JP5876280B2 - Laminated body - Google Patents

Description

  The present invention relates to a laminate including a fiber layer and a foam layer, and particularly relates to a laminate including a polypropylene fiber layer and a HIPE foam layer.

As a method for obtaining a porous polymer having fine and uniform bubble diameters and consisting of three-dimensionally continuous bubbles, a polymer is obtained from a water-in-oil type high internal phase emulsion (Water in Oil type High Internal Phase Emulsion). There is a way to get it. In this method, an oil layer is polymerized to form a porous structure, and then water is removed to form a porous polymer. The polymer obtained by this method is hereinafter referred to as HIPE foam. The HIPE foam has, for example, a void structure with a passing inner diameter of several tens of μm or less and a porosity of 75% or more. The HIPE foam wets and comes into contact with the liquid. It has the property of being pulled in and retained even when high pressure is applied. As long as the liquid has wettability and moderately low viscosity, it does not cause the swelling of the polymer as seen in SAP (high water absorption polymer) or the water absorption capacity of the electrolyte decreases. It is attracting attention as an absorbent material.
However, since the HIPE foam has a low density, it is very brittle and its strength is weak. Therefore, the HIPE foam falls off only by applying a small force to the HIPE foam. This powder fall is a state in which the fine bubble skeleton of the porous structure is broken.

  In order to cope with such a problem, for example, in Patent Document 1, in order to improve the strength of the HIPE foam, the activated carbon fiber, mineral fiber, polyethylene fiber, and acrylic fiber are dispersed in an emulsion and cured, so that the inside of the HIPE foam A fiber reinforced foam composite obtained from a high internal phase emulsion impregnated in is disclosed.

  Moreover, in patent document 2, the filter material which formed the HIPE foam on the support body by using felt as a support body, making a felt impregnate a water-in-oil type high internal phase emulsion, and polymerizing a monomer. It is disclosed.

Special table 2004-514006 gazette US Pat. No. 6,103,645

  However, even in such conventional technology, the strength of the HIPE foam is not sufficient. For example, since there is no stretchability and toughness, the HIPE foam may be broken when incorporated into a machine, or the surface may be cracked or cracked. is there. Further, since the HIPE foam is formed on the surface, when the liquid is continuously dropped onto the HIPE foam, the liquid is concentrated only in one place and does not spread over a wide area, and may spread to the back. In such a case, although it is an absorbent material having a predetermined area, only the dropped portion is used and does not function sufficiently as an absorbent material.

  Therefore, the present invention has been made in view of the above problems, and an object of the present invention is to improve the strength and toughness of the laminate in a laminate comprising a HIPE foam by producing and processing it. Furthermore, it is intended to provide a laminate capable of improving the absorbability of liquid and having no unevenness in absorbability and preventing leakage after absorption.

In order to solve the above problems, a foam layer obtained by curing a high internal phase emulsion, a polypropylene fiber layer on the surface of the foam layer, and the polypropylene fiber layer entangled and joined to the foam layer A laminate is provided.
According to this, a high-strength polypropylene fiber layer is provided on the surface, so that a high-strength laminate can be provided, and liquid can be absorbed by the surface polypropylene fiber layer, so that the liquid absorbency of the laminate is improved. In addition, since it does not have a layer such as an adhesive, there is no unevenness in absorbability, and since the polypropylene fiber layer is all provided on the surface of the foam, a laminate that can prevent leakage after absorption can be provided. Furthermore, the foam layer and the polypropylene fiber layer are intertwined and integrated, whereby the strength of the laminate is improved and the manufacturing processability is also improved.

  Furthermore, the polypropylene fiber layer may be a polypropylene woven fabric or a non-woven fabric, but the non-woven fabric can produce the laminate of the present invention at a lower cost.

  As described above, according to the present invention, in a laminate including a HIPE foam, the processability is improved by improving the strength and toughness of the laminate, and further the liquid absorbency is improved. It is possible to provide a laminate that has no unevenness in absorbability and can prevent leakage after absorption.

Hereinafter, the present invention will be described in more detail.
<High internal phase emulsion>
The high internal phase emulsion in the present invention is a water-in-oil type high internal phase emulsion (hereinafter referred to as HIPE), and is not particularly limited, and a conventionally known one is appropriately used. be able to. Accordingly, the composition of the water-in-oil high internal phase emulsion in the present invention may be a composition generally used, and the following is an example.

  The composition of HIPE is mainly composed of an oil phase component, an aqueous phase component, and other optional components. The continuous oil phase of HIPE contains monomers that polymerize to form a solid porous foam structure and emulsifiers necessary to stabilize the emulsion. In general, the monomers include from about 20 to about 95 weight percent of at least one water-insoluble monofunctional alkyl acrylate or alkyl methacrylate.

  Preferred monomers include 2-ethylhexyl acrylate, n-butyl acrylate, hexyl acrylate, n-octyl acrylate, n-nonyl acrylate, n-decyl acrylate, isodecyl acrylate, n-tetradecyl acrylate, benzyl acrylate, nonyl phenyl acrylate N-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, n-decyl methacrylate, isodecyl methacrylate, n-dodecyl methacrylate, n-tetradecyl methacrylate, and n-octadecyl methacrylate.

  The continuous oil phase also contains from about 2 to about 50% by weight of a water-insoluble multifunctional crosslinking agent (a crosslinking comonomer or crosslinking agent such as a multifunctional crosslinked alkyl acrylate or methacrylate). Exemplary cross-linking monomers include a wide variety of monomers containing two or more activated vinyl groups such as divinylbenzene and analogs thereof. These analogs include divinyl naphthalene, trivinyl benzene, divinyl alkyl benzene, and the like. The crosslinker can also be selected from the group derived from the reaction of acrylic acid or methacrylic acid with polyfunctional alcohols and amines.

  Preferred crosslinking monomers may include monomers containing two or more activated acrylate and / or methacrylate groups, such as 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, Examples include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,12-dodecyl dimethacrylate, 1,14-tetradecanediol dimethacrylate, ethylene glycol dimethacrylate, neopentyl triacrylate, glucose pentaacrylate, sorbitan pentaacrylate, and the like. .

  Other water-insoluble comonomers may be added to the oil phase as appropriate to change the properties. For example, monomers such as styrene, vinyl chloride, isoprene, and chloroprene may be included to impart toughness to the resulting foam.

  The oil phase further contains emulsifiers necessary for HIPE stabilization. Such emulsifiers are not particularly limited as long as they can emulsify the aqueous phase in the oil phase constituting HIPE, and those generally known to those skilled in the art can be used. For example, conventionally known nonionic surfactants, cationic surfactants, amphoteric surfactants, and the like can be used. Preferred emulsifiers include sorbitan monolaurate, sorbitan monooleate, diglycerol monooleate, diglycerol monoisostearate, diglycerol monomyristate, diglycerol cocoyl ethers, and mixtures thereof.

The oil phase is benzoyl peroxide, di-t-butyl peroxide, lauroyl peroxide, azoisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobisiso It may also contain butyronitrile and an oil soluble initiator which is a polymerization initiator well known to those skilled in the art. When using an oil phase polymerization initiator, the addition to the monomer phase is preferably immediately before or during emulsification in order to reduce the possibility of early polymerization. These may be used alone or in combination of two or more in the monomer composition.
The polymerization initiator may be a photoinitiator that can generate a radical, a cation, or the like that can start a polymerization reaction in response to a light source. Types of oil-soluble photoinitiators that are suitable when the photoinitiator is present in the oil phase include benzyl ketals, α-hydroxyalkylphenones, α-aminoalkylphenones, and acylphosphine oxides.

  The discontinuous aqueous phase component of HIPE is generally an aqueous solution containing one or more dissolved components. An essential dissolved component of the aqueous phase is a water-soluble electrolyte. This electrolyte reduces the tendency of mainly oil-soluble monomers, comonomers, and crosslinkers to dissolve in the aqueous phase. The aqueous phase may also contain a polymerization initiator known in the art. Suitable initiators include ammonium persulfate, sodium persulfate, potassium persulfate, 2,2'-azobis (N, N'-dimethyleneisobutylamidine) dihydrochloride, and other such azo initiators. Can be mentioned. The polymerization initiator may be contained in the oil phase, but is preferably contained in the aqueous phase because polymerization is initiated when the aqueous phase is dropped into the oil phase. The initiator may comprise an amount of about 0.05 to 15% by weight, preferably about 0.001 to about 10% by weight, based on the polymerizable monomers present in the oil phase. Moreover, these initiators may be used independently and may use 2 or more types together.

  The aqueous phase contains some electrolyte that can impart ionic strength. Preferred electrolytes are monovalent, divalent, or trivalent inorganic salts such as alkali metal and alkaline earth metal water soluble halides (eg, chlorides), nitrates, and sulfates. Examples include sodium chloride, calcium chloride, sodium sulfate, and magnesium sulfate, preferably calcium chloride. Generally, the electrolyte is about 0.2 to about 40% by weight, preferably about 1 to about 20% by weight of the aqueous phase.

  Water that is the main component of the aqueous phase is pure water, ion-exchanged water, or the like. The water content can be appropriately selected depending on the purpose of use of the foam produced by polymerization (for example, a water absorbing material, an oil absorbing material, a soundproof material, a filter, etc.). For example, what is necessary is just to determine so that HIPE may become the ratio of the desired water phase / oil phase (W / O) mentioned later.

  Various optional ingredients may also be included in the water and / or oil phase for various reasons. For example, as an optional component that composes the HIPE, salts may be used if necessary to improve the stability of the HIPE. Specific examples of such salts include water-soluble salts such as alkali metals such as calcium chloride, sodium sulfate, sodium chloride and magnesium sulfate, halides of alkaline earth metals, sulfates and nitrates. These salts may be used alone or in combination of two or more. These salts are preferably added to the aqueous phase. Of these, polyvalent metal salts are preferred from the viewpoint of the stability of HIPE during polymerization. The content of these salts is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of water.

  Optional components include, for example, antioxidants (for example, hindered amine light stabilizers, UV absorbers), plasticizers (for example, dioctyl phthalate), flame retardants (for example, inorganic salts such as magnesium hydroxide), Dyes and pigments, fluorescent agents, filler particles (eg starch, titanium dioxide, carbon black, or calcium carbonate), odor absorbers such as activated carbon particulates, dissolved polymers and oligomers, and generally for polymers for various reasons Other agents to be added may be mentioned.

  The water phase / oil phase ratio (mass ratio) of the HIPE (hereinafter also simply referred to as “W / O”) can be appropriately selected depending on the intended purpose of use of the foam, For example, if W / O is in the range of 10/1 to 100/1, a foam suitable for use as various absorbent materials such as diapers and sanitary materials can be obtained. However, since the void ratio is determined by W / O, it is preferably 3/1 or more, more preferably 10/1 to 250/1, and particularly preferably 10/1 to 100/1. When W / O is less than 3/1, the ability of the foam to absorb water and energy is insufficient, the degree of opening is low, and the degree of opening on the surface of the resulting foam is low. Liquid performance may not be obtained.

  The manufacturing method of HIPE that can be used in the present invention is not particularly limited, and a conventionally known HIPE manufacturing method can be appropriately used. The typical manufacturing method will be described below. First, with a content suitable for the purpose, the components constituting the oil phase composed of monomers, emulsifiers and the like are stirred at a predetermined temperature to prepare a uniform oil phase. On the other hand, with a content suitable for the purpose, the mixture is stirred while adding a water-soluble polymerization initiator and, if necessary, a component on the water phase side consisting of salts, and heated to a predetermined temperature to obtain a uniform aqueous phase. To prepare.

  Next, the HIPE is stably prepared by mixing the aqueous phase and the oil phase and stirring the mixture by applying an appropriate shearing force. This shear agitation is generally performed for the amount and time required to form a stable HIPE. Such a process can be carried out by known methods, such as batch or continuous, and generally requires suitable conditions, ie water phase droplets, resulting foam to produce HIPE. It is carried out under such conditions that it is dispersed to such an extent that it exhibits structural characteristics. Equipment suitable for making continuously includes static mixers, rotor-stator mixers, and pin mixers. Moreover, in a batch type, it can produce by dripping and mixing by hand or a machine. For example, stronger stirring can be realized by using a driven impeller mixer and a propeller mixing blade.

  The preferable temperature of these water phase and oil phase is in the range of 20 to 100 ° C., and preferably in the range of 40 to 95 ° C. from the viewpoint of HIPE stability. The temperature of the oil phase and / or aqueous phase is adjusted in advance to be mixed. In the manufacture of HIPE, since the amount of the aqueous phase is large, it is preferable to adjust the temperature of the aqueous phase to a predetermined temperature. The HIPE obtained by stirring the aqueous phase and the oil phase is usually a white, high-viscosity emulsion.

<Foam layer>
The foam forming the foam layer used in the laminate according to the present invention is obtained by curing the HIPE (high internal phase emulsion) obtained as described above. Curing refers to the process of converting HIPE to HIPE foam, including the process of polymerizing monomers to polymer and the process of crosslinking. Generally, curing is accomplished by applying heat. Polymerization is the process by which oil phase monomers are converted to relatively high molecular weight polymers. Crosslinking is the process whereby monomers having one or more functional groups with respect to radical polymerization are copolymerized with one or more chains of the growing polymer.

  The curing conditions vary depending on the monomer, the composition of the oil phase / aqueous phase, the type and amount of the polymerization initiator used, and the preferred curing conditions are HIPE above about 50 ° C., more preferably about 65 ° C. At a high temperature above, most preferably above about 80 ° C. for a time in the range of tens of seconds to tens of hours.

  The foam layer is formed as a foam layer intertwined with the polypropylene fiber layer by bringing the HIPE in an emulsion state before curing into contact with one surface of the following polypropylene fiber layer and curing the HIPE in that state. The Here, entangled integration means that at least a part of polypropylene fibers is entangled and bonded to the cured foam without using an adhesive, and the continuous network structure of the foam is polypropylene fibers. Is a state in which at least a part of the fiber is wrapped, or a state in which a continuous network structure of a foam is entangled with at least a part of the polypropylene fiber.

<Polypropylene fiber layer>
The polypropylene fiber layer includes a woven fabric, a nonwoven fabric, a knitted fabric made of polypropylene fibers, and widely includes a liquid-permeable film, a felt, and the like, and preferably a nonwoven fabric. Polypropylene fiber has the lightest specific gravity among fibers, is excellent in elasticity and flexibility, is resistant to friction, and has hydrophobicity. Non-woven fabric is a fiber sheet, web or pad, in which fibers are unidirectionally or randomly oriented, without interweaving and / or fusing and / or chemical / physical adhesion without weaving the fibers. Are combined.

The nonwoven fabric made of polypropylene fibers used in the present invention preferably has an average fiber diameter of 1 μm to 36 μm and 0.006 to 6 dtex, a basis weight of 7 to 400 g / m ² , and a thickness of 0.08 mm to 4.0 mm. It is preferable that the ultrafine fibers are uniformly dispersed and have the same directionality, and the structure is dense and uniform. The production method is not particularly limited, and the needle punch method for entanglement of fibers, the melt blow method for entanglement by blowing off with a high-speed air current, the spunbond method for producing fibers by bonding the fibers in air, and the entanglement of fibers with high-pressure water flow Any method such as a spunlace method may be used.

<Laminate>
In the laminate according to the present invention, the HIPE in the emulsion state is impregnated into the polypropylene fiber by bringing the HIPE in the emulsion state into contact with one surface of the polypropylene fiber layer, and the HIPE is cured in this state to cure the foam after curing. A continuous network structure and polypropylene fibers are formed by intertwining each other. A polypropylene fiber layer made of polypropylene fibers is provided on the surface of a foam layer made of a foam obtained by curing HIPE. The foam is formed into a sheet-like foam layer, and is provided on one (one side), preferably both (both sides) surfaces of the foam layer.

  The foam layer in the laminate has a fine and uniform bubble diameter, and is a porous body composed of three-dimensionally continuous bubbles. Therefore, the foam layer absorbs liquids such as water and oil and has a high liquid absorbency. The polypropylene fiber layer in the laminate reinforces the foam layer having poor stretchability and toughness from the surface, and improves the strength and toughness of the laminate. As a result, the foam layer alone may be broken when incorporated into a machine, or the surface may be cracked or cracked, but the manufacturing processability is improved. In addition, since the surface is a polypropylene fiber layer, it is easy to get wet, and the dropped liquid first propagates through the fibers on the surface, so that the liquid does not concentrate in one place but spreads over a wide area, and the possibility of spreading to the back is reduced. Further, the foam layer having a strong liquid absorption performance and the polypropylene fiber layer having a hydrophobic surface reduce the possibility that the liquid contained in the foam layer leaks from the polypropylene fiber layer to the outside. Furthermore, since the foam layer and the polypropylene fiber layer are intertwined and integrated as defined above without using an adhesive, the liquid absorbability is improved and the absorbability is not uneven.

  Therefore, according to the present invention, a high-strength polypropylene fiber layer is provided on the surface, so that a high-strength laminate can be provided, and liquid can be absorbed by the surface of the polypropylene fiber layer. Providing a laminate that prevents leakage after absorption because there is no unevenness in absorbability because there is no layer of adhesive, etc., and preferably there is a polypropylene fiber layer on the entire surface of the foam. it can. Furthermore, when the foam layer and the polypropylene fiber layer are intertwined and integrated, the strength and liquid absorbency of the laminate are further improved, and the manufacturing processability is also improved. Furthermore, a laminated body can be produced at low cost by using a polypropylene nonwoven fabric for the polypropylene fiber layer.

  Sheet-like laminates are used in various applications such as ink-absorbing sheets, disposable diapers, sanitary products, medical clothing, towels, masks, chemical wipes, flooring wipers, and kitchen paper.

  In addition, after HIPE hardens | cures and forms a foam layer, in order to remove the water phase substance which remains in a porous body bubble, a laminated body is normally compression-dehydrated with a roll etc., wash | cleaned, and heat-dried. However, it is not limited to this, For example, you may use vacuum dehydration and a microwave.

<Example 1>
The laminated body of the present Example used the high internal phase emulsion adjusted as follows. The oil phase of this high internal phase emulsion is 2.8 g of 2-EHA (2-ethylhexyl acrylate: manufactured by Toagosei Co., Ltd.), 1.2 g of MMA (methyl methacrylate: manufactured by Mitsubishi Rayon Co., Ltd.), EGM (ethylene glycol). It consists of 0.9 g of dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.), 0.3 g of BM (benzyl methacrylate: manufactured by Kyoeisha Chemical Co., Ltd.), and 0.3 g of DO-100 (diglycerin monooleate: RIKEN vitamin) as an emulsifier.

  The aqueous phase of the high internal phase emulsion was prepared by dissolving 1.98 g of calcium chloride and 0.5 g of sodium persulfate (manufactured by Adeka) as a polymerization initiator in 150 g of distilled water. The oil phase was placed in a 500 ml beaker, and the entire aqueous phase was dropped into the beaker containing the oil phase with a dropping funnel over 15 minutes while stirring at a stirring speed of 300 rpm.

As the polypropylene fiber layer, a polypropylene nonwoven fabric (PO20SW-00X: manufactured by Tapirs) was used. This PO20SW-00X has a basis weight of 20 g / m ² , a thickness of 0.23 mm, an air permeability of 65 cc / cm ² / sec, and a maximum bubble diameter of 45 μm. The above-mentioned polypropylene non-woven fabric is placed on a PET film, and a spacer having a thickness of 3 mm is further placed. The above high internal phase emulsion is poured between the spacers, the same polypropylene nonwoven fabric is placed thereon, and the PET film is placed thereon. From there, it was flattened with a roller, and a glass plate was placed on it and thermally cured at 80 ° C. for 30 minutes while applying its own weight. The laminate including the cured foam was dehydrated with a roll and then dried at 75 ° C. for 1 hour to obtain a laminate sample. The size of this laminate sample is 180 mm × 30 mm (thickness 8 mm). The laminate thus produced comprises a foam layer obtained by curing a high internal phase emulsion and a polypropylene fiber layer on the surface of the foam layer, and the foam layer and the polypropylene fiber layer are intertwined. It is an integrated laminate.

  As shown in Table 1, the laminate in this example has excellent adhesion, and the delamination force is 2.00 N / 30 mm. The measurement method and the evaluation method will be described later.

<Example 2>
In this example, a polypropylene nonwoven fabric (PO30FW-00X: manufactured by Tapirs) was used for the polypropylene fiber layer. This PO30FW-00X has a basis weight of 30 g / m ² , a thickness of 0.38 mm, a fiber diameter of 4 μm, an air permeability of 27 cc / cm ² / sec, and a maximum bubble diameter of 31 μm. Other than this, the second embodiment is the same as the first embodiment.
The laminated body in a present Example is excellent in adhesiveness, and the delamination force is 2.00 N / 30mm.

<Example 3>
In this example, a polypropylene nonwoven fabric (PO45CW-00X: manufactured by Tapirs) was used for the polypropylene fiber layer. This PO45CW-00X has a basis weight of 45 g / m ² , a thickness of 0.64 mm, and a fiber diameter of 30 μm. Other than this, the second embodiment is the same as the first embodiment.
The laminate in this example is excellent in adhesion, and the delamination force is 0.18 N / 30 mm.

<Example 4>
In this example, a polypropylene nonwoven fabric (PK-103: manufactured by Mitsui Chemicals) was used for the polypropylene fiber layer. This PK-103 has a basis weight of 15 g / m ² , a thickness of 0.15 mm, and a fiber diameter of 34 μm. Other than this, the second embodiment is the same as the first embodiment.
The laminate in this example has excellent adhesion, and the delamination force is 0.10 N / 30 mm.

<Example 5>
In this example, a polypropylene nonwoven fabric (PS-103: manufactured by Mitsui Chemicals) was used for the polypropylene fiber layer. Other than this, the second embodiment is the same as the first embodiment. This PS-103 has a basis weight of 16 g / m ² , a thickness of 0.18 mm, and a fiber diameter of 21 μm.
The laminated body in a present Example is excellent in adhesiveness, and the delamination force is 0.15 N / 30mm.

<Example 6>
In this example, a polypropylene nonwoven fabric (PS-108: manufactured by Mitsui Chemicals) was used for the polypropylene fiber layer. Other than this, the second embodiment is the same as the first embodiment. This PS-108 has a basis weight of 40 g / m ² , a thickness of 0.35 mm, and a fiber diameter of 33 μm.
The laminated body in a present Example is excellent in adhesiveness, and the delamination force is 2.00 N / 30mm.

<Example 7>
In this example, a polypropylene nonwoven fabric (PS-120: manufactured by Mitsui Chemicals) was used for the polypropylene fiber layer. Other than this, the second embodiment is the same as the first embodiment. This PS-120 has a basis weight of 100 g / m ² , a thickness of 0.6 mm, and a fiber diameter of 22 μm.
The laminate in this example is excellent in adhesion, and the delamination force is 0.18 N / 30 mm.

<Example 8>
In this example, a polypropylene nonwoven fabric (MPEA04: manufactured by Mitsui Chemicals) was used for the polypropylene fiber layer. Other than this, the second embodiment is the same as the first embodiment. This MPEA04 has a basis weight of 20 g / m ² , a thickness of 0.24 mm, and a fiber diameter of 22 μm.
The laminate in this example is excellent in adhesion, and the delamination force is 0.12 N / 30 mm.

<Comparative Example 1>
In this comparative example, a polyethylene nonwoven fabric (Tyvek: manufactured by DuPont) was used for the fiber layer. Other than this, the second embodiment is the same as the first embodiment.
As shown in Table 1, the laminate in this comparative example is extremely inferior in adhesion, and the delamination force cannot be measured. That is, the adhesion in the laminate of the comparative example is that the HIPE porous layer and the polyethylene nonwoven fabric are not entangled and joined, and when the end of the nonwoven fabric is picked up, only the nonwoven fabric is lifted and the HIPE porous layer is separated and left. .

<Comparative Example 2>
In this comparative example, the fiber layer was pulp (B-50: manufactured by Toyo Shoji Co., Ltd.). Other than this, the second embodiment is the same as the first embodiment.
The laminate in this comparative example is inferior in adhesion, and the delamination force cannot be measured.

<Comparative Example 3>
In this comparative example, a rayon nonwoven fabric (3020: manufactured by Toyo Shoji Co., Ltd.) was used for the fiber layer. Other than this, the second embodiment is the same as the first embodiment.
The laminate in this comparative example is inferior in adhesion, and the delamination force cannot be measured.

<Comparative example 4>
In this comparative example, nylon was used for the fiber layer. Other than this, the second embodiment is the same as the first embodiment.
The laminate in this comparative example is inferior in adhesion, and the delamination force cannot be measured.

<Comparative Example 5>
In this comparative example, hemp was used for the fiber layer. Other than this, the second embodiment is the same as the first embodiment.
The laminate in this comparative example is inferior in adhesion, and the delamination force cannot be measured.

<Comparative Example 6>
In this comparative example, polyester was used for the fiber layer. Other than this, the second embodiment is the same as the first embodiment.
The laminate in this comparative example is inferior in adhesion, and the delamination force cannot be measured.

<Comparative Example 7>
In this comparative example, the fiber layer used was a blend of silk and cotton (20:80). Other than this, the second embodiment is the same as the first embodiment.
The laminate in this comparative example is inferior in adhesion, and the delamination force cannot be measured.

<Comparative Example 8>
In this comparative example, cotton was used for the fiber layer. Other than this, the second embodiment is the same as the first embodiment.
The laminate in this comparative example is inferior in adhesion, and the delamination force cannot be measured.

<Comparative Example 9>
In this comparative example, the fiber layer used acrylic. Other than this, the second embodiment is the same as the first embodiment.
The laminate in this comparative example is inferior in adhesion, and the delamination force cannot be measured.

<Contrast of Examples and Comparative Examples>
The fiber layers in Examples 1 to 8 are all polypropylene nonwoven fabrics. None of the polypropylene nonwoven fabrics has a fiber diameter of 3 to 37 μm, a basis weight of 13 to 130 g / m ² , and a thickness of 0.15 to 0.70 mm. Therefore, regardless of the fiber diameter, basis weight, and thickness, if the fiber layer is a polypropylene fiber layer, the laminate can be said to have excellent adhesion and strong delamination force.

  On the other hand, in comparative examples, when evaluated against many types of fibers other than polypropylene fibers, excluding inorganic fibers (asbestos fibers, glass fibers, carbon fibers, ceramic fibers, metal fibers, whiskers, rock wool, etc.) In any fiber, the adhesion is poor and there is almost no delamination force. Although not shown as experimental results, organic fibers such as polyamide fibers, acetate fibers, vinyl chloride fibers and vinylidene chloride fibers, and natural fibers such as wool, palm fibers and bamboo fibers also have poor adhesion and delamination. There is little power.

<Adhesion evaluation method>
As for the adhesiveness, when the two fiber layers positioned on the front and back surfaces of the obtained laminate sample are pulled and the HIPE foam layer between the fiber layers breaks down, the adhesiveness is excellent. In the case where only the fiber layer peeled without breaking the material and separated into three layers of two fiber layers and a HIPE foam layer, “x” was given as being inferior in adhesion.

<Measurement method of delamination force>
The delamination force between the fiber layer and the HIPE foam layer was measured by a 180 ° peel test with an autograph. The laminate sample was peeled 80 mm in the vertical direction, and the peel test of the remaining 100 mm was performed at a peel speed of 300 mm / min.
<Method for measuring thickness of nonwoven fabric>
Page: 10 Thickness of non-woven fabric is measured according to JIS K 6402: 1976, “Soft urethane foam for clothing”, using a constant pressure thickness measuring instrument (TECLOCK Co., Ltd., Model J Type PG-11) at a pressing force of 363 Pa. Did.

  In addition, this invention is not limited to the illustrated Example, The implementation by the structure of the range which does not deviate from the content described in each item of a claim is possible.

Claims (3)

A foam layer obtained by curing the high internal phase emulsion;
A polypropylene fiber layer is provided on the surface of the foam layer,
A laminate in which the polypropylene fiber layer is entangled and joined to the foam layer .   The laminate according to claim 1, wherein the polypropylene fiber layer is a polypropylene nonwoven fabric. The high internal phase emulsion in an emulsion state before curing is brought into contact with one surface of the polypropylene fiber layer,
Impregnating the polypropylene fiber layer with the high internal phase emulsion in the emulsion state;
In that state, the high internal phase emulsion is cured to form a foam layer,
The manufacturing method which manufactures the laminated body which the said polypropylene fiber layer entangled and joined to the said foam layer.