
The heat-sensitive gelation temperature of the obtained composite resin emulsion, 90% of the film obtained by drying the composite resin emulsion
The elastic modulus (E ') and α-dispersion temperature (Tα) at ° C and 160 ° C were as shown in Table 4 below. (2) Production of a leather-like sheet material: The heat-sensitive gelling composite resin emulsion obtained in the above (1) on the entangled nonwoven fabric obtained in the reference example 1 in the same manner as in (2) of Example 1. After impregnating with, a fine fiber treatment was performed to produce a leather-like sheet. The attached weight of the composite resin in the leather-like sheet was 71% by weight based on the weight of the nonwoven fabric after the ultrafine fiber treatment. The leather-like sheet was measured or evaluated for flexural modulus, flex resistance, hand feeling, dyeability, and light-dye fastness by the methods described above.
As shown in the table, the leather-like sheet has flexibility and fullness, has a very good feel and feel similar to natural leather, and also has excellent durability, dyeability and light-fastness to light dyeing. It was a thing.

<< Comparative Example 1 >> [Production of leather-like sheet] (1) Production of composite resin emulsion: (i) P obtained in Reference Example 3 was placed in a flask equipped with a cooling tube.
240g of U emulsion, ferrous sulfate heptahydrate _{(FeSO 4 · 7H 2 O)} 0.020g, potassium pyrophosphate 0.294 g, Rongalite (dihydrate of sodium formaldehyde sulfoxylate) 0.451 g, ethylenediamine Tetraacetic acid disodium salt (EDTA ・ 2
Na) 0.020 g and 244 g of distilled water were weighed and
After the temperature was raised to 0 ° C., the inside of the system was sufficiently purged with nitrogen. (Ii) Then, 180.3 g of methyl methacrylate, 5.88 g of diethylaminoethyl methacrylate, 1,6-
9.80 g of hexanediol diacrylate and the same anionic emulsifier used in Reference Example 3 (“ECT-
3NEX ") 1.96 g mixture (monomer mixture)
And 0.392 g of cumene hydroperoxide, ECT-
An emulsion (initiator) composed of 0.392 g of 3NEX and 20.0 g of distilled water was dropped into the flask from separate dropping funnels over 5 hours, and after completion of the dropping, the mixture was kept at 50 ° C. for 60 minutes for polymerization. Was completed to produce a composite resin emulsion having a solid content of 40% by weight. (Iii) 4 parts by weight of Emulgen 109P (a nonionic surfactant manufactured by Kao Corporation) and 1 part by weight of calcium chloride were mixed with 100 parts by weight of the composite resin emulsion obtained in (ii) above, A composite resin emulsion having gelling properties was obtained. The thermal gelation temperature of this composite resin emulsion, the modulus of elasticity (E ') at 90 ° C. and 160 ° C. and the α-dispersion temperature (Tα) at 90 ° C. and 160 ° C. of the film obtained by drying the composite resin emulsion are shown in Table 5 below. It was as follows.

(2) Production of leather-like sheet: Example 1
In the same manner as in (2) above, the entangled nonwoven fabric obtained in Reference Example 1 was impregnated with the thermogelling composite resin emulsion obtained in (1) above, and then subjected to ultrafine fiber treatment to produce leather. A sheet-like material was produced. The attached weight of the composite resin in the leather-like sheet was 58% by weight based on the weight of the nonwoven fabric after the ultrafine fiber treatment. When the flexural modulus, flex resistance, hand feeling, dyeing property and light-fastness to light of this leather-like sheet were measured or evaluated by the above-mentioned methods, the results are as shown in Table 5 below, and there was no flexibility. Had a hard and poor texture.

<< Comparative Example 2 >> [Production of leather-like sheet material] (1) Production of composite resin emulsion: (1) of Comparative Example 1
In the same manner as described above, a composite resin emulsion having heat-sensitive gelling property was produced using the raw materials shown in Table 3 below.
The heat-sensitive gelation temperature of the obtained composite resin emulsion, 90% of the film obtained by drying the composite resin emulsion
The elastic modulus (E ') and α-dispersion temperature (Tα) at ° C and 160 ° C were as shown in Table 5 below. (2) Production of a leather-like sheet material: The heat-sensitive gelling composite resin emulsion obtained in the above (1) on the entangled nonwoven fabric obtained in the reference example 1 in the same manner as in (2) of Example 1. After impregnating with, a fine fiber treatment was performed to produce a leather-like sheet. The attached weight of the composite resin in the leather-like sheet was 57% by weight based on the weight of the nonwoven fabric after the ultrafine fiber treatment. The leather-like sheet was measured or evaluated for the flexural modulus, flex resistance, hand feeling, dyeability and light fastness by the above-mentioned methods.
As shown in Fig. 5, sagging occurred, and the overall feeling was paper-like, lacking in fullness and lacking flexibility.

<< Comparative Example 3 >> [Production of leather-like sheet material] (1) Production of composite resin emulsion: (1) of Example 1
(I) to (iii) were carried out to produce a composite resin emulsion containing no heat-sensitive gelling agent (Emulgen 109P and calcium chloride). This composite resin emulsion does not exhibit heat-sensitive gelling property, and the resulting composite resin emulsion has a 90
The elastic modulus (E ') and α-dispersion temperature (Tα) at ° C and 160 ° C were as shown in Table 5 below. (2) Production of leather-like sheet material: Non-thermosensitive gel obtained in (1) above on entangled nonwoven fabric obtained in Reference Example 1 in the same manner as in (i) of (2) of Example 1 When the treatment was performed in a hot water bath after impregnating the composite resin emulsion, the composite resin emulsion flowed out into the hot water bath and contaminated the bathtub. This sheet-like material was used in Example 1 (2) (ii).
Ultrafine fiber treatment was performed in the same manner as described above to produce a leather-like sheet. The adhesion weight of the composite resin in the leather-like sheet is 32 to the weight of the nonwoven fabric after the ultrafine fiberizing treatment.
% By weight. Flexural modulus of this leather-like sheet,
When the flex resistance, hand, dyeability and light fastness to light were measured or evaluated by the above-described methods, the results are as shown in Table 5 below. The texture was inflexible and poor.

<< Comparative Example 4 >> [Production of leather-like sheet material] (1) Production of composite resin emulsion: (1) of Example 1
In the same manner as described above, a composite resin emulsion having heat-sensitive gelling property was produced using the raw materials shown in Table 3 below.
The heat-sensitive gelation temperature of the obtained composite resin emulsion, 90% of the film obtained by drying the composite resin emulsion
The elastic modulus (E ') and α-dispersion temperature (Tα) at ° C and 160 ° C were as shown in Table 5 below. (2) Production of a leather-like sheet material: The heat-sensitive gelling composite resin emulsion obtained in the above (1) on the entangled nonwoven fabric obtained in the reference example 1 in the same manner as in (2) of Example 1. After impregnating with, a fine fiber treatment was performed to produce a leather-like sheet. The attached weight of the composite resin in the leather-like sheet was 55% by weight based on the weight of the nonwoven fabric after the ultrafine fiber treatment. The leather-like sheet was measured or evaluated for the flexural modulus, flex resistance, hand feeling, dyeability and light fastness by the above-mentioned methods.
Was as shown in FIG.

The abbreviations and types of compounds in Tables 2 and 3 below are as shown in Table 1 below.

[0089]

[Table 1]

[0090]

[Table 2]

[0091]

[Table 3]

[0092]

[Table 4]

[0093]

[Table 5]

From the results of Examples 1 to 4 shown in Table 4 above, a thermosensitive gelling composite resin emulsion satisfying the above-mentioned requirements was impregnated into a fibrous base material composed of ultrafine fiber-forming fibers. After heating and coagulation, the leather-like sheet materials of Examples 1 to 4 produced by converting the ultrafine fiber-forming fibers constituting the fibrous base material into ultrafine fibers have flexibility and a sense of fulfillment, and It can be seen that the leather has a high-grade feel and feel similar to leather, and also has excellent dyeability, light fastness, and durability (light fastness to light dyeing). On the other hand, from the results of Comparative Example 1 shown in Table 5 above, 90% of the film obtained by drying the composite resin emulsion was obtained.
When a composite resin emulsion having an elastic modulus at ℃ of 6.9 × 10 ⁸ dyn / cm ² and not satisfying the above requirements was used, the obtained leather-like sheet material had a flexural modulus of elasticity. It can be seen that the texture is high, lacks flexibility, is hard and has a poor feel, and is inferior in bending resistance.

From the results of Comparative Example 2 shown in Table 5, the elastic modulus at 160 ° C. of the film obtained by drying the composite resin emulsion was 3.9 × 10 ⁶ dyn / c.
A m ^2, and in the case of using the composite resin emulsion does not satisfy the above requirements, the resulting leather-like sheet is a hard and bad feeling lacks flexibility high flexural modulus You can see that there is. From the results of Comparative Example 3 shown in Table 5, when a composite resin emulsion that is non-thermosensitive and does not satisfy the above requirements is used, the obtained leather-like sheet has a high flexural modulus. It turns out that it is hard and lacks flexibility and has a poor texture. Also, from the results of Comparative Example 4 shown in Table 5 above, when the composite resin in the composite resin emulsion impregnated and adhered to the fibrous base material does not contain a tertiary amino group, the dyeability of the leather-like sheet material It can be seen that the light fastness to light was inferior.

[0096]

According to the present invention, the above-mentioned requirements
By producing a leather-like sheet using a specific thermosensitive gelling aqueous composite resin emulsion that satisfies the requirements, during the impregnation of the composite resin into the fibrous base material and during the coagulation of the impregnated composite resin, Eliminates the need to use organic solvents that cause deterioration and pollution of the global environment and work environment. Simple and safe process. It has flexibility and a sense of quality. It is possible to produce a leather-like sheet having a combined and tactile feel with high productivity. Moreover, the leather-like sheet obtained according to the present invention has excellent properties such as dyeability, light fastness and durability.

Claims (9)

[Claims] 1. A fibrous base material composed of ultrafine fiber-forming fibers is impregnated with a composite resin emulsion satisfying the following requirements and heat-coagulated. A method for producing a leather-like sheet, characterized in that fibers are converted to ultrafine fibers; a thermosensitive gelling composite resin emulsion; a 100 μm-thick film obtained by drying the composite resin emulsion at 50 ° C. The elastic modulus at 90 ° C. is 5.0 × 10 ⁸ dyn / cm ² or less; The 100 μm-thick film obtained by drying the composite resin emulsion at 50 ° C. has an elastic modulus at 160 ° C. of 5.0 × 10 5 dyn / cm ^2. is ⁶ dyn / cm ² or more; in the presence of a polyurethane-based emulsion (a), the polyurethane of the ethylenically unsaturated monomer (B), in polyurethane-based emulsion (a) The weight ratio of the ethylenically unsaturated monomer (B)] = 70: 30~10: 90
And the composite resin in the composite resin emulsion has tertiary amino groups at a ratio of 0.1 to 50 mmol per 100 g of the composite resin. 2. The method according to claim 1, wherein the ultrafine fiber forming fibers constituting the fibrous base material are ultrafine fiber forming fibers containing polyamide as one component. 3. The method according to claim 1, wherein the α-dispersion temperature of a 100 μm-thick film obtained by drying the composite resin emulsion at 50 ° C. is −10 ° C. or less. 4. A polyurethane emulsion (A) comprising:
The production method according to any one of claims 1 to 3, wherein the emulsion is a polyurethane emulsion formed using an aromatic polyisocyanate compound. 5. The method according to claim 1, wherein the ethylenically unsaturated monomer (B) is a monofunctional ethylenically unsaturated monomer (B1) composed mainly of (meth) acrylic acid and / or a derivative thereof.
The method according to any one of claims 1 to 4, comprising 99.9% by weight and 0.1 to 10% by weight of a bifunctional or higher-functional polyfunctional ethylenically unsaturated monomer (B2). 6. An ethylenically unsaturated monomer (B) comprising 3
The method according to any one of claims 1 to 5, comprising 0.1 to 10% by weight of an unsaturated monomer having a secondary amino group. 7. The microfiber-forming fibers constituting the fibrous base material are sea-island mixed spun fibers and / or sea-island composite spun fibers, and after the fibrous base material is impregnated with a composite resin emulsion and heat-coagulated. The method according to any one of claims 1 to 6, wherein sea components in the ultrafine fiber-forming fibers constituting the fibrous base material are removed to form ultrafine fibers. 8. The composite resin emulsion has a thermosensitive gelation temperature of 30 to 70 ° C., and after impregnating the fibrous base material with the composite resin emulsion, heating the composite resin emulsion to a temperature higher than the thermosensitive gelation temperature by 10 ° C. or more. The method according to any one of claims 1 to 7, wherein the resin emulsion is solidified. 9. A leather-like sheet obtained by the production method according to any one of claims 1 to 8.