WO2010137264A1 - Method for producing polyurethane laminate, and polyurethane laminate obtained by the production method - Google Patents

Method for producing polyurethane laminate, and polyurethane laminate obtained by the production method Download PDF

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WO2010137264A1
WO2010137264A1 PCT/JP2010/003393 JP2010003393W WO2010137264A1 WO 2010137264 A1 WO2010137264 A1 WO 2010137264A1 JP 2010003393 W JP2010003393 W JP 2010003393W WO 2010137264 A1 WO2010137264 A1 WO 2010137264A1
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polyurethane
layer
temperature
urethane
surface
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PCT/JP2010/003393
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French (fr)
Japanese (ja)
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米田久夫
井上和正
芦田哲哉
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株式会社クラレ
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/12Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/22Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
    • B29C43/28Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length incorporating preformed parts or layers, e.g. compression moulding around inserts or for coating articles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/40Layered products comprising a layer of synthetic resin comprising polyurethanes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00Layered products comprising a layer of paper or cardboard
    • B32B29/02Layered products comprising a layer of paper or cardboard next to a fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form ; Layered products having particular features of form
    • B32B3/26Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form ; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/266Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form ; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers, i.e. products comprising layers having different physical properties and products characterised by the interconnection of layers
    • B32B7/04Layered products characterised by the relation between layers, i.e. products comprising layers having different physical properties and products characterised by the interconnection of layers characterised by the connection of layers
    • B32B7/06Layered products characterised by the relation between layers, i.e. products comprising layers having different physical properties and products characterised by the interconnection of layers characterised by the connection of layers permitting easy separation, e.g. releasable layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/24Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of material
    • B29C67/246Moulding high reactive monomers or prepolymers, e.g. by reaction injection moulding [RIM], liquid injection moulding [LIM]
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS
    • B29K2075/00Use of PU, i.e. polyureas or polyurethanes or derivatives thereof as moulding material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00Impregnation or embedding of a layer; Bonding a fibrous, filamentary or particulate layer by using a binder
    • B32B2260/02Composition of the impregnated, bonded or embedded layer
    • B32B2260/021Fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00Impregnation or embedding of a layer; Bonding a fibrous, filamentary or particulate layer by using a binder
    • B32B2260/04Impregnation material
    • B32B2260/046Synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/748Releasability
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2437/00Clothing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2437/00Clothing
    • B32B2437/02Gloves, shoes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00Containers; Receptacles
    • B32B2439/02Open containers
    • B32B2439/06Bags, sacks, sachets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00Containers; Receptacles
    • B32B2439/40Closed containers
    • B32B2439/46Bags
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2479/00Furniture

Abstract

Disclosed is a method for producing a polyurethane laminate, which comprises: a melt-mixing step in which a urethane resin composition is formed by heating and melt-mixing a urethane prepolymer that is in a semi-solid state or in a solid state at room temperature, a chain extender and a temperature-sensitive urethanization catalyst exhibiting a specific exothermic peak temperature, within a temperature range lower than the exothermic peak temperature by 10-30˚C; a resin layer-forming step in which a urethane resin layer is formed on a sheet surface using the urethane resin composition; and a heating step in which the urethane resin layer is heated at a temperature not less than the exothermic peak temperature. Also disclosed is a polyurethane laminate that is a laminate of a composite fiber sheet, which is obtained by integrating a fiber sheet and a polymer elastic material by impregnation and has a plurality of pores in the surface layer, and a polyurethane resin layer that is arranged on the composite fiber sheet. The polyurethane laminate has a mixed layer having a thickness of not less than 10 μm. In the mixed layer, some parts of the polyurethane resin layer and the surface layer of the composite fiber sheet are present in an incompatible state since the parts of the polyurethane resin layer have entered into the pores.

Description

Polyurethane laminate obtained by the production method and the production method of the polyurethane laminate

The present invention relates to a polyurethane laminate obtained by the production method and the production method of the polyurethane laminate.

Conventionally, footwear, clothing, bags, polyurethane laminate is widely used as a surface material for furniture.

Typical construction of such a polyurethane laminate, a nonwoven fabric, a woven fabric, a polyurethane or the like on the surface of the composite fiber base material impregnated in the fibrous base material such as knitted fabric, such as by laminating a polyurethane layer structure and the like. The polyurethane layer, the composite fiber base material surface, after coating a solvent type polyurethane and aqueous polyurethane, drying and a method of, in the composite fiber base material surface, a polyurethane film formed in advance release paper surface by an adhesive It is formed using a method of bonding.

In recent years, in order to reduce the environmental impact, in the production of polyurethane laminates, the process of using a solvent-free urethane prepolymer which does not use organic solvents has been demanded.

For example, the following Patent Document 1, at normal temperature as the A component semisolid or an isocyanate group-containing urethane prepolymer in a solid state, the compound capable of reacting with isocyanate groups and / or heating and melting the urethane curing catalyst as component B after a process for producing the polyurethane porous body is mechanically foamed by stirring and mixing is disclosed. According to such a method, without using a solvent and drying machine, it is described that the polyurethane porous body of high strength can be manufactured efficiently.

Further, conventionally, a bag, shoes, clothing, the leather-like sheet using the polyurethane laminates are widely used as a surface material that resembles leather used for furniture and the like.

Examples of such a typical structure of a polyurethane laminate, the surface of the composite fiber sheet formed by impregnating a polyurethane porous fibrous base material such as a nonwoven fabric, and a structure obtained by laminating a polyurethane resin layer. Specific examples of the production method, for example, as disclosed in Patent Document 2, a polyurethane resin layer by bonding the thermoplastic polyurethane film immediately after extruded using a T-die on the surface of the composite fiber sheet a method of forming a known. As another method, as disclosed in Patent Document 3, a solvent type urethane resin on the surface of the release paper a polyurethane resin layer was formed by coating and drying, the resulting polyurethane resin layer, a solvent it is also known a method for producing a leather-like sheet by drying bonded using a mold urethane adhesive. As yet another alternative, for example, as disclosed in Patent Document 4, after coating the aqueous polyurethane resin on the surface of the release paper, a polyurethane resin layer was formed by drying, resulting polyurethane resin layer method of producing a leather-like sheet by the drying by bonding the composite fiber sheet using a water-based urethane adhesives are also known. Further, for example, as disclosed in Patent Document 5, on the surface of the composite fiber sheet, after applying the hot-melt type urethane resin was melted, it is also known a method of forming a polyurethane resin layer by crosslinking there.

JP 2002-249534 JP JP 9-24590 discloses JP 2005-113318 JP JP 2005-264371 JP International Publication WO2005 / 083173 pamphlet

In the method for producing the polyurethane porous body as described in Patent Document 1, indeed, it can realize solvent-free. However, according to the study by the present inventors, using the method described above, if the industrial continuous production of polyurethane laminate, has the following problems.

Urethane prepolymer at ordinary temperature as described in Patent Document 1 is a semi-solid or solid state into a low viscosity by heating to a relatively high temperature, is adjusted to a viscosity capable of mechanical foaming. When heating the urethane resin composition comprising a urethane prepolymer and a urethane curing catalyst to the extent possible mechanical foaming, crosslinking reaction by urethane curing catalyst is activated to proceed. In this manner, when heating the urethane resin composition to a temperature that enables the mechanical foaming, in order to melt viscosity crosslinking reaction proceeds in the urethane prepolymer is gradually increased, the pot life of the urethane resin composition shorter, there is a problem that for a long time of continuous production is difficult.

Further, in the case of producing the polyurethane porous body according to the method described in Patent Document 1, the pores obtained due to the use of mechanical foaming becomes communicating hole, a porous body having a uniform closed pores there was also a problem that can not be obtained.

The present invention, in the case of forming a polyurethane layer formed by using the urethane prepolymer is a semi-solid or solid at room temperature on a sheet, a continuous by maintaining long pot life of the urethane resin composition applied stably can form a polyurethane layer of non-crosslinked, also aims to increase productivity by crosslinking quickly by heat treatment polyurethane layer of uncrosslinked coated.

Method for producing a polyurethane laminate which is one aspect of the present invention, sensitive indicating the predetermined exothermic peak temperature room temperature a semi-solid or solid at which the urethane prepolymer (A) and the chain extender (B) and by differential scanning calorimetry a melt mixing step of forming a urethane resin composition by heating melted and mixed at a temperature range of less 10 ~ 30 ° C. relative to the temperature urethane catalyst (C) the exothermic peak temperature, the urethane resin composition wherein a resin layer forming step of forming a urethane resin layer on the sheet surface such as a release paper or fibrous substrate with, that and a heat treatment step of heat-treating the urethane resin layer by the exothermic peak temperature or higher to.

Further, according to the study by the present inventors, as disclosed in Patent Document 2, a polyurethane resin layer by bonding the thermoplastic polyurethane film immediately after extruded by T-die on the surface of the composite fiber sheet According to the method of forming, in order to thermoplastic polyurethane film is rapidly cooled when in contact with the surface of the composite fiber sheet, is crimped in a state in which proceeds to some extent solidify. Therefore, the interface between the composite fiber sheet and the thermoplastic polyurethane film becomes a two-dimensional planar surface. The difference in elastic modulus and elongation of the composite fiber sheet and the polyurethane film when bending the polyurethane laminate Therefore, at the interface between the composite fiber sheet and the thermoplastic polyurethane film, occurs misalignment or separation. Such interfacial displacement or separation of the layers in the results in the following problems. Specifically, for example, it occurs broken grain when folding the leather as compared to fine wrinkles as shown in FIG. 7, in the case of the polyurethane laminate obtained by the method as described above, as shown in FIG. 8, a large wrinkles such as bending the cardboard. Further, after the bending, there is a problem that creases are many remain.

Further, according to the study by the present inventors, as disclosed in Patent Document 3, according to the method of forming a polyurethane resin layer by applying and drying a solvent type urethane resin on the surface of the release paper, the coating and to repeat the drying process a number of times, a polyurethane resin layer of sufficient thickness having smooth on the surface there is a problem that is not obtained. Moreover, in this way releasing the polyurethane resin layer formed on the paper it is bonded with a solvent-type urethane adhesive composite fiber sheet surface. According to the method of laminating by such adhesive, the adhesive layer is present between the polyurethane resin layer and the composite fiber sheet. Therefore, the gap of the surface layer portion of the composite fiber sheet to the polyurethane resin layer is hardly permeated and filling, the sense of unity with the polyurethane resin layer and the composite fiber sheet was not obtained. Therefore, it tended to be inferior to the texture and creases feeling of leather-like. Furthermore, as another problem, the pore structure pores partition wall is dissolved by the solvent in the adhesive of the polyurethane porous impregnated fiber composite sheet is broken, texture and surface smoothness was also lowered .

Furthermore, according to the study by the present inventors, as disclosed in Patent Document 4, after coating the aqueous polyurethane resin on the surface of the release paper, in a method of forming a polyurethane resin layer by drying, polyurethane resin layer having a sufficient thickness with a smooth property to the surface to be repeated many times coating and drying steps were not be obtained. Moreover, such a polyurethane resin layer is laminated through an adhesive layer using a water-based urethane adhesive composite fiber sheet surface. Therefore, the sense of unity with the polyurethane resin layer and the composite fiber sheet was not obtained.

Further, according to the study by the present inventors, as disclosed in Patent Document 5, on the surface of the composite fiber sheet, after applying the hot-melt type urethane resin was melted, the polyurethane resin layer by crosslinking According to the method of forming, just to the polyurethane resin layer by applying a hot-melt type urethane resin was melted on the surface of the composite fiber sheet only are stacked, and the composite fiber sheet and the polyurethane resin layer in the interface, a problem that the shift or peeling occurs has not been resolved.

The present invention has been made in view of the above problems, similar to leather, and the crease feeling when bending a texture with a dense feel good, after the bending, hardly remains crease polyurethane laminate an object of the present invention is to provide a body.

Method for producing a polyurethane laminate which is another aspect of the present invention, release paper by applying a crosslinkable hot-melt type urethane resin in a molten state to the release paper surface - coating film forming step of forming a coating film laminate When a heat treatment step of partial crosslinking the crosslinkable hot-melt type urethane resin, a fiber sheet and the elastic polymer is impregnated integrated, the voids of the composite fiber sheet having numerous voids in the surface layer, release paper - pressure, such as a portion of the coating film of the coating film stack entering, comprise a laminating step of laminating the coating on the surface of the composite fiber sheet, a cooling step of cooling and solidifying the cross-linkable hot-melt type urethane resin, a It is preferred.

Further, the coating film forming step, feeling indicating the predetermined exothermic peak temperature by differential scanning calorimetry melting viscosity of 10000 mPa · sec or less for hot melt urethane prepolymer (A) and chain extender (B) and at 100 ° C. a melt mixing step of forming a crosslinkable hot-melt type urethane resin by heating melted and mixed at 10 ~ 30 ° C. lower range of temperatures for the temperature urethane catalyst (C) exothermic peak temperature, the release paper surface release paper by applying a crosslinkable hot-melt type urethane resin in a molten state - and a coating film forming step of forming a coating film laminate, the heat treatment step, release paper - a film laminate wherein the exothermic peak temperature or higher it is preferred by a heat treatment at a temperature which is a step of partially crosslinking the coating film.

Furthermore polyurethane laminate which is another aspect of the present invention, the fiber sheet and the elastic polymer is impregnated integrated composite fiber sheet having numerous voids in the surface layer, laminated on the composite fiber sheet a laminate of the polyurethane resin layer, wherein by a portion of the polyurethane resin layer from entering, a portion of the polyurethane resin layer and the surface layer of the composite fiber sheet are mixed in a non-compatible state in the gap, 10 [mu] m above, preferably have a mixed layer having a thickness of at least 30 [mu] m.

An object of the present invention, features, aspects, and advantages, the following detailed description and the accompanying drawings, become more apparent.

Figure 1 is a schematic process diagram illustrating a method of manufacturing a polyurethane laminate according to the first embodiment of the present invention. Figure 2 is a schematic cross-sectional view of the resulting polyurethane laminate by the production method of Embodiment 1 of the present invention. Figure 3 is a schematic cross-sectional view of the resulting polyurethane laminate by the method for producing a polyurethane laminate according to the second embodiment of the present invention. Figure 4 is an explanatory view illustrating an example of a manufacturing process of a polyurethane laminate according to the second embodiment of the present invention. Figure 5 is a SEM photograph of a cross section of the obtained leather-like sheet in Examples 2-1. Figure 6 is a SEM photograph of a cross section of the obtained leather-like sheet in Comparative Example 2-1. Figure 7 is a schematic diagram for explaining how the grain break occurs when the folded leather. Figure 8 is a schematic diagram for explaining how the grain break occurs when bending the conventional leather-like sheet.

[Embodiment 1]
Method for producing a polyurethane laminate of the first embodiment, temperature sensitive urethane indicating a predetermined exothermic peak temperature room temperature a semi-solid or solid at which the urethane prepolymer (A) and the chain extender (B) and by differential scanning calorimetry a melt mixing step of forming a urethane resin composition by heating melted and mixed at catalyst (C) and the temperature of the lower 10 ~ 30 ° C. range for the exothermic peak temperature, away with the urethane resin composition comprising a resin layer forming step of forming a urethane resin layer on the sheet surface such as paper or fibrous substrate, and a heat treatment step of heat-treating the urethane resin layer by the exothermic peak temperature or higher.

First, the urethane prepolymer at room temperature is used in this embodiment is a semi-solid or solid (A), a chain extender (B), the temperature-sensitive urethane catalyst (C) will be described.

Urethane prepolymer used in the present embodiment (A) is a urethane prepolymer having an isocyanate group obtained by reacting a polyol with a polyisocyanate, substantially solvent-free semi-solid or solid at room temperature which is a polyurethane-forming component. Such urethane prepolymer is in the normal temperature is a property of the semi-solid with a solid or difficult degree of viscous coating is low viscosity enough to allow the coating by heating.

Specific examples of the polyols include polyester polyols, polyether polyols, high molecular weight polyol such as polycarbonate polyol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,4 - bis (hydroxyethoxy) benzene, 1,3-bis (hydroxymethyl) benzene, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol Nord, glycerol, trimethylol propane, trimethylol ethane, hexane triol, pentaerythritol, sorbitol, low-molecular-weight polyol such as methyl glycoside. These may be used in combination of two or more kinds thereof may be used alone.

Specific examples of the polyisocyanate, for example, phenylene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, aromatic diisocyanates such as xylylene diisocyanate; hexamethylene diisocyanate , lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, aliphatic diisocyanate or alicyclic diisocyanates such as tetramethylxylylene diisocyanate; dimer and trimer, etc. of polymeric diphenylmethane diisocyanate 4,4'-diphenylmethane diisocyanate etc. the. These may be used in combination of two or more kinds thereof may be used alone.

Preparation of the urethane prepolymer can be usually carried out in the absence of a solvent, it may be prepared in an organic solvent. When producing an organic solvent is ethyl acetate as it does not inhibit the reaction between the chain extender and a polyisocyanate, acetate n- butyl, methyl ethyl ketone, can be used an organic solvent such as toluene, the course of the reaction or by a method such as heating under reduced pressure after the completion of the reaction it is necessary to remove the organic solvent.

The reaction ratio of the polyol and the polyisocyanate, and an isocyanate group in the polyisocyanate, is equivalent ratio [NCO / OH] of the hydroxyl groups in the polyol is preferably in the range 1.1 to 5.0 1 and more preferably in the range of .2 to 3.0.

The number average molecular weight of the urethane prepolymer, 500 to 30,000, more easily adjust the melt viscosity in the range of 1000 to 10,000, also, excellent flexibility, mechanical strength, wear sex, from the viewpoint of capable of forming a polyurethane layer having a hydrolysis resistance.

Urethane The melt viscosity of the prepolymer, the melt viscosity at 120 ° C. as measured by cone-plate viscometer, 500 ~ 100,000 mPa · s, more 1000 - it is the adjustment of the film thickness in the range of 10,000 mPa · s from the viewpoint it is easy.

Examples of commercially available products of such a urethane prepolymer, DIC (trade name) manufactured by the Task Force KMM-100, Thailand Force NH-122A, NH-200, NH-300, H-1041 and Takeda Chemical Industries, Ltd. of Takedameruto SC-13, SL-01, SL-02, SL-03, SL-04, and the like.

The urethane prepolymer (A) is an isocyanate group in the urethane prepolymer (A) and the like hydroxyl group or an amino group in the later-described chain extender (B) is a high molecular weight is promoted reaction by urethanization catalyst. Also, high molecular weight polymer is carried out crosslinking reaction by reacting with the isocyanate groups still present in the system.

Chain extender used in the present embodiment (B) is a compound having two or more functional groups having active hydrogen such as a hydroxyl group or an amino group reactable to the isocyanate group of the urethane prepolymer (A).

Specific examples of the chain extenders, various other polyols mentioned above, ethylenediamine, 1,3-propylenediamine, 1,2-propylenediamine, hexamethylenediamine, Roh Rubo nen diamine, hydrazine, piperazine, N, N' diamino piperazine, 2-methylpiperazine, 4,4'-diaminodicyclohexylmethane, isophoronediamine, diaminobenzene, diphenylmethane diamine, methylene bis-dichloroaniline, triethylenediamine, tetramethyl hexamethylene diamine, triethylamine, tripropylamine, trimethyl aminoethylpiperazine , N- methylmorpholine, N- ethylmorpholine, polyamine such as di (2,6-dimethyl morpholinoethyl) ether. These may be used in combination of two or more kinds thereof may be used alone.

Differential scanning calorimetry temperature-sensitive urethane catalysts showing a predetermined exothermic peak temperature by measurement used in this embodiment (C) is under a blanket of nitrogen, at a heating rate 10 ° C. / 1 ​​min, 200 ° C. from 0 ℃ when differential scanning calorimetry in the range up to a urethanization catalysts having predetermined exothermic peak temperature. The exothermic peak temperature, from the viewpoint of 50 ~ 160 ° C., it still is in the range of 80 ~ 140 ° C. excellent performance and stabilization of urethanization.

Specific examples of the urethanization catalyst, 1,8-diazabicyclo (5,4,0) - undecene-7 salts of organic acids (DBU), specifically phenol salt (exothermic peak temperature 88 ° C. of DBU ), octyl salt of DBU (same 99 ° C.), phthalate of DBU (same 138 ° C.), and oleic acid salts of DBU (same 110 ° C.) and the like. Such urethane catalysts, in consideration of the softening temperature of the urethane prepolymer used (A), are appropriately selected.

In this embodiment, the polyurethane layer obtained in order to porous, the urethane resin composition applied, if necessary, it is preferable to blend a foaming agent. The type of blowing agent is not particularly limited, from the viewpoint uniformity of control of pores is easy, it is preferable to use a thermally expandable microcapsule. Such thermally expandable microcapsules, for example, at the same time enclosed hydrocarbons is expanded by heating, to start the expansion by the thermoplastic resin forming the outer shell is softened, microcapsules pressure and external pressure predetermined expansion ratio commensurate, preferably by expansion more than doubled, temperature sensitive foaming agent for forming a uniform closed cells and the like. Specific examples of such heat-expandable microcapsules, for example, Matsumoto Microsphere F-series, such as manufactured by Matsumoto Yushi-Seiyaku Co., Ltd. can be mentioned.

In the present embodiment, in addition to the above-described various components, as necessary, a coloring agent such as a pigment, a thickener may be blended with additives such as antioxidants.

An example of a method of manufacturing the polyurethane laminate of the present embodiment implemented using the above-described various components will be described with reference to FIG.

Figure 1 is a schematic process diagram for explaining a manufacturing method of a polyurethane laminate of the present embodiment. In Figure 1, 1 is release paper, 2 is the urethane prepolymer is a semi-solid or solid at room temperature, 3 chain extender, the temperature-sensitive urethane catalysts having a predetermined exothermic peak temperature 4, 5 heat-expandable it is a micro capsule. Further, a first nozzle 6a for supplying a urethane prepolymer, and the second nozzle 6b for supplying a chain extender, the mixing head 6 and a mixing chamber 6c is constructed. Incidentally, 6a, 6b, 6c is provided with a respective view unillustrated heater. Further, 7 is a substrate sheet, reel 8 sends out the base sheet 7, 9a is touch roll, 9b are reverse roll, 10 urethane resin composition (urethane resin layer), the feed rolls 11, 12 of the heating means, 13 polyurethane laminate 14 is a take-up reel of the polyurethane laminate 13, 16 is a cooling roll, PR is a press roll. In FIG. 1, a reverse roll coater is constituted by a combination of a touch roll 9a and reverse roll 9b.

In the production method of the polyurethane laminate of the present embodiment, initially, 10 to a urethane prepolymer 2 and chain extender 3 and the temperature-sensitive urethane catalyst 4 and the thermal expandable microcapsules 5 to the exothermic peak temperature 30 ° C. heated melt mixed in a low range of temperatures (melt mixing step).

Specific examples of the method of heating melt mixing, for example, include the following methods.

The mixing method is warmed at a temperature such that the urethane prepolymer 2 at a predetermined viscosity, whereas, chain extenders 3, after the temperature-sensitive urethane catalyst 4, and the thermally expandable microcapsule 5 kept, they the method is employed as stirring and mixing mixing or mixing or a method of stirring after, simply melted state using known mixing head as shown in FIG. 1 for mixing by impinging by high-pressure injection of .

A method of mixing using a mixing head, as shown in FIG. 1, a urethane prepolymer 2 in a heated molten state is atomized by pressurized injection from the first nozzle 6a is supplied to the mixing chamber 6c, whereas, the temperature sensitive and sex urethanization catalyst 4 and thermally expandable microcapsule 5 from the second nozzle 6b is mixed with chain extender 3 pressurized including fluid shines supplied to the mixing chamber 6c by atomization. Then, to collide with each component that is atomized in the mixing chamber 6c and mixed. The thermal expandable microcapsule 5 is formulated as needed when intended to form the porous urethane layer. In this case, as the temperature of the urethane resin composition formed by mixing is heated melt mixed at a temperature lower 10 ~ 30 ° C. range for the exothermic peak temperature, the first nozzle 6a of the mixing head, the second nozzle 6b, and it controls the temperature of the mixing chamber 6c. According to the mixing method using the mixing head allows more uniform mixing.

Further, as a method of stirring at simply molten state include the following methods.

First, a urethane prepolymer 2 warmed at a temperature such that the predetermined viscosity to a predetermined vessel, and stored. On the other hand, the other in the container, the chain extender 3, temperature-sensitive urethane catalyst 4, and thermally expandable microcapsule 5 temperature sensitive urethane catalyst 4 does not activate, and thermally expandable microcapsule 5 There should be kept at a temperature that does not expand. Then, the urethane prepolymer 2 and the temperature-sensitive urethane catalyst 4, a mixture containing heat-expandable microcapsule 5 and chain extender 3 is fed into a vessel equipped with a heater and a stirrer. Then, in the container, the urethane prepolymer 2 and chain extender 3 and the temperature-sensitive urethane catalyst 4 and the thermally expandable microcapsule 5, 10 relative to the exothermic peak temperature of the temperature-sensitive urethane catalyst 4 - It is heated and melted mixture at 30 ° C. lower range of temperatures.

In the melt mixing step, the temperature of the lower 10 ~ 30 ° C. than the exothermic peak temperature of the temperature-sensitive urethane catalyst 4 is activated, preferably in the range of 10 ~ 25 ° C. lower range urethane prepolymer 2 at a temperature of the chain extender 3 and a temperature-sensitive urethane catalyst 4 and the thermal expandable microcapsule 5 is heated melt mixing. Progress of the crosslinking reaction is inhibited by heating melted mixture at such temperatures. Therefore, it is possible to increase the pot life of the urethane resin composition prepared in the mixing chamber 6c. Note that in the case of blending thermally expandable microcapsule 5, it is preferable to select a substantially thermally expandable microcapsules that does not expand to a expansion ratio of the target in the melt-mixing step.

Further, on the other hand, as shown in FIG. 1, feeding from an unillustrated sheet feed reel release paper 1 continuously, the release paper 1 to be continuously fed, sent by feed roll 11 rotates in the direction indicated by the arrow after, is taken up by the take-up reel 14, advance a continuous line of release paper 1, previously formed.

Then, as shown in FIG. 1, toward the release paper 1 is conveyed continuously, urethane resin composition 10 prepared in the mixing chamber 6c in is formed between the touch roll 9a and reverse roll 9b are flow down towards the clearance, is applied in a uniform thickness in the release paper first surface reverse roll 9b, urethane resin layer 10 is formed (resin layer forming step). The coating thickness is controlled by the spacing of the clearance formed between the reverse roll 9b and the touch roll 9a.

The release paper 1, other surface smooth release paper, for the purpose of imparting surface design properties, may be used release paper so as to have an embossed pattern. Further, it may be formed a layer of a known elastic polymer typified in advance release paper surface with polyurethane resin or an acrylic resin. Advance, when forming a layer of the elastic polymer to release paper surface, obtained by heating and melting mixing the urethane prepolymer (A) and the chain extender (B) and temperature-sensitive urethane catalyst (C) since the surface layer of the urethane resin composition is coated with polymer elastic layer is preferable in that the modification of surface properties is made possible. Especially when it is coated with the polymer elastic layer, it is possible to prevent a decrease in adhesion to the other resin layer surface made of the urethane resin composition due to having a crosslinked structure.

If the surface layer of the urethane resin composition is coated with an elastic polymer layer, with the layer made from the urethane resin composition is not sufficiently crosslinked, to be coated with the polymer elastic layer, said improved adhesion made of urethane resin composition layer and the polymer elastic layer, further embossing surface (uneven pattern transfer) is improved.

Further, by being coated with the polymer elastic layer it is preferable in that it is possible to suppress the tack of the surface.

By further previously formed a layer made of a known water-dispersible polymer elastic body and solventless cured elastic polymer as a surface layer, that it is possible to produce a polyurethane laminate comprising all the solventless process in a more preferred.

As specific examples of the coating mechanism for applying the urethane resin composition 10 of the heated molten state to the release paper first surface, instead of the reverse roll coater as shown in FIG. 1, for example, a knife coater, roll coater, reverse coater, a kiss roll coater, a spray coater, T-die coater, or a comma coater or the like can be used. Incidentally, in these coating mechanism, from the viewpoint of capable of controlling the melt viscosity of the urethane resin composition, the coating mechanism having heating means are preferred.

The thickness of the urethane resin layer 10 formed, 5 ~ 800 [mu] m, more preferable from the viewpoint of excellent polyurethane laminate flexibility and mechanical strength in the range of 10 ~ 500 [mu] m is obtained.

By bonding the substrate sheet 7 on the surface of the urethane resin layer 10 formed on the surface of the release paper 1, a polyurethane laminate 13 urethane resin layer 10 is formed on the substrate sheet 7 is formed on the surface .

Bonding of the urethane resin layer 10 and the base sheet 7, specifically, for example, as shown in FIG. 1, the base sheet 7 from the delivery reel 8 is fed out, the urethane resin layer 10 is melted or softened They are bonded to each other by a press roll PR in with that state.

Specific examples of the base sheet 7 used in this embodiment, for example, nonwoven fabric or woven fabric, typically fibrous base material used in the leather-like sheet such as knitted fabrics; solvent system to the fiber substrate , aqueous, emulsion-based or solventless polyurethane resins, acrylic resins, and butadiene resins (SBR, NBR, MBR) composite fiber substrate like impregnated with, and the like. Among these, from the viewpoint of polyurethane laminate having better mechanical strength and soft hand is obtained, the composite fiber base material impregnated with a polyurethane nonwoven fabric formed from microfine fibers are particularly preferably used. The nonwoven fabric may short fiber webs conventionally known, a web obtained by a known method such as spun bond method and melt blow method are used without any particular limitation. If necessary, after forming the web, or may be obtained by entangling by needle punching or the like stacked a plurality of webs. Specific examples of the fibers forming the nonwoven fabric, for example, polyurethane fibers, polyethylene terephthalate (PET) fibers, various polyamide fibers, polyacrylic fibers, various polyolefin fibers, polyvinyl alcohol fibers, and the like. The fibers forming the nonwoven fabric, the fiber diameter of 0.1 ~ 50 [mu] m, further is preferably ultrafine fiber such that 1 ~ 15 [mu] m. Such microfibers low rigidity, the softer, from the viewpoint of polyurethane laminate having a soft texture is obtained. Range of 50 ~ 2000g / m 2 as a weight per unit area of the nonwoven fabric, more in the range of 100 ~ 1000g / m 2, from the viewpoint of polyurethane laminate soft hand can be obtained.

Next, heat treatment of the polyurethane laminate 13 urethane resin layer 10 is formed on the substrate sheet 7 surface exothermic peak temperature above the temperature of the temperature-sensitive urethane catalyst (C) (heat treatment step). By thus releasing the urethane resin layer 10 formed on the surface of the paper 1 is heat treated at a temperature higher than the exothermic peak temperature of the temperature-sensitive urethane catalyst (C), the urethane resin layer 10 formed by coating cross-linking is promoted.

The heat treatment temperature, the temperature of the urethane resin layer 10 is at a temperature higher than the exothermic peak temperature of the temperature-sensitive urethane catalyst (C), and is not particularly limited as long as the temperature does not degrade the polyurethane layer to be cured formed heat treatment but, specifically, 0 ~ 30 ° C. higher temperature ranges for the exothermic peak temperature of the temperature-sensitive urethane catalyst (C), further in the range of high 0 ~ 15 ° C. relative to the exothermic peak temperature temperature it is preferable to.

Specific examples of the heat treatment time, e.g., about 15 seconds to 10 minutes, more to be about 30 seconds to 5 minutes, that can promote sufficient crosslinking reaction without lowering productivity preferable from.

Heat treatment is performed, for example, by the heating device 12, such as a hot air heating drier.

After the forced cooling in this way was bonded body of the urethane resin layer 10 in a state of being coated with the resulting release paper 1 substrate sheet 7 by using a cooling roll 16, up by a take-up reel 14 take. By aging a polyurethane laminate 13 is wound a predetermined time, the crosslinking reaction of the urethane resin layer 10 is a high molecular weight in progress.

The ripening conditions of the polyurethane laminate 13, temperature 20 ~ 40 ° C., under the conditions of a relative humidity of 50-80%, preferably aged about 20 to 50 hours. Thus, a polyurethane laminate having excellent mechanical strength and water resistance can be obtained.

It shows a cross-sectional schematic view of a polyurethane laminate 13 obtained by such process in FIG.

Polyurethane laminate as shown in FIG. 2 13 is completed by peeling the release paper 1 coated on the surface. Such in polyurethane laminate 13, a uniform closed cell 21 is formed in the cross-linked polyurethane layer 20.

In the present embodiment, in advance a continuous line of release paper 1 to form a urethane resin layer 10 is formed on the continuous release paper 1 of a surface delivered, the surface of the formed urethane resin layer 10 It has been representatively described the steps as bonding the base sheet 7, by replacing the order of bonding the release paper 1 and the base sheet 7, previously formed a continuous line of the base sheet 7, the continuous manner delivered by forming a urethane resin layer 10 on the surface of the base sheet 7, the surface of the formed urethane resin layer 10 may be a process such as bonding a release paper 1. In the present embodiment, representative steps such as heat treatment after bonding the base sheet 7 to form an urethane resin layer 10 on the surface of the release paper 1, the surface of the formed urethane resin layer 10 has been described, it may be subjected to a heat treatment before bonding the base sheet 7 to the urethane resin layer 10.

Incidentally, with respect to the resulting polyurethane laminate, the more conventionally known methods, or impart surface design property, or to adjust the tactile, to add color correction, solvent-based surface layer portion, an aqueous emulsion or by coating a polyurethane resin or an acrylic resin systems or solvent-free, or buffing processing after processing or embossing may be carried out appropriately.

The thus obtained polyurethane laminate, footwear, clothing, bags, can be used preferably as a leather-like sheet comprising the surface material of the furniture.

[Embodiment 2]
Method for producing a polyurethane laminate of the present embodiment 2 is preferably a release paper by applying a crosslinkable hot-melt type urethane resin in a molten state to the release paper surface - and a coating film forming step of forming a coating film laminate , a heat treatment step of partial crosslinking the crosslinkable hot-melt type urethane resin, a fiber sheet and the elastic polymer is impregnated integrated into the voids of the composite fiber sheet having numerous voids in the surface layer, release paper - coating pressure, such as a portion of the coating film stack enters comprises a lamination step of laminating a coating film on the surface of the composite fiber sheet, a cooling step of cooling and solidifying the cross-linkable hot-melt type urethane resin.

That is, in the method for producing a polyurethane laminate embodiment 2, the coating film forming step, and corresponds to a resin layer forming step in the manufacturing method of Embodiment 1 described above, a heat treatment step in the second embodiment of the first embodiment preferably it corresponds to the heat treatment step. At the same time, the production method of Embodiment 2, it is preferable to newly provided with the specific lamination step and a cooling step.

Further, the melt mixing process in the first embodiment described above, in the second embodiment, preferably, melt viscosity at 100 ° C. The following 10000 mPa · sec hot-melt urethane prepolymer (A) and chain extender (B) and the crosslinkable hot-melt by heating melted and mixed at a temperature lower 10 ~ 30 ° C. range and temperature-sensitive urethane catalyst (C) relative to the exothermic peak temperature indicative of a predetermined exothermic peak temperature by differential scanning calorimetry a melt mixing step of forming a mold urethane resin. Further, the resin layer forming step of Embodiment 1, in Embodiment 2, preferably, the release paper by applying the crosslinkable hot-melt type urethane resin in a molten state to the release paper surface - a film laminate formed a film forming step for. The heat treatment step in the first embodiment, in the second embodiment, preferably, the release paper - in the heat treatment step of partial crosslinking of the coating film by heat-treating the coating stack by the exothermic peak temperature or higher is there.

With reference to the accompanying drawings, it will be described in detail an example of a preferred method for producing a polyurethane laminate embodiment 2.

First, a description will be given crosslinkable hot-melt type urethane resin used in the present embodiment.

Crosslinkable hot-melt type urethane resin used in the present embodiment, a polyol and a polyisocyanate are reacted optionally and urethane prepolymer having an isocyanate group obtained by, for curing and crosslinking the urethane prepolymer a composition containing a chain extender and a catalyst, a polyurethane-forming component of the semi-solid or solid solventless at room temperature. Such crosslinkable hot-melt type urethane resin is at room temperature a semi-solid nature having a solid or viscous degree is difficult coating results in a viscosity which can be applied by heating, the coating after Engineering is viscous resolidify or increased by being cooled.

Specific examples of the polyol, for example, a polyol described in the first embodiment. These may be used in combination of two or more kinds thereof may be used alone.

Specific examples of the polyisocyanate, for example, polyisocyanates described in the first embodiment. These may be used in combination of two or more kinds thereof may be used alone.

Production of the urethane prepolymer can be usually carried out in the absence of a solvent, it may be prepared in an organic solvent. When producing an organic solvent is ethyl acetate, n- butyl, methyl ethyl ketone, can be used an organic solvent such as toluene, removing the organic solvent by a method such as heating under reduced pressure during or after the reaction of the reaction it is necessary to.

The reaction ratio of the polyol and the polyisocyanate, and an isocyanate group in the polyisocyanate, is equivalent ratio [NCO / OH] of the hydroxyl groups in the polyol is preferably in the range of 1.1-5, 1.2 more preferably in the range of 1-3.

The number average molecular weight of the urethane prepolymer, 500 to 30,000, more easily adjust the melt viscosity in the range of 1000 to 10,000, also, excellent flexibility, mechanical strength, wear sex, from the viewpoint of capable of forming a polyurethane resin layer having a hydrolysis resistance.

Examples of commercially available products of such a urethane prepolymer, DIC manufactured by (Corporation) trade name Task Force KMM-100, KMM-100LV, Thailand force NH-122A, NH-200, NH-300, H-1041 and Takeda Takedameruto SC-13 of industry Co., Ltd., SL-01, SL-02, SL-03, SL-04, and the like.

Chain extenders are compounds having two or more functional groups having active hydrogen such as a hydroxyl group or an amino group reactable to the isocyanate group of the urethane prepolymer. The urethane prepolymer is a hydroxyl group or an amino group or the like is promoted reaction by urethanization catalyst molecular weight of the chain in the extender which will be described later with the isocyanate groups in the urethane prepolymer. Also, high molecular weight polymer is carried out crosslinking reaction by reacting with the isocyanate groups still present in the system.

Specific examples of the chain extenders, various other polyols described above, polyamines such as described in Embodiment 1 can be cited. These may be used in combination of two or more kinds thereof may be used alone.

Among the crosslinkable hot-melt type urethane resin, especially, moisture-curing hot-melt type urethane resin having a moisture curable and heat-fusible is preferred.

Incidentally, the moisture (humidity) curing with the moisture-curing hot-melt type urethane resin, an isocyanate group-terminated and moisture in the urethane prepolymer (water) is cured by reaction to form a urethane bond or a urea bond . Also, a urethane bond or a urea bond is formed, a crosslinking reaction by reacting with the isocyanate groups still present in the system. Through such a curing reaction and the crosslinking reaction, the urethane prepolymer excellent polyurethane resin mechanical properties and water resistance, etc. is formed by high molecular weight.

Crosslinkable hot-melt type urethane resin of the present embodiment, a urethane catalyst, especially preferably contains a temperature-sensitive urethane catalysts. Temperature-sensitive urethane catalysts, under a blanket of nitrogen, at a heating rate 10 ° C. / 1 ​​minute, when the differential scanning calorimetry in the range from 0 ℃ to 200 ° C., urethanization catalysts having predetermined exothermic peak temperature it is. The exothermic peak temperature, from the viewpoint of 50 ~ 160 ° C., it still is in the range of 80 ~ 140 ° C. excellent performance and stabilization of urethanization.

Specific examples of such temperature-sensitive urethane catalyst, 1,8-diazabicyclo (5,4,0) - organic acid salts, in particular DBU phenol salt (exothermic peak undecene -7 (DBU) temperature 88 ° C.), octyl salt of DBU (same 99 ° C.), phthalate of DBU (same 138 ° C.), and oleic acid salts of DBU (same 110 ° C.) and the like. Such temperature-sensitive urethane catalysts, in consideration of the softening temperature of the urethane prepolymer used is appropriately selected.

Crosslinkable hot-melt type urethane resin, a polyurethane resin layer obtained to a porous, if necessary, it preferably contains a foaming agent. The type of blowing agent is not particularly limited, from the viewpoint uniformity of control of pores is easy, it is preferable to use a thermally expandable microcapsule. Such thermally expandable microcapsules, for example, at the same time enclosed hydrocarbons is expanded by heating, to start the expansion by the thermoplastic resin forming the outer shell is softened, microcapsules pressure and external pressure predetermined expansion ratio commensurate, preferably by expansion more than doubled, temperature sensitive foaming agent for forming a uniform closed cells and the like. Specific examples of such heat-expandable microcapsules, for example, Matsumoto Microsphere F-series, such as manufactured by Matsumoto Yushi-Seiyaku Co., Ltd. can be mentioned.

Crosslinkable hot-melt type urethane resin of the present embodiment, in addition to the above-described various components, as necessary, a coloring agent such as a pigment, a thickener may be blended with additives such as antioxidants.

The melt viscosity of such crosslinkable hot-melt type urethane resin, melt viscosity at 100 ° C. as measured by cone-plate viscometer, 500 ~ 12,000 mPa · s, it still is in the range of 1000 ~ 10000 mPa · s, from the viewpoint adjustment point and thickness and excellent coating properties it is easy.

The method for producing a polyurethane laminate of the present embodiment implemented using the above-described crosslinkable hot-melt type urethane resin, it will be described with reference to FIG.

Figure 4 is a schematic explanatory view for explaining a manufacturing method of a polyurethane laminate of the present embodiment. In Figure 4, 120 is crosslinkable hot-melt type urethane resin, the release paper 121, 122 is a urethane prepolymer, 123 chain extender, 124 temperature-sensitive urethane catalysts having a predetermined exothermic peak temperature, 125 heat expandable microcapsule is. Note that the 123 chain extenders, if necessary, and a pigment for imparting a desired color tone, to the desired physical properties, may be contained in limits that do not impair the effect of the present invention the polyol . Further, the first nozzle 136a for supplying a urethane prepolymer 122, a second nozzle 136b for supplying a chain extender 123 or the like, is the mixing head 136 and a mixing chamber 136c is configured. Incidentally, 136a, 136b, 136c has a respective view unillustrated heater. Further, the composite fiber sheet 103, the delivery reel of the composite fiber sheet 103 138, 139a is touch roll, 139b are reverse roll, 140 release paper - coating stack, the feed roll 141, 142 heater, 143 polyurethane laminate precursor, 144 take-up reel of the polyurethane laminate precursor 143, 146 cooling roll, PR is a press roll. In FIG. 4, a reverse roll coater is constituted by a combination of a touch roll 139a and reverse roll 139b.

In the production method of the polyurethane laminate of the present embodiment, initially, the release paper by applying a crosslinkable hot-melt type urethane resin 120 in a molten state on the surface of the release paper 121 - to form a coating film stack 140 (the coating film forming step).

As a method for preparing the crosslinkable hot-melt type urethane resin 120 (melt mixing step), for example, urethane prepolymer 122 and chain extender 123 and the temperature-sensitive urethane catalyst 124 and the thermal expandable microcapsules 125 and the temperature sensitive sex urethanization catalyst 124 include a method of heating molten mixture at a temperature that does not activate.

The heating melt mixing method, for example, heated at a temperature such that the urethane prepolymer 122 to a predetermined viscosity, whereas, chain extenders 123, temperature-sensitive urethane catalyst 124, and the thermally expandable microcapsule 125 after incubation, they and a method of stirring after mixing or mixed with a mixing head such as shown in FIG. 4 for mixing by impinging by high-pressure injection of the molten state simply vessel equipped with a heating device in such a way that stirring and mixing are employed.

A method of mixing using a mixing head, as shown in FIG. 4, the urethane prepolymer 122 in a heated molten state is atomized by pressurized injection from the first nozzle 136a is supplied to the mixing chamber 136c, whereas, the temperature sensitive supplied to the mixing chamber 136c by sex urethanization catalyst 124 and heat-expandable microcapsules 125 is atomized from a second nozzle 136b is mixed with the chain extender 123 pressurized including fluid shines. Then, to collide with each component that is atomized in the mixing chamber 136c to mix. The thermal expandable microcapsules 125 are components that are blended as required in the case of forming the porous polyurethane resin layer. In this case, as the temperature of the crosslinkable hot-melt type urethane resin 120 that is prepared by mixing to a temperature lower than the temperature that activates the thermosensitive urethane catalyst 124, the first nozzle 136a of the mixing head, the second nozzle 136 b, and to control the temperature of the mixing chamber 136c. According to the mixing method using the mixing head allows more uniform mixing.

Further, as a method of stirring at simply molten state include the following methods.

First, heating at a temperature to melt the urethane prepolymer 122 to a predetermined vessel, and stored. On the other hand, in another vessel, chain extenders 123, temperature-sensitive urethane catalyst 124, and thermally expandable microcapsule 125 temperature-sensitive urethane catalyst 124 is not activated, and thermally expandable microcapsule 125 There should be kept at a temperature that does not expand. Then, the urethane prepolymer 122 and the temperature-sensitive urethane catalyst 124, a mixture containing heat-expandable microcapsules 125 and a chain extender 123 is supplied to a vessel equipped with a heater and a stirrer. Then, in the vessel, and a urethane prepolymer 122 and chain extender 123 and the temperature-sensitive urethane catalyst 124 and the thermal expandable microcapsules 125, the heating at a temperature that does not activate the thermosensitive urethane catalyst 124 It is melt mixed.

In the melt mixing step, the temperature at which the temperature sensitive urethane catalyst 124 is activated, the temperature of the lower 10 ~ 30 ° C. range than the exothermic peak temperature, preferably urethane prepolymer at a temperature in the lower range 10 ~ 25 ° C. 122 it is preferable to heat and melt mixed with a chain extender 123 and the temperature-sensitive urethane catalyst 124 and the thermal expandable microcapsules 125 and. Progress of the crosslinking reaction is inhibited by heating melted mixture at such temperatures. Thus, it is possible to improve the coating stability of the mixing chamber 136c crosslinking were prepared in the hot-melt type urethane resin 120. Note that in the case of blending thermally expandable microcapsule 125, in the melt-mixing step, it is preferable to select a thermally expandable microcapsule that initiates inflation.

Further, on the other hand, as shown in FIG. 4, feeding from an unillustrated sheet feed reel release paper 121 continuously, release paper 121 is continuously sent out, sent by rolls 141 feed rotates in the direction of the arrow after, it is wound by the winding reel 144, advance successive line of the release paper 121, previously formed.

Then, as shown in FIG. 4, towards the release paper 121 to be conveyed continuously, the mixing chamber crosslinkable hot-melt type urethane resin 120 that is prepared during 136c is between the touch roll 139a and the reverse roll 139b are flow down toward the clearance being formed, is coated with a uniform thickness in the release paper 121 surface by a reverse roll 139b, the release paper - coating stack 140 is formed. Coating thickness is controlled by the spacing of the clearance formed between the reverse roll 139b and the touch roll 139a.

The release paper 121, other surface smooth release paper, for the purpose of imparting surface design properties, may be used release paper so as to have an embossed pattern.

As specific examples of the coating mechanism for applying a crosslinkable hot-melt type urethane resin 120 of heated molten state release paper 121 surface, instead of the reverse roll coater as shown in FIG. 4, for example, a knife coater, a roll coater, reverse coater, kiss roll coater, a spray coater, may be used T- die coater, or a comma coater or the like. Incidentally, in these coating mechanism, from a viewpoint of controlling the molten state of crosslinkable hot-melt type urethane resin 120, coating mechanism having heating means are preferred.

Release paper - The thickness of the coating film 132 of the coating film stack 140, from the viewpoint of 10 ~ 1000 .mu.m, more excellent polyurethane laminate flexibility and mechanical strength in the range of 50 ~ 500 [mu] m is obtained .

Next, the partially crosslinking the crosslinkable hot-melt type urethane resin 120 (heat treatment step). Specifically, release paper - the coating stack 140, by the heat treatment at a temperature that activates the thermosensitive urethanization catalyst 124 contained in the crosslinkable hot-melt type urethane resin 120, to form a coating film 132 crosslinking of the crosslinkable hot-melt type urethane resin 120 is promoted that. Accordingly, the viscosity of the coating 132 is increased to some extent. When the foaming agent such as heat-expandable microcapsules 125 are contained during the crosslinkable hot-melt type urethane resin 120, it is preferred to foam in the heat treatment step.

The heat treatment temperature, the temperature of the coating film 132 becomes a temperature higher than the exothermic peak temperature of the temperature-sensitive urethane catalyst 124, and is not particularly limited as long as the temperature does not degrade the polyurethane resin layer to be cured formed, Specifically, 0 ~ 30 ° C. higher temperature ranges for the exothermic peak temperature of the temperature-sensitive urethane catalyst 124, it further to heat treatment in the range of 0 ~ 15 ° C. higher temperatures for the exothermic peak temperature preferably .

Specific examples of the heat treatment time, e.g., about 15 seconds to 10 minutes, more to be about 30 seconds to 5 minutes, that can promote sufficient crosslinking reaction without lowering productivity preferable from. In the present embodiment, a heat treatment process release paper - is provided after formation of the coating stack, by providing a heat treatment step immediately before coating the crosslinkable hot-melt type urethane resin, initiate the partial crosslinking before application such as by, it may be provided at any step.

Heat treatment is performed, for example, by the heating device 142 such as a hot air heating drier.

Then, the number of voids in the surface layer of the composite fiber sheet 103 described above, the release paper - a pressure such as a portion of the partially crosslinked coating film 132 of the coating film stack 140 enters the surface of the composite fiber sheet 103 the coating film 132 is laminated (lamination step).

Release paper - bonding of the coating stack 140 and the composite fiber sheet 103, specifically, for example, as shown in FIG. 4, the composite fiber sheet 103 from the reel 138 feed is fed, the release paper - coating Although the coating 132 of the stack 140 surface is the partial crosslinking is bonded by a press roll PR at a state of being softened to a certain extent.

Further, when bonding, release paper - the pressure applied during the bonding of the coating stack 140 and the composite fiber sheet 103 is appropriately set depending on the viscosity of the coating 132 when the press roll or the like. This pressure can be adjusted by adjusting the clearing Alan scan spacing between the press roll roll made of, for example, a combination of two rolls. Clearance gap between the two rolls, the release paper - is adjusted according to the total thickness or the like of the coating film stack 140 and the composite fiber sheet 103, for example, it is preferable to employ a clearance distance as follows. Clearance gap between the two rolls, the release paper before it is press roll - 70-99% of the total thickness of the coating stack 140 and the composite fiber sheet 103, and further, a thickness of about 80 to 97% it is preferable to set in.

In the present embodiment, the crosslinkable hot-melt type urethane resin 120 after the heat treatment step of partially crosslinked, the release paper - manufacturing process of performing coating stack 140 and laminate stroke of attaching the composite fiber sheet 103 It has been representatively described, and the laminate process may be performed before the heat treatment step.

Thus obtained, the release paper - polyurethane laminate precursor 143 is bonded body of the paint film laminate 140 and the composite fiber sheet 103 is forcibly cooled using a cooling roll 146 (cooling step). In the cooling step, the crosslinkable hot-melt type urethane resin 120 is solidified or thickens.

After the cooling step, it is wound by the winding reel 144. The polyurethane laminate precursor 143 wound, by being aged predetermined time as necessary, the crosslinking reaction of the polyurethane resin layer further progresses are high molecular weight, cured. In the case of using the moisture-curing hot-melt type urethane resin as a crosslinking hot-melt urethane resin, moisture curing progresses.

The ripening conditions of the polyurethane laminate precursor 143, temperature 20 ~ 40 ° C., under the conditions of a relative humidity of 50-80%, preferably aged about 20 to 50 hours. Thus, a polyurethane laminate having excellent mechanical strength and water resistance can be obtained.

After aging, by peeling off the release paper 121 from polyurethane laminate precursor 143, a polyurethane laminate is obtained.

Incidentally, with respect to the resulting polyurethane laminate, by further known conventional methods, in order to impart surface design properties, solvent-based surface layer portion, an aqueous, emulsion-based or solventless urethane resin or an acrylic resin or providing a skin layer by coating, or buffing processing after processing or embossing may be carried out appropriately.

The thus obtained polyurethane laminate may be used bag, footwear, clothing, as leather-like sheet for use in furniture or the like.

[Embodiment 3]
In the embodiment 3 will be described polyurethane laminate obtained by the production method of the polyurethane laminate embodiment 2 above. Polyurethane laminate according to the present embodiment 3 preferably has a fiber sheet and the elastic polymer is impregnated integrated composite fiber sheet having numerous voids in the surface layer, a polyurethane resin is laminated on the composite fiber sheet a laminate of a layer having a mixture layer portion of the polyurethane resin layer has a surface layer of 10μm or more thick, which is formed to penetrate the voids of the composite fiber sheet.

With reference to the drawings, it will be described in detail polyurethane laminate according to the present embodiment. Figure 3 is a schematic cross-sectional view of the polyurethane laminate 110, 101 fiber sheet 102 is porous polyurethane (elastic polymer), porous polyurethane 102 is integrated by impregnating the fiber sheet 101 composite fiber sheet 103 is formed by. Also, 104 is a polyurethane resin layer, by the lower layer of the polyurethane resin layer 104 are mixed of entering an upper layer of the void 106 of the composite fiber sheet 103, mixed layer 105 is formed.

Specific examples of the fiber sheet 101, for example, nonwoven fabric or woven fabric, typically fibrous base material used in the leather-like sheet such as knitted fabrics and the like. Among these, from the viewpoint of composite fiber sheets having excellent mechanical strength and soft hand can be obtained, a nonwoven fabric formed from microfine fibers or microfine fiber bundles are preferred. Such nonwoven fabric may short fiber webs conventionally known, a web obtained by a known method such as spun bond method and melt blow method are used without any particular limitation. If necessary, after forming the web, or may be obtained by entangling by needle punching or the like stacked a plurality of webs. Specific examples of the fibers forming the nonwoven fabric, for example, polyurethane fiber, polyester fiber such as PET fibers, polyamide fibers, polyacrylic fibers, polyolefin fibers, polyvinyl alcohol fibers, and the like. The fibers forming the nonwoven fabric, the fiber diameter of 0.1 ~ 50 [mu] m, further is preferably fine fibers or ultrafine fibers such that 1 ~ 15 [mu] m. Such fine fibers or ultrafine fibers are less stiff, the softer, from the viewpoint of composite fiber sheet is obtained which has a soft texture. As the cross-sectional shape of the fibers, other conventional circular or elliptical cross-section, may also be used as star, From the viewpoint that a composite fiber sheet having both lightweight and mechanical strength can be obtained, hollow or it may also be used as lotus root type of multi-air sky shape.

Range of 50 ~ 2000g / m 2 as a weight per unit area of the nonwoven fabric, more in the range of 100 ~ 1000g / m 2, from the viewpoint of composite fiber sheets soft hand can be obtained.

Also, the fiber sheet 101 of the present embodiment is a porous polyurethane 102 is impregnated as the polymeric elastomer. As the elastic polymer, but is not limited to the porous. Instead of polyurethane, acrylonitrile - butadiene copolymer, styrene - butadiene copolymer, copolymers of acrylic acid esters or methacrylic acid esters may be a silicon rubber. Particularly preferred polyurethane in that good feeling can be obtained.

Specific examples of the porous polyurethane 102, solvent-based, water-based, include emulsion system or a solventless urethane resin was coagulated or solidified obtained porous polyurethane resins. Composite fiber sheet 103 formed by the porous polyurethane 102 into fiber 101 are integrated is impregnated, porous polyurethane 102 impregnated into voids formed between fibers or fiber bundles constituting the fiber sheet 101 are made by and includes numerous voids porous polyurethane 102 is not impregnated. As described later, the number of voids 106 that exist in the surface layer is lower polyurethane resin layer 104 penetrates, mixed layer 105 is formed.

But the thickness of the composite fiber sheet 103 is limited, 100 ~ 2000 .mu.m, further, in the range of 200 ~ 1500 .mu.m, texture is soft, from the viewpoint of not easily become a rubber-like texture.

Further, before the mixed layer 105 is formed, the porosity of 20 to 85 vol% of the composite fiber sheet 103, and further, 35 to 80% by volume, in particular is preferably 40 to 80 volume%. In the case of such a porosity that the break down of the resulting polyurethane laminate is particularly fine, for excellent texture balance, from the viewpoint of excellent strong peeling. Incidentally, the porosity is determined from the following equation.
Porosity (%) = [1- composite fiber sheet density ÷ {specific gravity × of the fibers constituting the composite fiber sheet (mass ratio of the fibers occupying in the composite fiber sheet) + of the elastic polymer constituting the composite fiber sheet specific gravity × (the mass ratio of the elastic polymer occupying in the composite fiber sheet)}] × 100

On the other hand, specific examples of the polyurethane resin layer 104 is made of a hot-melt type urethane resin, thermoplastic polyurethane resin, solvent-based urethane resin, water-based urethane resin or emulsion-based urethane resin coagulation or solidified so obtained polyurethane resin, the layer and the like. Among these, the polyurethane resin layer derived from the terms of excellent industrial productivity in hot-melt type urethane resin is particularly preferably used.

The thickness of the polyurethane resin layer 104 including the thickness of the mixed layer 105, 30 ~ 1000μm, more 100 ~ 800 [mu] m, polyurethane laminate particularly excellent in flexibility and mechanical strength in the range of 0.99 ~ 700 .mu.m from the viewpoint that can be obtained.

Polyurethane resin layer 104 is preferably a resin layer of porous. 10 ~ 500 [mu] m as the average diameter of the void by the porous formed polyurethane resin layer 104, more preferably from the point where it is 20 ~ 200 [mu] m is excellent in smoothness and surface touch of the processing stability, resin layer. Moreover, 10 to 90% by volume as the porosity of the polyurethane resin layer 104, further, 20 to 80% by volume, in particular 30 to be bending of the surface is 70% by volume, texture and surface touch, bending wrinkles fineness, from the viewpoint of excellent physical properties.

As shown in FIG. 3, a polyurethane laminate 110 includes a composite fiber sheet 103, the composite fiber sheet 103 contains a polyurethane resin layer 104 laminated on the surface, the surface of the composite portion of the polyurethane resin layer 104 is a fiber sheet 103 having a mixture layer 105 formed by filling from entering the air gap 106 from. Such mixed layer 105 is a layer having a 10μm thickness of at least formed by a portion of the polyurethane resin layer 104 from penetrating into numerous voids 106 of the composite fiber sheet 103, combined with a portion of the polyurethane resin layer 104 a portion of the fiber sheet 103 is a layer having a three-dimensional thickness formed by mixing with a non-compatible state. Further, by polyurethane resin layer 104 from entering the air gap 106 of the composite fiber sheet 103, the deep portion from the surface layer of the polyurethane laminate 110, so that the bottom surface 107 of the mixture layer 105 is present. The voids of the composite fiber sheet 103 by polyurethane constituting the polyurethane resin layer 104 is filled intrusion, a state of the elastic polymer and the fiber sheet constituting the composite fiber sheet 103 are mixed. To interface of these with a polyurethane resin layer and the composite fiber sheet does not exist in the vicinity of the surface layer, the influence of the interface becomes difficult exposed on the surface layer of the polyurethane laminate 110.

The thickness of the mixed layer 105, 10 ~ 800μm, more preferably from the point where it is 30 ~ 500 [mu] m exhibits a high anchoring effect. When the thickness of the mixed layer 105 is too thin, the anchor effect is weakened, no adhesion is sufficiently improved in the polyurethane resin layer 104 and the composite fiber sheet 103, inferior feeling crease, tend to crease remains There, when the thickness of the mixed layer 5 is too thick, there is a tendency that the texture becomes hard.

Further, with respect to the polyurethane resin layer 104 overall total thickness, the ratio of the thickness of the mixed layer 105 10 to 80%, more preferable from the viewpoint that it is 30-70% exhibit high anchoring effect. When the ratio of the thickness of the mixed layer 105 is too low, there is a tendency that adhesion force is not sufficiently improved in the polyurethane resin layer 104 and the composite fiber sheet 103, also the interface 107 of the mixed layer becomes near surface Tend. When the ratio of the thickness of the mixed layer 105 is too high, there is a tendency that the texture becomes harder rubber-like.

Note that in the mixed layer 105, a porous polyurethane 102 and a polyurethane resin layer 104 is present in a substantially non-compatible state. By forming such a mixed layer 105, it exhibits a higher anchoring effect. Further, in order partition walls forming a porous structure formed on the porous polyurethane 102 is maintained, and that the mechanical properties of the mixed layer 105 is excellent.

For polyurethane laminate 110, by further known conventional methods, in order to impart surface design properties, its surface layer, coating a solvent-based, water-based, polyurethane resin or an acrylic resin emulsion based or solventless or by laminating a skin layer, or the post-processing such as buffing or embossing may be carried out appropriately by.

The thickness of the entire polyurethane laminate 110, 100 ~ 3000 .mu.m, further, 200 ~ 2000 .mu.m, in particular, from the viewpoint of texture that is in the range of 500 ~ 1500 .mu.m similar to leather obtained.

Such polyurethane laminates, footwear, clothing, bags, can be used preferably as a leather-like sheet similar to natural leather comprising the surface material of the furniture.

Hereinafter, specifically describes the invention based on examples, but the invention is not in any way limited to the examples.

First, a description will be given of an embodiment 1-1 to 1-5 corresponding to the first embodiment.

[Raw materials used in Examples 1-1 to 1-5]
<Urethane prepolymer>
Task Force KMM-100 (DIC (KK) of hot-melt urethane prepolymer, 3200 · s the melt viscosity at 120 ° C.)
<Chain extender>
Polyol (DIC (KK) of the pigment-dispersed polyol, Black Exp.7457, polyol 70% by mass, the pigment 30 wt%)
<Temperature-sensitive urethane catalyst>
Of DBU oleate (manufactured by San-Apro Ltd., an exothermic peak temperature of 110 ° C.)
<Thermal expansion microcapsules>
Matsumoto Microsphere F-36 (Matsumoto Yushi-Seiyaku Co., Ltd., outer shell softening temperature 80 ~ 90 ° C.)
<Base sheet>
The average fineness of 0.07 to entangled nonwoven fabric composed of ultrafine fibers of dtex was impregnated with water-soluble polyurethane (DIC (Ltd.) manufactured by HYDRAN WLI612), thickness 1 mm, basis weight, 550g / m 2, a specific gravity of 0.55 g / cm 3 base fabric of.
<Release paper>
Lintec Co., Ltd. of the embossed release paper R-8

[Example 1-1]
To produce a polyurethane laminate using a manufacturing process as shown in FIG.

More specifically, initially, to supply a urethane prepolymer 2 at heating the melt kept at a temperature of 100 ° C. to the first mixing chamber 6c by atomizing from the nozzle 6a by pressure injection, while kept at 50 ° C. 16. to chain extenders 3 2 parts by weight of pressurized mixture obtained by mixing thermally expandable microcapsule 5 0.9 parts by weight of the temperature-sensitive urethane catalyst 4, and 0.8 part by weight from the second nozzle 6b injection to supplied to the mixing chamber 6c, which is maintained at 100 ° C. by atomization. The atomized in the mixing chamber 6c were mixed to collide each component. The mixing ratio, with respect to 2100 parts by weight of urethane polymer, a mixing ratio of the mixture 15 parts by weight of the chain extender 3 and the temperature-sensitive urethane catalyst 4 and the thermal expandable microcapsules and 5. Collision mixed urethane resin composition 10 was prepared was further stirred at the mixing chamber 6c. Incidentally, stirring, mixing chamber a provided stirrer in 6c the (T. K. homodisper Primix) was carried out for 15 seconds at 4000rpm using. After stirring, was a surface temperature of the urethane resin composition 10 is 100 ° C. as measured by a thermometer of the non-contact type.

Next, as shown in FIG. 1, the release paper 1 to be continuously fed from an unillustrated release paper delivery reel, after being fed by the feed roll 11 rotates in the arrow direction, taken up by the take-up reel 14 Te, continuous line of release paper 1 is formed.

Then, as shown in FIG. 1, toward the release paper 1 to be continuously fed, reverse roll 9b of the urethane resin composition 10, which is melt-mixed in the mixing chamber 6c it is heated to 100 ° C. and the touch roll 9a It flows down toward a clearance formed between, to form a urethane resin layer 10 by applying so as to the coating amount of 500 g / m 2 to release paper 1 surface by reverse roll 9b. In this case the coating thickness of the urethane resin layer 10 on the substrate was about 300 [mu] m.

Then, toward the surface of the urethane resin layer 10 formed on the release paper first surface, feeding a base sheet 7 from delivery reel 8 was bonded by the press rolls PR.

Next, in order to inflate the thermally expandable microcapsule 5 with activated temperature-sensitive urethane catalyst 4 was treated for 60 seconds in the heating apparatus 12 of 115 ° C..

The wound by bonding winding the body reel 14 and the urethane resin layer 10 and the base sheet 7 in a state where this way is coated with the resulting release paper 1. Then, in a state where the wound was aged 48 hours aging chamber 40 ° C., a black polyurethane laminate 13 was obtained by peeling off the release paper 1.

In case that the polyurethane laminate 13 was continuously produced by a method as described above, urethane resin composition 10 in the mixing chamber 6c is at least about 3 hours maintaining the viscosity in the range that can be applied in succession, the pot life It was excellent. Further, the resulting cross-section of the polyurethane laminate 13 was observed by a scanning electron microscope, the average diameter uniform closed pores of approximately 80μm had been formed.

[Example 1-2]
The mixing chamber 6c intima-media of the polyurethane resin composition instead of kept to 100 ° C., except that was kept at 80 ° C., and continuous production of polyurethane laminate 13 in the same manner as in Example 1-1.

In case that the polyurethane laminate 13 was continuously produced by a method as described above, the viscosity of the resin was somewhat reduced than in the case of Example 1 slightly higher coatability, there was no problem in continuous productivity. Further, the urethane resin composition in the mixing vessel is at least about 4 hours maintaining the viscosity range which can be applied continuously, it was excellent in pot life.

[Example 1-3]
Instead of performing the heat treatment step of treating 60 seconds heating apparatus 12 of 115 ° C. after bonding the base sheet 7 to the urethane resin layer 10 formed on the release paper first surface, the before bonding the base sheet 7 after the heat treatment step under conditions, except that bonding the base sheet 7, the continuous production of polyurethane laminate 13 in the same manner as in example 1-1. The resulting cross section of the polyurethane laminate 13 was observed uniform closed pores had been formed.

[Example 1-4]
Instead of forming a continuous line of release paper 1, except that initially forms the line of the base sheet 7 to form a urethane resin layer 10 on the surface of the base sheet 7 to be continuously fed in Example 1- 3 and in the same manner to form a urethane resin layer 10.

Then, toward the surface of the urethane resin layer 10 formed on the substrate sheet 7 surface, feed from the feed reel 8 release paper 1 was bonded by the press rolls PR.

Then, in order to inflate the thermally expandable microcapsule 5 with activated temperature-sensitive urethane catalyst 4 was treated for 60 seconds in the heating apparatus 12 of 115 ° C..

Then, after the forced cooling to around normal temperature by using a cooling roll 16, and wound up. Then, in a state where the wound was aged 48 hours aging chamber 40 ° C., a black polyurethane laminate 13 was obtained by peeling off the release paper 1. The resulting cross section of the polyurethane laminate 13 was observed uniform closed pores had been formed.

[Example 1-5]
The release paper first surface, was blended with pre-water-dispersible polyurethane-D-6065 (Dainichi manufactured Seika Kogyo Co., Ltd.) / thickening agent D-890 (manufactured by Dainichi manufactured Seika Kogyo Co., Ltd.) = 100/2 skin the use liquid combination thickness after drying to be 10 [mu] m, by performing a 2-minute drying at 120 ° C., to prepare the skin layer with release paper to form a skin layer made of elastic polymer release paper surface , except for forming a urethane resin layer 10 on a release paper with said surface skin layer, the continuous production of multi-layer polyurethane laminate in the same manner as in example 1-1. The resulting uniform closed pores in the multilayer polyurethane laminates within the urethane resin layer 10 where the cross section is observed in had been formed. Then, the skin part had a smooth touch.

[Comparative Example 1-1]
To produce a polyurethane laminate using a manufacturing process as shown in FIG.

More specifically, initially, to supply a urethane prepolymer 2 at heating the melt kept at a temperature of 120 ° C. to a mixing chamber 6c by atomized by pressurized injection from the first nozzle 6a, whereas, it kept at 50 ° C. 16. to chain extenders 3 2 parts by weight of a mixture obtained by mixing thermally expandable microcapsule 5 temperature sensitive urethane catalysts 4 and 0.8 parts by weight of 0.9 parts by weight from the second nozzle 6b pressurizing including fluid shines which was supplied to the mixing chamber 6c, which is kept at 110 ° C. by atomization. The atomized in the mixing chamber 6c were mixed to collide each component. The mixing ratio, with respect to 2100 parts by weight of urethane polymer, the proportion of the mixture 15 parts by weight of a chain extender 3 and the temperature-sensitive urethane catalyst 4 and thermally expandable microcapsule 5 supplied from the second nozzle 6b in were mixed. Collision mixed urethane resin composition 10 was prepared was further stirred at the mixing chamber 6c. After stirring, was a surface temperature of the urethane resin composition 10 is 110 ° C. as measured by a thermometer of the non-contact type. At this time, heat-expandable microcapsules had expanded to more than twice.

Subsequent steps, to form a polyurethane laminate except for not performing the heat treatment in the same manner as in Example 1-1.

In case of continuous production of polyurethane laminate by the method as described above, the urethane resin composition in the mixing vessel viscosity increased to a viscosity such that the coating becomes difficult within about 5 minutes.

From the results of Examples 1-1 to 1-5 and Comparative Examples 1-1, it can be seen that below.

According to the present invention, Examples 1-1, such as in-1-4 to prepare a temperature-sensitive urethane polyurethane resin composition applied at 10 ~ 30 ° C. lower such temperature than the exothermic peak temperature of the catalyst case, the pot life of the polyurethane resin composition prepared becomes very long, it can be seen that excellent continuous productivity. On the other hand, in Comparative Example 1-1 was prepared polyurethane resin composition at the exothermic peak temperature of the temperature-sensitive urethane catalysts, the pot life of the polyurethane resin composition prepared becomes very short, continuous production It was poor in sex. And by placing a heat treatment step of heat-treating a urethane resin layer by the exothermic peak temperature or more, it is possible to optimize the resin layer forming speed, thereby improving productivity.

Next, a description will be given of an embodiment 2-1 to 2-5 corresponding to the second and third embodiments.

[Raw materials used in Examples 2-1 to 2-5]
<Urethane prepolymer>
Task Force KMM-100LV (DIC (KK) of the moisture-curable hot-melt urethane prepolymer, a melt viscosity at 100 ° C. is 2500 mPa · s)
<Chain extender>
Butanediol (manufactured by Mitsubishi Chemical Corporation)
<Temperature-sensitive urethane catalyst>
Of DBU oleate (manufactured by San-Apro Ltd., U-CAT SA-106, the exothermic peak temperature 110 ° C.)
<Thermal expansion microcapsules>
Matsumoto Microsphere F-36 (Matsumoto Yushi-Seiyaku Co., Ltd., outer shell softening temperature 80 ~ 90 ° C.)
<Pigment>
Dairakku black RHM-7944 (DIC (Ltd.))
<Composite fiber sheet>
The average fineness 2 dtex lotus root-shaped nylon microfine fibers (specific gravity: 1.14) composed of entangled nonwoven fabric and polyether porous polyurethane (specific gravity: 1.2) 12 and a 1: complexed in a weight ratio of comprising a thickness of about 800 [mu] m, basis weight 250 g / m 2, a density 0.315 g / cm 3, a porosity of about 73 volume percent of the composite fiber sheet.
<Release paper>
Lintec Co., Ltd. of release paper R-70N (thickness 200μm)

[Example 2-1]
To produce a polyurethane laminate using a manufacturing process as shown in FIG.

More specifically, first, the mixing head (Maruka Kakoki Co., MEG-HK-55S type) was used to prepare a crosslinkable hot-melt type urethane resin 120. Specifically, 100 parts of urethane prepolymer was kept in 115 ° C. (parts by weight hereinafter the same) were fed into the mixing chamber 136c by atomized by pressure inject from the first nozzle 136a, whereas, 15.7 parts of pigment , thermally expandable microcapsule 0.8 parts, 0.25 parts of the temperature-sensitive urethane catalyst, and a chain extender 0.25 parts mixture was mixed at 50 ° C. and pressurized including fluid shines from the second nozzle 136b atomization by and mixed by colliding the components which are atomized. The mixing ratio with respect to 100 parts by mass of the urethane prepolymer, in a mixing ratio of the mixture 17 parts by weight.

Next, the release paper 121 fed out at a line speed 5 m / min from an unillustrated release paper feed reel, after being fed by the roll 141 feeding rotated in the arrow direction, it is wound by the winding reel 144, the release paper 121 continuous line is formed.

Then, toward the release paper 121 is continuously fed, reverse roll 139b and the touch roll rotating the mixing chamber crosslinkable hot-melt type urethane resin 120 that is melt-mixed in a 36c at 12m / min, which is heated to 100 ° C. flows down toward a clearance formed between the 139a, the coating film 132 was formed by coating so that the coating amount of 280 g / m 2 release paper 121 surface by reverse roll 139b, the release paper surface by forming a coating film 132 release paper - to form a coating film stack 140. In this case, a thickness of the coating film 132 was about 450 [mu] m.

Next, it causes partially crosslinked urethane prepolymer temperature sensitive urethane catalyst 124 is activated, in order to complete the expansion of the thermal expandable microcapsules 125, release paper - of the coating stack 140 125 ° C. It was treated for 90 seconds in the heating apparatus 142.

Next, the release paper - Towards coating formed on stack 140 surface of the coating film 132, the delivery reel 138 feeds the composite fiber sheet 103 was bonded by a press roll PR consisting of two rolls. In this case, the clearance gap between the two rolls was 1410Myuemu.

Release paper states was thus coated with a release paper 121 obtained - polyurethane laminate precursor 143 is bonded body of the paint film laminate 140 and the composite fiber sheet 103, forced by using a cooling roll 146 after being cooled to, wound by the winding reel 144. Then, in a state where the wound was aged at aging room temperature 40 ° C. 48 hours, polyurethane laminate black was obtained by peeling off the release paper 121.

Thus carbonate system on the surface of the resulting polyurethane laminate yellowing type urethane (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. NES9950) urethane adhesive skin layer having a thickness of 20μm consisting mainly of (Dainichi Seika by bonding with Kogyo Co., Ltd. ME8116), leather-like sheet 117 of the code burn tone was obtained. Then, the cross section of the leather-like sheet 117 was observed with a scanning electron microscope (SEM) (see Figure 5).

From the obtained SEM photograph, the leather-like sheet 117 are laminated from the surface in this order, the skin layer having a thickness of about 20 [mu] m 109, the polyurethane resin layer 114 having a thickness of about 650 .mu.m, and is composed of a composite fiber sheet 113 having a thickness of about 800μm and is the underlying polyurethane resin layer 114 were mixed layer 115 of about 300μm thickness penetrated filled in the upper layer of the void 116 of the composite fiber sheet 113 is formed. Further, the polyurethane resin layer 114 is uniform closed pores with an average diameter of about 180μm was formed. Furthermore, in the mixed layer 115, and a porous polyurethane and the polyurethane resin layer 114 was present in a non-compatible state. Each of the above thickness is an average value measured from the SEM photograph at any ten sectional chose the obtained leather-like sheet 117. Representative micrographs at this time is shown in FIG.

In addition, to evaluate the texture of when folding the leather-like sheet obtained in this way. Specifically was observed grain breakage occurs when folded in half leather-like sheet was cut into a square shape of a side 200 mm. In this case, the same fine wrinkles in the case of leather, as shown in FIG. 7 has occurred. In addition, after putting the folds by suppressing strongly with a finger is bent, when you open also, does not remain crease at all, it was to maintain a smooth surface.

[Example 2-2]
And except for changing the clearance distance between two rolls of the press roll PR from 1410μm to 1310μm in the same manner as in Example 2-1 to prepare a leather-like sheet evaluated. Then, the resultant leather-like sheet of a cross section was observed by a scanning electron microscope (SEM). Obtained leather-like sheet was laminated from the surface in this order, the skin layer having a thickness of about 20 [mu] m, a polyurethane resin layer having a thickness of about 650 .mu.m, and is composed of a composite fiber sheet having a thickness of about 800 [mu] m, the lower layer of the polyurethane resin layer There mixed layer having a thickness of about 400μm invade filled in the upper layer of voids of the composite fiber sheet was formed. We have also measured the texture when folding the leather-like sheet thus obtained, the fine wrinkles as shown in FIG. 7 has occurred. In addition, after putting the folds by suppressing strongly with a finger is bent, when you open also, does not remain crease at all, it was to maintain a smooth surface.

[Example 2-3]
And except for changing the clearance distance between two rolls of the press roll PR from 1410μm to 1450μm in the same manner as in Example 2-1 to prepare a leather-like sheet evaluated. Then, the resultant leather-like sheet of a cross section was observed by a scanning electron microscope (SEM). Obtained leather-like sheet was laminated from the surface in this order, the skin layer having a thickness of about 20 [mu] m, a polyurethane resin layer having a thickness of about 650 .mu.m, and is composed of a composite fiber sheet having a thickness of about 800 [mu] m, the lower layer of the polyurethane resin layer There mixed layer having a thickness of about 40μm to penetrate filled in the upper layer of voids of the composite fiber sheet was formed. We have also measured the texture when folding the leather-like sheet thus obtained, the fine wrinkles as shown in FIG. 7 has occurred. Moreover, after putting the folds by suppressing strongly with a finger bent, when opened also, break does not remain wrinkles, but there was intended to maintain a smooth surface, balanced texture Example 2-1 compared to the leather-like sheet 117 were those slightly inferior.

[Example 2-4]
And except for changing the clearance distance between two rolls of the press roll PR from 1410μm to 1200μm in the same manner as in Example 2-1 to prepare a leather-like sheet evaluated. Then, the resultant leather-like sheet of a cross section was observed by a scanning electron microscope (SEM). Obtained leather-like sheet was laminated from the surface in this order, the skin layer having a thickness of about 20 [mu] m, a polyurethane resin layer having a thickness of about 650 .mu.m, and is composed of a composite fiber sheet having a thickness of about 800 [mu] m, the lower layer of the polyurethane resin layer There mixed layer having a thickness of about 600μm invade filled in the upper layer of voids of the composite fiber sheet was formed. We have also measured the texture when folding the leather-like sheet thus obtained, the fine wrinkles as shown in FIG. 7 has occurred. Moreover, after putting the folds by suppressing strongly with a finger bent even when opened, it does not remain crease, but was to maintain a smooth surface, as compared to Example 2-1 texture It was hard ones of.

[Example 2-5]
The release paper 121 surface, was blended with pre-water-dispersible polyurethane-D-6065 (Dainichi manufactured Seika Kogyo Co., Ltd.) / thickening agent D-890 (manufactured by Dainichi manufactured Seika Kogyo Co., Ltd.) = 100/2 skin the use liquid combination thickness after drying to be 10 [mu] m, by performing a 2-minute drying at 120 ° C., was prepared release paper with the skin layer the skin layer was formed of a polymer elastic body release paper surface . And, except for forming a layer comprising a crosslinkable hot-melt type urethane resin 120 on release paper with said surface skin layer, the continuous production of multi-layer polyurethane laminate in the same manner as in Example 2-1. Obtained multilayer polyurethane laminate, without later forming a skin layer as in Example 2-1, it was possible to produce a leather-like sheet continuously without a solvent. Observation of the obtained leather-like sheet of the cross-section, are laminated from the surface in this order, the skin layer, a polyurethane resin layer, and is composed of a composite fiber sheet, the gap of the upper lower layer of the composite fiber sheet of the polyurethane resin layer mixed layer having a thickness of about 300μm was formed invade filled in. Further, the polyurethane resin layer, uniform closed pores with an average diameter of about 180μm was formed. Furthermore, in the mixed layer, and a porous polyurethane and the polyurethane resin layer was present in a non-compatible state. Also, texture when folded, broken grain, also crease feeling and smoothness were evaluated as described in Example 2-1.

[Comparative Example 2-1]
After the thermoplastic polyurethane resin (manufactured by Kuraray Co., Ltd. Kuramilon U3119-000) 100 parts of a black pigment 3 parts were dry blended, a thermoplastic polyurethane film from an extruder equipped with a T die set at a cylinder temperature of 230 ° C. extruded, and immediately thereafter, to produce a polyurethane resin layer by bonding to the surface of the composite fiber sheet. Incidentally, crimping was performed using the press roll PR with the same clearance gap as used in Example 2-1. The surface to Example 2-1 of the resulting polyurethane resin layer and in the same manner to produce a leather-like sheet by forming a skin layer. Then, it was evaluated in the same manner as in Example 2-1. Cross-sectional SEM photograph of the obtained leather-like sheet 118 shown in FIG. The leather-like sheet 118 are laminated from the surface in this order, the skin layer 109 having a thickness of about 20 [mu] m, the polyurethane resin layer 111 having a thickness of about 350 .mu.m, and it was composed of a composite fiber sheet 113 having a thickness of about 800 [mu] m, Example 2 mixed layer as being formed on the polyurethane laminate -1 to 2-5 was not formed. We have also measured the texture when folding the leather-like sheet obtained in this manner, a large wrinkles as shown in FIG. 8 has occurred. In addition, when you put a wrinkle fold by suppressing strongly with a finger is bent, a large number of fine creases remaining when opened.

[Comparative Example 2-2]
After solvent type polyurethane solution containing a black pigment (solid content 15 wt%) was applied on the release paper, to form a polyurethane resin layer having a thickness of 300μm by repeating three times to dry. Then, using the solvent-based 2-component polyurethane adhesive to a surface of the composite fiber sheet, bonding the resulting polyurethane resin layer. Then, to obtain a polyurethane laminate by ripening. Although resulting polyurethane resin layer of polyurethane laminate is observed portion extending as invading slightly in length of about 10μm fiber composite sheet, continuous layer, such as entry portion having a thickness In did not. Also, it was not filled in the gaps of the composite fiber sheet. Furthermore, the porous structure of the porous polyurethane to be contained in the composite fiber sheet in the entrance portion is destroyed is dissolved by the solvent of a solvent-type polyurethane solution, the polyurethane porous polyurethane constituting the polyurethane resin layer surface to form one another was compatible state does not.

[Comparative Example 2-3]
By repeating the coating and drying so that the water-based polyurethane dispersion (solid concentration 45%) substantially the same thickness as Comparative Example 2-2 on release paper in place of solvent-based polyurethane solution of Comparative Example 2-2, to form a polyurethane resin layer having a thickness of 350 .mu.m. Then, the resulting polyurethane resin layer was laminated to the composite fiber sheet 3 via the water-based polyurethane adhesive. Then, to obtain a polyurethane laminate by ripening. Although resulting polyurethane resin layer of polyurethane laminate was observed portion extending as a slight penetration depth of about 10μm from Similarly composite fiber sheet surface of Comparative Example 2-2, the composite not filled in the voids of the fiber sheet, entering part was not a continuous layer such as to have a thickness.

From the results of Examples 2-1 to 2-5 and Comparative Examples 2-1 to 2-3, it can be seen that below.

According to this embodiment, when folding the leather-like sheet mainly resulting polyurethane laminate in Examples 2-1 to 2-5, with both fine broken grain-like leather occurs, crooked wrinkle broken when you open after wearing the type Te did not remain. This is because the mixed layer and the lower layer of the upper layer and the polyurethane resin layer of the composite fiber sheet having a certain thickness that is integrated is formed, with the composite fiber sheet and the polyurethane resin layer is high adhesion It seems to be due to forming a laminate structure with a dense feel.

On the other hand, extruding a thermoplastic polyurethane film from an extruder equipped with a T-die, leather mainly resulting polyurethane laminate in Comparative Example 2-1 obtained by crimping the thermoplastic polyurethane film composite fiber sheet like sheet, to the thermoplastic polyurethane film is the surface upon contact with the surface of the composite fiber sheet rapidly thicken, or solidify, the voids of the composite fiber sheet as was crimped at a certain high pressure thermoplastic polyurethane film will not penetrate, a mixed layer such as formed of polyurethane laminate of example was formed. Also in the polyurethane laminates obtained in Comparative Examples 2-2 and 2-3, a mixed layer such as formed of polyurethane laminate of Example it was formed. Therefore, in Comparative Examples 2-1 to 2-3, not obtain a high adhesion and sense of unity with the composite fiber sheet and the polyurethane resin layer, similar to leather when folded, texture with fullness obtained did not.

As has been described, one aspect of the present invention, sensitive indicates a predetermined exothermic peak temperature room temperature a semi-solid or solid at which the urethane prepolymer (A) and the chain extender (B) and by differential scanning calorimetry temperature a melt mixing step of forming a urethane resin composition by heating melted and mixed and sex urethane catalyst (C) at a temperature of lower 10 ~ 30 ° C. range for the exothermic peak temperature, using the urethane resin composition Te and the resin layer forming step of forming a urethane resin layer on the sheet surface such as a release paper or fibrous base material, a heat treatment step of heat-treating the urethane resin layer by the exothermic peak temperature or higher, the comprises polyurethane laminate it is a manufacturing method.

According to such a manufacturing method, a temperature-sensitive urethane catalyst (C) is 10 ~ 30 ° C. lower range temperature urethane prepolymer than the exothermic peak temperature that activates (A) a chain extender and (B) to prepare the urethane resin composition and a temperature-sensitive urethane catalyst (C) heating and melting a mixture thereof, the progress of the crosslinking reaction the urethane resin composition to be subjected to the coating is inhibited. Pot life of the urethane resin composition is subjected to coating for the longer. The urethane resin layer which is formed on the substrate surface after the by temperature-sensitive urethane catalyst (C) is heat treated at a temperature higher than the exothermic peak temperature activated, crosslinked quickly, thereby producing sex can be improved.

Further, the temperature sensitive urethane catalyst is 1,8-diazabicyclo (5,4,0) - in the case of organic acid salts of undecene-7, the predetermined exothermic peak temperature becomes sharp by differential scanning calorimetry from the viewpoint of easier control of the cross-linking reaction by.

Also, in the melt-mixing step, the thermally expandable microcapsule further mixed in the urethane resin composition, the thermal expandable microcapsules, it is intended to expand at least twice the expansion rate in the heat treatment step preferable. By mixing such a thermally expandable microcapsule in the urethane resin composition, it is possible to form a polyurethane layer having a uniform closed cell.

Further, the melt-mixing step, from the first nozzle of the mixing head and the urethane prepolymer heated and melted state of being atomized by being pressurized injection (A), by being pressurized injected from the second nozzle by colliding a mixture containing atomized the chain extender (B) and a temperature-sensitive urethane catalyst (C), heated and melted at a temperature lower 10 ~ 30 ° C. range for the exothermic peak temperature it is preferably a mixing process. According to such a method enables more uniform mixing.

Further, the polyurethane laminate of the present invention, it is preferable that the polyurethane laminate obtained by any of the manufacturing methods.

Further, another aspect of the present invention, release paper by applying a crosslinkable hot-melt type urethane resin in a molten state to the release paper surface - and a coating film forming step of forming a coating film laminate, crosslinkable hotmelt a heat treatment step of the type urethane resin is partially crosslinked, fiber sheets and the elastic polymer is impregnated integrated, the voids of the composite fiber sheet having numerous voids in the surface layer, release paper - coating of the coating stack pressure, such as a portion of the film enters a laminating step of laminating the coating on the surface of the composite fiber sheet, the crosslinkable hot-melt type urethane resin and a cooling step of cooling and solidifying, in the manufacturing method of the polyurethane laminate comprising is there.

According to such a manufacturing method, it is possible to easily manufacture a polyurethane laminate having a mixed layer as described above.

Further, the coating film forming step, sensitive indicates a predetermined exothermic peak temperature melt viscosity at 100 ° C. The following 10000 mPa · sec hot-melt urethane prepolymer (A) and the chain extender (B) and by differential scanning calorimetry temperature a melt mixing step of forming a crosslinkable hot-melt type urethane resin by heating and melting mixing and sex urethane catalyst (C) at a temperature of lower 10 ~ 30 ° C. range for exothermic peak temperature, melt release paper surface release paper by applying the state of the crosslinkable hot-melt type urethane resin - and a coating film forming step of forming a coating film laminate, the heat treatment process, the release paper - coating a laminate of more than the exothermic peak temperature it is preferably a step of partially crosslinking the coating film by heat treatment at a temperature.

According to such a manufacturing method, a temperature-sensitive urethane catalyst (C) is 10 ~ 30 ° C. lower range temperature urethane prepolymer than the exothermic peak temperature that activates (A) a chain extender and (B) to a temperature-sensitive urethane catalyst (C) heating and melting mixed to prepare a crosslinkable hot-melt type urethane resin, progress of the crosslinking reaction of the crosslinkable hot-melt type urethane resin to be used in the coating is suppressed . Its viscosity required for coating to be maintained. The coating film formed on the release paper surface by temperature-sensitive urethane catalyst (C) is heat treated at a temperature higher than the exothermic peak temperature of activating, viscosity adjustment of the coating film is partially cross-linked It is. Then, the coating film is adjusted to an appropriate viscosity by pressing, it is possible to easily adjust the amount of coating entering the gap of the surface layer portion of the composite fiber sheet.

The temperature-sensitive urethane catalysts, for example, 1,8-diazabicyclo (5,4,0) - organic acid salts such undecene-7 is preferably used.

In the melt mixing step, the thermally expandable microcapsule further mixed into the crosslinkable hot-melt type urethane resin, thermally expandable microcapsules, more than twice the expansion rate in the melt-mixing step and / or heat treatment step it is preferable that the expanding. By mixing such a thermally expandable microcapsule in the crosslinkable hot-melt type urethane resin, it is possible to form a polyurethane resin layer having a uniform closed cell.

Further, the melt mixing step, the first nozzle of the mixing head and a pressure of heating molten state of being atomized by being injected hot-melt urethane prepolymer (A), which is pressurized jetted from the second nozzle by colliding a mixture containing atomized chain extender (B) and the temperature-sensitive urethane catalyst (C), the heated and melted mixture at 10 ~ 30 ° C. lower range of temperatures for the exothermic peak temperature it is preferably a step. According to such a method enables more uniform mixing.

Moreover, yet another aspect of the present invention, the fiber sheet and the elastic polymer is impregnated integrated composite fiber sheet having numerous voids in the surface layer, a polyurethane resin layer laminated on the composite fiber sheet and a laminate of, by a portion of the polyurethane resin layer in the gap to penetrate, a portion of the polyurethane resin layer and the surface layer of the composite fiber sheet are mixed in a non-compatible state, 10 [mu] m or more, preferably is a polyurethane laminate having a mixed layer having a thickness of at least 30 [mu] m.

According to such a polyurethane laminates, the interface between the composite fiber sheet and the polyurethane resin layer, rather than two-dimensional ones, such as a conventional polyurethane laminate obtained by the method, as shown in FIG. 3, it can be present as a three dimensionally formed mixed layer 105 having a sufficient thickness randomly to deeply penetrate the polyurethane constituting the polyurethane resin layer in the thickness direction of the composite fiber sheet. Moreover, such a mixed layer is a portion of the polyurethane resin layer penetrates into the gap of the composite fiber sheet, because it is formed so as to fill the void, the polyurethane resin layer is supported by a high anchoring effect by composite fiber sheet It is. Furthermore, by a polyurethane resin layer from penetrating into the composite fiber sheet, the deep portion from the surface layer of the polyurethane laminate, the bottom surface of the mixed layer is located (e.g., bottom surface 107 of FIG. 3). Thus the influence of the mismatch at the interface between the polyurethane resin layer which has been a problem conventionally a composite fiber sheet is less likely to exposed on the surface layer of the polyurethane laminate. Polyurethane laminate, by improving the adhesion between the composite fiber sheet and the polyurethane resin layer is provided such a mixed layer, and a texture with a satisfaction similar to leather, good crease feeling when bent in, after the bending, hard polyurethane laminate remainder crease is obtained. In the mixed layer, and the elastic polymer and the polyurethane resin layer is present in a substantially non-compatible state. Here, the non-compatible state means that the state in which the polyurethane resin constituting the elastic polymer and the polyurethane resin layer constituting the composite fiber sheet not mixed substantially with melted together with one another. Incidentally, the elastic polymer and the polyurethane resin layer may be in close contact or crosslinking, be present so as to cover the well be simply filled in a gap elastic polymer or the elastic polymer good. If the result of applying a solvent type urethane adhesive to the surface of the composite fiber sheet, dissolved elastic polymer of the composite fiber in the sheet by solvent, high in the composite fiber sheet with the applied polyurethane molecular elastic member is likely to be compatible state in admixture. When it becomes compatible state in the case of the elastic polymer is particularly porous state of the composite fiber in the sheet, collapsed porous state, it tends to be inferior in texture and creases feeling.

Further, occupying in the total thickness of the polyurethane resin layer, the thickness ratio of the mixed layer is preferably 10 to 80%. If this higher mixed layer thickness ratio to the total thickness of the polyurethane resin layer is formed so, that sense of unity with the polyurethane resin layer and the composite fiber sheet becomes higher. The total thickness of the polyurethane resin layer is, referring to FIG. 3, when a cross section parallel to the thickness direction of the polyurethane laminate was observed with a scanning electron microscope, the surface of the polyurethane resin layer 104, a polyurethane resin layer 104 location but a thickness up to which the most deeply enters inside the composite fiber sheet 103, the thickness of the mixed layer from the surface of the composite fiber sheet 103, the polyurethane resin layer 104 is most deeply enters inside the composite fiber sheet 103 it is the thickness of up to.

It polyurethane resin layer is a layer formed by crosslinking the hot-melt type urethane resin is excellent in penetration and filling of the mixed layer, also incompatible with the elastic polymer constituting the composite fiber sheet from the viewpoint of easily obtaining the state.

Further, it is preferable from the viewpoint of suppressing the generation of Arabidopsis when narrowing fishing and flexible texture and natural leather-like crease feeling at least one of the polyurethane resin layer and the elastic polymer is porous.

In addition, when the porosity of the composite fiber sheet is in the range of 30 to 85% by volume, that the breaking down of the resulting polyurethane laminate becomes finer, for excellent texture balance, from the viewpoint of excellent strong peeling.

According to the production method of polyurethane laminate of the present invention, stable on the substrate surface in forming a polyurethane layer with a solventless, continuous by long maintain the pot life of the urethane resin composition to be used for coating manner can be processed, also improves the productivity of the polyurethane laminate by crosslinking quickly by heat treatment polyurethane layer of uncrosslinked coated.

Further, according to the manufacturing method of the polyurethane laminate of the present invention, a polyurethane laminate showing a texture similar to leather when folded can be obtained. In particular, along with broken grain is generated fine similar to leather, creases remaining hard polyurethane laminate after foldability is obtained.

Claims (22)

  1. A semi-solid or solid at which the urethane prepolymer (A) and the chain extender (B) and differential scanning calorimetry temperature-sensitive urethane catalysts showing a predetermined exothermic peak temperature by measuring (C) the exothermic peak temperature at room temperature urethane resin composition and the melt-mixing step of forming, the urethane resin composition resin layer forming step of forming a urethane resin layer on the sheet surface using by heating melted and mixed at 10 ~ 30 ° C. lower range of temperatures for When producing a polyurethane laminate, characterized in that it comprises a heat treatment step of heat-treating the urethane resin layer by the exothermic peak temperature or higher.
  2. Method for producing a polyurethane laminate according to claim 1 wherein the sheet is a release paper.
  3. Said sheet is a sheet made of a elastic polymer layer previously formed on the surface of the release paper and 該離 paper, according to claim 1 to form a urethane resin layer on the surface of the elastic polymer layer method of manufacturing a polyurethane laminate.
  4. Method for producing a polyurethane laminate according to claim 1 wherein the sheet is a fibrous substrate.
  5. The temperature sensitive urethane catalyst is 1,8-diazabicyclo (5,4,0) - producing a polyurethane laminate according to any one of claims 1 to 4, which is an organic acid salt of undecene-7.
  6. In the melt mixing step, further mixing the thermally expandable microcapsule to the urethane resin composition,
    The thermally expandable microcapsule production method of the polyurethane laminate according to any one of claims 1 to 5 is intended to expand at least twice the expansion rate in the heat treatment step.
  7. Atomizing said melt mixing step, and the urethane prepolymer heated and melted state of being atomized by being the first nozzle of the mixing head pressure injection (A), by being pressurized injected from the second nozzle by the impinging a mixture wherein comprising a chain extender (B) and temperature-sensitive urethane catalyst (C), heated melt mixed in 10 ~ 30 ° C. lower range of temperatures for the exothermic peak temperature method for producing a polyurethane laminate according to any one of claims 1 to 6, which is a process.
  8. Polyurethane laminate obtained by the production method described in any one of claims 1 to 7.
  9. The claims are sheet release paper according to claim 1, method for producing a polyurethane laminate comprising a step of bonding further fiber substrate to the surface of the obtained the urethane resin layer.
  10. The method of manufacturing a polyurethane laminate according to claim 1,
    And a coating film forming step of forming a coating film laminate, - release paper by applying a crosslinkable hot-melt type urethane resin in a molten state to the release paper surface
    A heat treatment step of partial crosslinking the crosslinkable hot-melt type urethane resin,
    Fiber sheet and the elastic polymer is impregnated integrated, the voids of the composite fiber sheet having numerous voids in the surface layer, the release paper - a pressure such as a portion of the coating film of the coating film stack invading a lamination step of laminating the coating film on the surface of the composite fiber sheet,
    Method for producing a polyurethane laminate and a cooling step of cooling and solidifying the cross-linkable hot-melt type urethane resin.
  11. The release paper, which has previously formed a elastic polymer layer on its surface, the polyurethane according to claim 10 for applying a crosslinkable hot-melt type urethane resin in a molten state on the surface of the elastic polymer layer method for producing a laminate.
  12. The method of manufacturing a polyurethane laminate according to claim 1,
    The melt mixing step, temperature-sensitive urethane indicating a predetermined exothermic peak temperature melt viscosity of 10000 mPa · sec or less for hot melt urethane prepolymer (A) and chain extender (B) and by differential scanning calorimetry at 100 ° C. a melt mixing step of forming the crosslinkable hot-melt type urethane resin by heating melted and mixed at 10 ~ 30 ° C. lower range of temperature and catalyst (C) with respect to the exothermic peak temperature,
    A film forming step of forming a coating film stack, - the resin layer forming step is the release paper by applying the crosslinkable hot-melt type urethane resin in a molten state to the release paper surface
    It said heat treatment step, the release paper - producing a polyurethane laminate is a heat treatment step of partial crosslinking of the coating film by heat-treating the coating stack by the exothermic peak temperature or higher.
  13. The method of manufacturing a polyurethane laminate according to claim 12,
    After the heat treatment process,
    Fiber sheet and the elastic polymer is impregnated integrated, the voids of the composite fiber sheet having numerous voids in the surface layer, the release paper - a pressure such as a portion of the coating film of the coating film stack invading a lamination step of laminating the coating film on the surface of the composite fiber sheet,
    Method for producing a polyurethane laminate and a cooling step of cooling and solidifying the cross-linkable hot-melt type urethane resin.
  14. The temperature sensitive urethane catalyst is 1,8-diazabicyclo (5,4,0) - producing a polyurethane laminate according to any one of claims 10-13 which is an organic acid salt of undecene-7.
  15. In the melt mixing step, further mixing the thermally expandable microcapsule in the crosslinkable hot-melt type urethane resin,
    The thermally expandable microcapsule production method of the polyurethane laminate according to any one of the melt mixing step and / or is intended to expand at least twice the expansion rate in the heat treatment process according to claim 10-14.
  16. The melt mixing step, and the from the first nozzle of the mixing head of heating molten state of being atomized by being pressurized injection hot-melt urethane prepolymer (A), being pressurized injected from the second nozzle heated atomized the chain extender (B) and by impinging the mixture containing the temperature sensitive urethane catalyst (C), the temperature of the lower 10 ~ 30 ° C. relative to the exothermic peak temperature range by method for producing a polyurethane laminate according to any one of claims 10 to 15, which is a step of melt-mixing.
  17. A polyurethane laminate obtained by the production method described in any one of claims 10-16,
    Fiber sheet and the elastic polymer is impregnated integrated a laminate of a composite fiber sheet having numerous voids in the surface layer, and the composite fiber sheet polyurethane resin layer laminated on,
    By a portion of the polyurethane resin layer in the gap to penetrate, polyurethane having a mixture layer having a polyurethane portion of the resin layer and the surface layer of the composite fiber sheet are mixed in a non-compatible state, 10 [mu] m or more in thickness laminate.
  18. Polyurethane laminate according to claim 17 the thickness of the mixed layer is 30μm or more.
  19. Total occupied in thickness, polyurethane laminate according to claim 17 or 18 thickness ratio of the mixed layer is 10 to 80% of the polyurethane resin layer.
  20. Polyurethane laminate according to any one of claims 17 to 19, wherein the polyurethane resin layer is a layer formed by crosslinking hot-melt type urethane resin.
  21. Polyurethane laminate according to any one of the preceding claims 17-20, at least one of the polyurethane resin layer and the elastic polymer is porous.
  22. Polyurethane laminate according to any one of claims 17-21 porosity in the range of 30 to 85 vol% of the composite fiber sheet.
PCT/JP2010/003393 2009-05-29 2010-05-20 Method for producing polyurethane laminate, and polyurethane laminate obtained by the production method WO2010137264A1 (en)

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JP2000303368A (en) * 1999-04-26 2000-10-31 Kuraray Co Ltd Suede finish leather-like sheet
JP2003220670A (en) * 2002-01-29 2003-08-05 Kuraray Co Ltd Laminate
JP2003246830A (en) * 2002-02-25 2003-09-05 Dainippon Ink & Chem Inc Highly durable solvent-free moisture-curing hot-melt urethane resin composition, foam and sheet structure using this
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JP2007092195A (en) * 2005-09-27 2007-04-12 Dai Ichi Kogyo Seiyaku Co Ltd Aqueous resin composition for fiber laminate skin, method for producing fiber laminate, and synthetic leather

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