JP6131163B2 - Synthetic resin skin material and method for producing the same - Google Patents

Description

  The present invention relates to a synthetic resin skin material and a method for producing the same.

In recent years, automobile interior parts (instrument panels, door trims, seats, ceilings, etc.), railway vehicle / aircraft interior parts (trims, seats, ceilings, etc.), furniture, shoes / footwear / bags, interior / exterior components for construction, clothing cover materials -For the lining and wall coverings, synthetic resin skin materials with excellent durability are often used instead of natural leather and fibrous sheets. Such a synthetic resin skin material has irregularities similar to natural leather on the outermost surface, that is, a squeezed pattern, and this squeezed pattern characterizes the appearance.
For example, with respect to automobile interior parts, it has become important to give a high-class feeling to the interior skin material as the vehicle is upgraded.
FIG. 2 is a schematic cross-sectional view of a synthetic resin skin material 30 having a conventional vinyl chloride resin layer 18. The synthetic resin skin material 30 is bonded to the surface of the base fabric 12 via the adhesive layer 14 with the elastic vinyl chloride foam layer 16 including air bubbles. The vinyl chloride resin layer 18 is attached to the surface of the vinyl chloride foam layer 16. The surface of the vinyl chloride resin layer 18 has a skin layer 24 for adjusting the appearance and feel.
Such a skin material requires a moist feel and soft texture that is not inferior to that of natural leather. In order to give a soft feel, for example, a thin-layer vinyl chloride resin sheet 18 having excellent flexibility is used. When is used in the vicinity of the surface, there is a problem that the wear resistance of the surface is lowered.
Since automobile interior parts and furniture used daily require durability, it is important to be able to maintain a good appearance and texture for a long period of time.
In order to improve the wear resistance, when the vinyl chloride resin layer 18 existing in the vicinity of the surface is thickened or a high strength vinyl chloride resin layer is used, not only the texture is impaired, but also flexibility and flexibility are obtained. As a result, it has become difficult to apply as a skin material to a molded article having complicated irregularities such as a vehicle sheet, and a synthetic resin skin material having higher flexibility and superior durability has been demanded.

  As a technique for improving flexibility and elasticity using a vinyl chloride resin layer, a method of producing vinyl leather by a calendar method by adding an acrylic resin and glass microspheres to a vinyl chloride resin (see, for example, Patent Document 1) Or vinyl leather (for example, see Patent Document 2) in which a large amount of plasticizer and glass microspheres are contained in a vinyl chloride resin.

JP-A-6-116876 JP-A-6-116875

However, when the vinyl chloride resin layer contains fragile glass microspheres, the resulting vinyl leather is lightweight and has a good initial texture, but when compressive stress is repeatedly applied, its elasticity and flexibility gradually decrease. Therefore, it was not suitable for application to automobile interior parts and furniture such as chairs.
The object of the present invention made in consideration of the above-mentioned prior art is to provide a synthetic resin skin material that is compatible with wear resistance, excellent texture and flexibility, and can be suitably used for a molded article having complicated irregularities, and An object of the present invention is to provide a method for producing a synthetic resin skin material excellent in wear and texture.

As a result of intensive studies, the present inventors have been able to solve the above-mentioned problems by applying a wear resistance treatment to the surface of the vinyl chloride resin layer and providing a surface treatment layer containing organic particles having a good feel on the outermost surface. The present invention has been completed.
That is, the present invention has the following configuration.
The invention according to the first embodiment of the present invention includes a vinyl chloride foam layer, a vinyl chloride resin layer, a water-based crosslinked polyurethane layer, and a surface treatment layer containing a resin and organic particles on a base fabric. It is a synthetic resin skin material provided in order.

In the invention according to the second embodiment of the present invention, the water-based crosslinked polyurethane layer is a layer having a thickness of 2 μm to 15 μm formed by crosslinking water-based polyurethane with a carbodiimide-based crosslinking agent. The synthetic resin skin material described in 1.
In the invention according to the third embodiment of the present invention, the organic particles are organic particles having an average particle diameter of 1 μm to 10 μm selected from the group consisting of urethane resin particles, protein particles, and acrylic beads. It is a synthetic resin skin material as described in 1st Embodiment or 2nd Embodiment.
The invention according to a fourth embodiment of the present invention is the synthetic resin skin according to any one of the first to third embodiments, wherein the water-based crosslinked polyurethane layer further contains a silicone compound. It is a material.
The invention according to a fifth embodiment of the present invention includes any one of the first to fourth embodiments having an adhesive layer 14 between the base fabric and the vinyl chloride foam layer. The synthetic resin skin material described in 1.
In the invention according to the sixth embodiment of the present invention, the ratio of the vertical and horizontal elongation measured in accordance with JIS K6772 is in the range of vertical elongation: horizontal elongation = 1: 1 to 1: 2. It is a synthetic resin skin material of any one of 1st Embodiment-5th Embodiment.

The invention according to the seventh embodiment of the present invention is a laminate formation for forming a laminate of a vinyl chloride resin layer and a composition layer for forming a vinyl chloride foam layer comprising a composition containing a foaming agent and a resin. A base cloth bonding step for bonding a base cloth to the vinyl chloride foam layer forming composition layer side of the laminate, and a water-based polyurethane resin and a crosslinking agent on the surface of the laminate on the vinyl chloride resin layer side. A composition containing a resin and organic particles is applied to the surface of the water-based crosslinked polyurethane layer by providing a composition containing, and drying to form a water-based cross-linked polyurethane layer. A synthetic resin skin material comprising: a surface treatment layer forming step for forming a treatment layer; and a foaming step for foaming the foaming agent in the composition for forming a vinyl chloride foam layer by heating to form a vinyl chloride foam layer. It is a manufacturing method.
The invention according to an eighth embodiment of the present invention is the manufacture of the synthetic resin skin material according to the seventh embodiment, wherein the foaming step is performed after the cross-linked layer forming step and the surface treatment layer forming step. Is the method.
The ninth embodiment of the present invention relates to the seventh embodiment, wherein the foaming step is carried out after the base fabric bonding step and prior to the crosslinked layer forming step and the surface treatment layer forming step. It is a manufacturing method of the synthetic resin skin material as described in above.

  In the invention according to the tenth embodiment of the present invention, the base fabric bonding step includes the step of providing an adhesive layer between the vinyl chloride foam layer forming composition layer and the base fabric of the laminate. It is a synthetic resin skin material of any one of 7th Embodiment-9th Embodiment.

In the present invention, by providing the water-based crosslinked polyurethane layer 20 on the surface of the thin vinyl chloride resin layer 18 having excellent flexibility, the wear resistance is improved, the vinyl chloride resin layer is thickened, Necessary wear resistance and durability can be obtained without using a vinyl chloride resin layer. In a preferred embodiment of the present invention, by using a carbodiimide-based crosslinking agent for crosslinking of the water-based polyurethane, a high-density crosslinked structure is formed, and the wear resistance is further improved without reducing flexibility. Moreover, when a water-system crosslinked polyurethane layer contains a silicone compound further, surface energy falls more and abrasion resistance improves more.
In addition, the resin matrix that forms the surface treatment layer contains organic particles with excellent flexibility and nearly spherical shape, compared to the case of using amorphous inorganic particles that have been widely used as matting agents. Thus, the texture and feel are excellent.
Although there is no restriction | limiting in particular in the base fabric 12 used for the synthetic resin skin material of this invention, By using a knitted fabric as the base fabric 12, it has the advantage that elasticity and a stretching property improve more.
As described above, the synthetic resin skin material of the present invention is excellent in surface wear resistance and durability, and is flexible and excellent in texture. Therefore, the interior material for vehicles such as a vehicle seat and the surface material of a chair are used. Is preferably used.

  ADVANTAGE OF THE INVENTION According to the present invention, a synthetic resin skin material that has both wear resistance, excellent texture and flexibility, and can be suitably used for a molded article having complex irregularities, and a synthetic resin excellent in wear resistance and texture. A method for producing a skin material can be provided.

It is a schematic sectional drawing which shows the one aspect | mode of the synthetic resin skin material of this invention. It is a schematic sectional drawing which shows the one aspect | mode of the conventional synthetic resin skin material.

Hereinafter, preferred embodiments of the present invention will be described.
<Synthetic resin skin material>
First, the synthetic resin skin material will be described with reference to FIG. FIG. 1 is a schematic cross-sectional view showing one embodiment of the layer structure of the synthetic resin skin material 10 of the present invention.
The synthetic resin skin material 10 of the present invention has a vinyl chloride foam layer 16, a vinyl chloride resin layer 18, a water-based crosslinked polyurethane layer 20, a surface treatment layer 22 containing a polyurethane resin and organic particles on a base fabric 12. Are provided in this order.
In the present invention, “providing in this order” means having the above-described layers on the base fabric 12 in this order, and denying the presence of any layer provided as desired, for example, an adhesive layer. It is not a thing.
The surface treatment layer 22 located on the outermost surface of the synthetic resin skin material 10 may be colored according to the purpose, printed, or formed with natural leather-like irregularities represented by a drawn pattern. .
As shown in FIG. 1, the synthetic resin skin material 10 of the present invention has an adhesive layer 14 between the base fabric 12 and the vinyl chloride foam layer 16 in terms of durability and shape followability improvement. To a preferred embodiment.
The adhesive layer 14 is formed by laminating an adhesive on the surface of the base fabric 12 and drying it. Lamination of the adhesive may be performed by a transfer method or a coating method.

Hereinafter, the synthetic resin skin material of the present invention (hereinafter sometimes simply referred to as “skin material”) will be sequentially described together with the materials constituting the same and the manufacturing method thereof.
(1. Base fabric)
As the base fabric 12 of the synthetic resin skin material 10 of the present invention, any fabric can be appropriately selected and used depending on the purpose as long as it has necessary strength and durability, and any of knitted fabric, woven fabric, and nonwoven fabric can be used. There may be.
When the skin material is to be contributed by an uneven molded body, it is preferable to use a knitted fabric or a woven fabric having a certain degree of elasticity, and from the viewpoint of feel and shape followability, the ratio of vertical to horizontal elongation is uniform. It is preferable to use a relatively thick base fabric 12. The synthetic resin skin material of the present invention preferably has a vertical and horizontal elongation ratio as detailed below, and the vertical elongation: horizontal elongation ratio is in the range of 1.5: 1 to 1: 2. In order to achieve such physical properties, it is preferable that the ratio of the vertical and horizontal elongations of the base fabric used is uniform.
Here, the vertical indicates the longitudinal direction of the apparatus for producing the synthetic resin skin material, and the horizontal indicates the direction perpendicular to the vertical, that is, the width direction.
As the base fabric, for example, when used as a skin material for a vehicle seat, a knitted fabric or a modified knitted fabric is preferable from the viewpoint of stretchability and ease of thickness control.
A three-dimensional nonwoven fabric may also be used from the viewpoint of easy thickness adjustment.
The material of the fiber (yarn) used for the base fabric 12 is preferably a yarn made of polyester, polyamide, rayon or the like, or a mixed yarn containing these.
As the base fabric 12, in addition to the above knitted fabric, for example, a synthetic leather base fabric using ponchiroma knitting described in Japanese Patent Laid-Open No. 2013-72141 previously proposed by the applicant of the present application can be used. .
The thickness of the base fabric 12 is appropriately selected according to the purpose of use of the skin material, but is preferably in a range that is excellent in touch and does not reduce flexibility, for example, a range of 0.15 mm to 0.6 mm, and 0.3 mm to 0 mm. A range of 0.5 mm is more preferable.

(2. Vinyl chloride foam layer)
As the vinyl chloride foam layer (hereinafter also referred to as “foam layer”) 16 in the skin material 10 of the present invention, a foam layer-forming composition layer containing a foaming agent and a resin is formed, and then the foaming agent is foamed by heating. And forming a vinyl chloride foam layer having fine bubbles.
The resin used for forming the foamed layer 16 includes a vinyl chloride resin.
The vinyl chloride resin that can be used to form the foam layer 16 will be described in detail in the description of the vinyl chloride resin layer 18 below. The vinyl chloride resin described in detail below can be suitably used for forming the foamed layer 16.
The foaming agent is not particularly limited as long as it can form fine bubbles that give the elasticity and thickness necessary for the vinyl chloride foam layer 16, but azodicarbonamide (ADCA), p, p that foams by heating. Examples thereof include chemical foaming agents such as' -oxybisbenzenesulfonyl hydrazide (OBSH), and thermally expanded beads.

The thermally expanded beads used in the coating liquid for forming the foamed layer are particles in which an organic solvent such as a hydrocarbon solvent is encapsulated in hollow thermoplastic resin particles. The volume is increased, and as a result, the foamed layer 16 in which bubbles are contained in the resin matrix (dispersion medium) is formed.
As the thermally expandable beads used in the present invention, any bead may be used as long as it expands by heating to form bubbles in the resin matrix and can maintain the state of the formed bubbles.
Thermally expanded beads are also available as commercial products, such as EXPANSEL series (trade name) manufactured by Nippon Ferrite Co., Ltd., any of which can be used in the present invention.
The addition amount of the thermally expanded beads is preferably 0.5 parts by mass to 10 parts by mass, and more preferably 1 part by mass to 7 parts by mass with respect to 100 parts by mass of the resin.

In the composition for forming a vinyl chloride foam layer in the present invention, from the viewpoint of efficient drying, it is preferable to use an organic solvent instead of water as a solvent, but this solvent does not dissolve the resin constituting the thermally expanded beads. Is preferably selected. This is because when the resin constituting the thermally expanded beads is dissolved by the organic solvent, the hollow portion cannot be maintained, and it becomes difficult to form the foamed layer 16 containing the desired bubbles.
As a method of selecting a solvent that does not dissolve the resin constituting the thermally expanded beads, the thermally expanded beads to be used are immersed in an organic solvent to be evaluated (including simple substances and mixtures) at room temperature (25 ° C.) for 3 days, and then visually determined. The method of selecting the organic solvent without the trace of foaming by is mentioned. When the resin constituting the thermally expandable beads is dissolved in an organic solvent, the outer surface of the resin beads is damaged, and bubbles are observed by flowing into the organic solvent in which the gas encapsulated in the thermally expanded beads or the hydrocarbon solvent is immersed. Such an organic solvent is not included in the “solvent that does not dissolve the resin constituting the thermally expanded beads” in the present invention.

For example, when the EXPANSEL manufactured by Nippon Ferrite Co., Ltd. is used as the thermal expansion bead, the usable solvents include methyl alcohol, ethyl alcohol, isopropyl alcohol (IPA), toluene, styrene, acetone, ethyl acetate, ethylene Examples include glycol, n-hexane, cyclohexane, methyl ethyl ketone (MEK), and propylene glycol monomethyl ether (PGME). One or more of these solvents may be appropriately selected and used.
The heating temperature for expanding the thermally expanded beads contained in the vinyl chloride foam layer forming composition layer is preferably in the range of 130 ° C to 230 ° C, and preferably in the range of 190 ° C to 230 ° C. More preferred.

  There is no restriction | limiting in particular in the film thickness of the foaming layer 16, Although it selects suitably according to the objective, Generally, it is the range of 150 micrometers-700 micrometers as a film thickness before foaming from a viewpoint of intensity | strength and tactile sense. Is preferable, and the range of 170 μm to 450 μm is more preferable. The film thickness of the vinyl chloride foam layer 16 containing bubbles after foaming is preferably in the range of 220 μm to 1300 μm, and more preferably in the range of 400 μm to 900 μm.

(3. Vinyl chloride resin layer)
The skin material 10 includes a vinyl chloride resin layer 18 adjacent to the vinyl chloride foam layer.
The vinyl chloride resin layer 18 may be formed as a laminate by calendering or simultaneous extrusion simultaneously with the vinyl chloride foam layer-forming composition layer, and paste on the surface of the vinyl chloride foam layer-forming composition layer. The vinyl chloride resin layer 18 may be formed by a processing machine or an extruder to form a laminate of the vinyl chloride foam layer forming composition layer and the vinyl chloride resin layer 18.
Since the abrasion resistance of the surface is improved by forming the water-based crosslinked polyurethane layer 20 described later, the vinyl chloride resin layer 18 is harder than necessary and does not require a thick layer, and can be obtained by making it soft and thin. The texture as the skin material 10 becomes soft and can be easily stuck on a sheet having a complicated shape.
Specifically, the thickness of the vinyl chloride resin layer 18 conventionally required from the viewpoint of wear resistance of 200 μm to 350 μm can be set in the range of 100 μm to 250 μm in the present invention. Preferably, it is the range of 100 micrometers-200 micrometers.
As the vinyl chloride resin forming the vinyl chloride resin layer 18, any vinyl chloride that is widely used for the skin material 10 can be used. A commercial item may be used as a vinyl chloride resin, for example, the brand name "TH-1300" by Taiyo PVC Co., Ltd. is mentioned.
In the method for manufacturing the skin material 10 of the present invention, as described above, first, a laminate of the vinyl chloride foam layer forming composition layer and the vinyl chloride resin layer 18 is formed.

(4. Water-based crosslinked polyurethane layer)
The skin material 10 of the present invention includes a water-based crosslinked polyurethane layer 20 for the purpose of improving wear resistance.
Examples of the water-based polyurethane used for forming the water-based crosslinked polyurethane layer 20 include polycarbonate-based polyurethane, polyether-based polyurethane, polyester-based polyurethane, and modified products thereof. When long-term durability is required, the polycarbonate-based polyurethane is used. Polyurethane is preferred.
The polyether-based or polycarbonate-based aqueous polyurethane in the present invention may be used alone or in combination with other polyurethane resins as long as the effects of the present invention are not impaired. Such a water-based polyurethane main component is preferably a so-called self-emulsifying water-based polyurethane in which one or two or more hydrophilic carboxyl groups are introduced into a part of the molecular chain to facilitate dispersion in water. The self-emulsifying water-based polyurethane is obtained by neutralizing a prepolymer prepared from a polyether-based or polycarbonate-based diol, a diol-containing low molecular weight material, dimethylolalkylcarboxylic acid and diisocineanate with an alkali or the like according to a conventional method. Thus, it can be obtained by dispersing in water with a nano-sized particle diameter while polymerizing with a diamine chain extender.

Examples of water-based polyurethanes suitable for the present invention include polycarbonate-based polyurethanes, polyether-based polyurethanes, polyester-based polyurethanes, and modified products thereof, which may be single or polyether-based and polycarbonate-based mixed or copolymerized products. Good. The aqueous polyurethane is part of the molecular chain of the urethane main agent and is 0.01% to 10%, preferably 0.05% to 5%, more preferably 0.1% to 0.1% by mass with respect to the aqueous polyurethane main agent. It is desirable to have 2% carboxyl groups introduced. Sufficient water dispersibility and dry film formability can be obtained within the above mass ratio range.
The water-based crosslinked polyurethane layer 20 is provided for imparting strength and wear resistance. From such a viewpoint, the water-based polyurethane needs to have a crosslinked structure.
That is, when the water-based crosslinked polyurethane layer 20 is formed, by using a urethane main component into which a carboxyl group is introduced, the composition for forming a cross-linked layer contains the water-based polyurethane and the cross-linking agent. The group and the crosslinking agent react to form a crosslinked structure, and the wear resistance of the crosslinked layer 20 is dramatically improved.
As a crosslinking agent for forming a crosslinked structure, conventionally known isocyanate crosslinking agents, epoxy crosslinking agents, aziridine crosslinking agents, carbodiimide crosslinking agents, and the like are suitable, and oxazoline-based crosslinking agents are also preferably used. Especially, it is more preferable to use a carbodiimide crosslinking agent from the viewpoint that a three-dimensional crosslinked structure is easily formed, a dense crosslinked structure is formed, and hydrolysis of the aqueous polyurethane can be suppressed.
The addition amount of a crosslinking agent typified by a carbodiimide crosslinking agent is preferably 2% by mass to 10% by mass with respect to the composition for forming a crosslinked layer.

The aqueous polyurethane used in forming the crosslinked layer 20 may be hardness measured by JIS K6772 is a water-based polyurethane which can form a film in the range of ^50N / cm ^{2 ~1200N} / cm 2 at 100% modulus it is ^preferred, more preferably in the range of ^{98N / cm 2 ~1176N / cm 2} , and more preferably in the range of ^{196N / cm 2 ~980N / cm 2} .
Moreover, it is preferable that the said water-based polyurethane used as a main ingredient at the time of forming the crosslinked layer 20 is the range whose weight average molecular weights measured by GPC method are 50,000-150,000.

The composition for forming the crosslinked layer 20 may contain various components in addition to the aqueous polyurethane, the crosslinking agent, and the solvent for forming the composition as long as the effects of the present invention are not impaired.
Examples of components that can be included in the crosslinked layer 20 include silicone compounds and colorants for improving slipperiness.
By containing the silicone compound, the slipperiness of the surface is improved and the wear resistance is further improved. Any silicone compound can be used without particular limitation as long as it has good affinity with other components contained in the crosslinked layer 20 and can improve the surface slipperiness of the formed crosslinked layer 20.
When the silicone compound is contained, the content is preferably 10% by mass to 30% by mass in the composition for forming a crosslinked layer.

Moreover, the skin material which has a desired hue can be obtained because the crosslinked layer 20 contains a coloring agent.
Examples of the colorant include pearl particles, metal powders such as aluminum powder, and pigments. Among these, pigments are generally used.
Examples of the pigment that can be used in the present invention include carbon black and titanium dioxide. For example, when carbon black is used, it is preferably used as a mixture in which carbon black, an ester dispersant, and an acrylic resin are mixed in advance.
If an example of the usage aspect of a pigment is given, with respect to 100 mass parts of water-based polyurethane used as a main ingredient, about 3 mass parts-5 mass parts of pigments will be thrown in, and a polyurethane will be colored by heat-mixing with a heat mixing roll.
When colorants such as pearl particles, aluminum powder, and pigments are used, their average particle size is generally preferably in the range of 0.5 μm to 100 μm, more preferably in the range of 3 μm to 50 μm. It is.
The cross-linked layer 20 may contain only one type of colorant, or may contain two or more types for purposes such as toning. There is no restriction | limiting in particular in content of a pigment, Although it selects suitably according to the hue of the target crosslinked layer 20, 3 mass%-20 mass in the total solid which comprises the crosslinked layer 20 generally. % Is preferred. In addition, solid content means all the components except a solvent in all the components which comprise a base material layer here.

Although there is no restriction | limiting in particular in the thickness of the bridge | crosslinking layer 20, Since it is excellent in abrasion resistance also by a thin layer resulting from a bridge | crosslinking structure, thickness should just be in the range of 2 micrometers-15 micrometers, and is the range of 5 micrometers-10 micrometers. It is more preferable.
When the film thickness of the crosslinked layer 20 is in the above range, a sufficient wear resistance effect is obtained, and the occurrence of problems such as whitening when the obtained skin material is bent is suppressed.
The crosslinked layer 20 is formed by a coating method, and gravure printing is generally used, but may be formed by reverse coating or direct coating.
After the layer made of the composition for forming a crosslinking agent is formed on the surface of the vinyl chloride resin layer 18, formation of a crosslinked structure by the crosslinking agent in the composition proceeds by heating and drying to form an aqueous crosslinked polyurethane layer. The
The heating temperature during drying is preferably 80 ° C. to 150 ° C., more preferably 100 ° C. to 120 ° C., from the viewpoint that the crosslinked structure proceeds efficiently.
The heating method may be non-contact heating such as warm air drying or zone drying with a heater, or contact heating with a hot roll or the like. In addition, a heated calender roll may be brought into contact with the surface, and the formation of an uneven pattern such as squeezing, heating, and drying may be performed simultaneously.

(5. Surface treatment layer)
The skin material 10 of the present invention includes a surface treatment layer 22 containing organic particles for the purpose of improving the appearance and feel.
The surface treatment layer 22 is a touch improving layer and includes a resin base material and organic particles.
Examples of the resin that can be included in the surface treatment layer 22 include polyurethane, acrylic resin, fluororesin, vinyl chloride resin, and the like. From the viewpoint of good feeling, it is preferable to use polyurethane as a main agent. Here, the “main agent” means a resin having the highest content ratio when a plurality of resins are used in combination.
As a polyurethane used for the surface treatment layer 22, a water-based polyurethane used for forming a water-based crosslinked polyurethane layer is preferable.
The acrylic resin used for the surface treatment layer 22 is, for example, a polymer or copolymer of methacrylic acid or a methacrylic ester represented by polymethyl methacrylate (PMMA), alkyl methacrylate, alkyl acrylate, and styrene. And the like.

By including the organic particles as the filler in the surface treatment layer 22, compared to the case where an amorphous inorganic filler that has been conventionally used as a matting agent is used, the skin material 10 has a moist and warm touch. Can be granted.
Examples of the organic particles include organic resin particles such as urethane beads and acrylic beads, and protein fillers such as collagen particles.
The shape of the organic particles is preferably a spherical shape or a spherical shape close to a true spherical shape, for example, the ratio of the major axis to the minor axis is preferably 1.5 or less, from the viewpoint that the feeling becomes better. The particle diameter is preferably in the range of 1 μm to 20 μm, and more preferably in the range of 5 μm to 10 μm. When the particle diameter is in the above range, drop-off of particles from the surface treatment layer 22 and adverse effects on the appearance can be suppressed, and a good appearance and excellent texture can be maintained for a long time.
In addition, the average particle diameter of the organic particles in the present invention is measured at a disk rotation speed of 3000 rpm by a light transmission centrifugal precipitation method using water as a dispersion medium, using an automatic particle size measuring apparatus (model number: CAPA-300) manufactured by Horiba. The value measured by the method of measuring the volume-based median diameter is used.
Only one type of organic particles may be used, or two or more types may be used in combination.

The surface treatment layer 22 may contain a colorant in order to impart design properties as necessary. As the colorant, general-purpose colorants mentioned in the cross-linked layer 20 can be used in the same manner, and the preferred addition amount is also the same.
The thickness of the surface treatment layer 22 is preferably in the range of 1 μm to 5 μm, and more preferably in the range of 2 μm to 3 μm.

(6. Physical properties of synthetic resin skin material)
Since the synthetic resin skin material of the present invention has the above-described layer structure, it has both wear resistance, excellent texture, and flexibility, and can be suitably used for a molded article having complicated irregularities.
In addition, it is preferable that the synthetic resin skin material of the present invention has a uniform ratio of vertical and horizontal elongation. For example, the vertical elongation measured by a method according to JIS K6772: the horizontal elongation ratio is 1.5: It is preferably in the range of 1: 1 to 2: 2, and more preferably in the range of 1: 1 to 1: 1.5. When the ratio of the vertical and horizontal elongation is within the above range, it can be more suitably used for forming a molded article having complicated irregularities.
Here, the vertical indicates the longitudinal direction of the apparatus for producing the synthetic resin skin material, and the horizontal indicates the direction perpendicular to the vertical, that is, the width direction.

[Method for producing synthetic resin skin material]
The method for producing a synthetic resin skin material of the present invention includes a laminate forming step of forming a laminate of a vinyl chloride resin layer and a composition layer for forming a vinyl chloride foam layer comprising a composition containing a foaming agent and a resin. A base cloth bonding step for bonding a base cloth to the vinyl chloride foam layer forming composition layer side of the laminate, and a water-based polyurethane resin and a crosslinking agent on the surface of the laminate on the vinyl chloride resin layer side A composition containing a resin and organic particles on the surface of the water-based crosslinked polyurethane layer, and a surface treatment. A surface treatment layer forming step of forming a layer, and a foaming step of foaming the foaming agent in the vinyl chloride foam layer forming composition by heating to form a vinyl chloride foam layer.
The manufacturing method of the present invention will be described in detail for each process.

(A. Laminate forming step)
A laminated body formation process is a process of forming the laminated body of the said vinyl chloride resin layer 18 and the composition layer for vinyl chloride foam layer formation which consists of a composition containing a foaming agent and resin.
The laminate may be formed by simultaneously calendering or simultaneously extruding the vinyl chloride resin layer 18 and the vinyl chloride foam layer forming composition layer, or first, the vinyl chloride foam layer is formed. A vinyl chloride resin layer 18 is formed on the surface of the composition layer using a paste processing machine or an extruder, and a laminate of the vinyl chloride foam layer forming composition layer and the vinyl chloride resin layer 18 is formed. Also good.

(B. Base fabric bonding process)
In this step, the base fabric 12 is adhered to the surface of the laminate of the vinyl chloride resin layer and the composition layer for forming the vinyl chloride foam layer formed in the laminate formation step on the foam layer forming composition layer side. It is a process.
The side of the base fabric 12 in contact with the foam layer forming composition layer may be subjected to raising treatment by a conventional method.
In the bonding step, for example, before the composition layer for forming a vinyl chloride foam layer is cured, it may be laminated together with the base fabric 12 and adhered to the surface of the composition layer for forming a vinyl chloride foam layer or the surface of the base fabric 12. After forming the agent layer 14, both may be bonded together via the adhesive layer 14.

The adhesive layer 14 is formed by laminating an adhesive on the surface of the vinyl chloride foam layer-forming composition layer or the surface of the base fabric 12 and drying it.
There is no restriction | limiting in particular as an adhesive agent used for formation of the adhesive bond layer 14 provided by necessity, Although it selects suitably according to the objective, For example, (1) Urethane type emulsion adhesive, (2) Vinyl chloride type adhesion | attachment An agent, (3) two-component curable polyester adhesive, and (4) two-component curable urethane adhesive are preferably used.
Usually, after forming the laminated body of the vinyl chloride resin layer 18 and the vinyl chloride foam layer forming composition layer, the adhesive layer 14 is formed by applying an adhesive to the surface of the vinyl chloride foam layer forming composition layer. Is formed. As a method for applying the adhesive, any known method such as a transfer method or a coating method can be used. From the viewpoint that the adhesive layer 14 having a uniform thickness can be easily formed, the transfer method is used. preferable.
Further, when the adhesive layer 14 is formed by a transfer method, a protective sheet may be provided on the surface of the adhesive layer 14 in order to protect the surface of the adhesive layer 14 prepared in advance. As the protective sheet, a resin film, release-treated paper, resin-laminated paper, or the like can be used as appropriate.

A. A laminate forming step; b. The bonding process of the base fabric and the laminate may be performed simultaneously or sequentially. That is, the laminate 12 is formed by a calendar method or the like, and the substrate 12 is heated and pressed with a nip roll or the like on the surface of the laminate on the vinyl chloride foam layer forming composition layer side while the laminate is conveyed. Adhesion may be performed. When the adhesive layer 14 is interposed, the adhesive layer 14 is formed on the surface of the laminate on the vinyl chloride foam layer forming composition layer side, and then the adhesive layer 14 and the base fabric 12 are combined. And may be pressure-bonded.
Thus, the vinyl chloride foam layer forming composition layer and the vinyl chloride resin layer 18 are provided on the base fabric 12.

(C. Crosslinking layer forming step)
Next, a cross-linked layer forming step of forming a water-based cross-linked polyurethane layer by applying a composition containing a water-based polyurethane resin and a cross-linking agent to the surface of the laminate on the vinyl chloride resin layer 18 side and drying. carry out.
Details of the composition containing the water-based polyurethane resin and the crosslinking agent are as described above. This composition is applied to the surface of the vinyl chloride resin layer 18 of the laminate bonded to the base material obtained above and dried to form a crosslinked structure, thereby forming a water-based crosslinked polyurethane layer.
The application of the composition is performed by a conventional method. For example, it may be applied by appropriately selecting from a method such as coating by a gravure printing method, coating by a reverse coater or a direct coater, and from the viewpoint that a uniform layer can be formed. Is preferably a gravure printing method.
After applying the composition for forming a water-based crosslinked polyurethane layer, the crosslinking agent contained in the composition forms a three-dimensional crosslinked structure with the water-based polyurethane by heating and drying, and the water-based crosslinked polyurethane layer is formed. The As described above, by using a carbodiimide progress learning material as a preferred embodiment, a dense three-dimensional cross-linked structure is formed, and the cross-linked layer 20 is a thin layer having excellent wear resistance. Moreover, by containing a silicone compound in the crosslinked layer 20, the surface energy of the crosslinked layer 20 is lowered, and the wear resistance is further improved.

(D. Surface treatment layer forming step)
In this step, the surface treatment layer (feel improvement layer) 22 is used to make the surface feel and appearance excellent on the surface of the water-based crosslinked polyurethane layer, which is the wear-resistant layer obtained in the crosslinked layer forming step. Is a step of forming. This step is performed by forming a surface treatment layer 22 by applying a composition containing a resin and organic particles.
The application of the composition can be performed in the same manner as in the cross-linked layer forming step. For example, the composition may be applied by appropriately selecting from a method such as coating by a gravure printing method, coating by a reverse coater or a direct coater. The gravure printing method is preferable from the viewpoint that it can be formed.

(E. Foaming process)
This step is a step of foaming the foaming agent in the composition for forming a vinyl chloride foam layer by heating to form a vinyl chloride foam layer. Heating is preferably performed by non-contact heating by conveying the inside of a heating furnace adjusted to a predetermined temperature.
When thermally expanded beads are used as a foaming agent in the vinyl chloride foamed layer forming composition layer, the heating temperature for expanding the thermally expanded beads is preferably in the range of 130 ° C to 230 ° C, and 190 ° C. More preferably, it is in the range of ~ 230 ° C. Moreover, when ADCA is used as the foaming agent, the heating temperature is preferably in the range of 180 ° C to 250 ° C, and more preferably in the range of 200 ° C to 230 ° C.
The foaming step of the vinyl chloride foam layer may be performed after the base fabric bonding step, prior to the cross-linked layer forming step and the surface treatment layer forming step, or after the cross-linking layer forming step and the surface treatment layer forming step. .

(F. Designability imparting step)
The synthetic resin skin material of this invention performs the designability provision process for improving an external appearance further as needed.
After completing the above steps a to e, on the surface treatment layer side of the laminate comprising at least the obtained base fabric 12, the vinyl chloride foam layer 16, the vinyl chloride resin layer 18, the crosslinked layer 20 and the surface treatment layer 22, By pressing an embossing roll engraved with a drawn shape while the surface is heated, a synthetic resin skin material having a drawn pattern formed on the surface is obtained.
The application of the drawn pattern may be performed prior to the cross-linked layer forming step and the surface treatment layer forming step after the base fabric adhering step, in which case the foam layer forming composition layer and After the foaming agent is foamed by heating the laminate having the vinyl chloride resin layer 18 to form a foamed layer having bubbles, the surface of the embossing roll engraved with the drawn shape is heated. To form a drawn pattern, and then the crosslinked layer 20 and the surface treatment layer 22 may be formed in this order.
By forming the natural leather-like unevenness on the squeeze roll in advance, embossing with this, the natural leather-like unevenness is transferred to the surface, and the synthetic resin skin material has an excellent appearance like natural leather It will be.
The heating temperature in embossing is preferably 100 ° C to 190 ° C.
Since the synthetic resin skin material 10 of the present invention has a surface-treated layer 22 containing resin particles that are appropriately matte and feel good on the outermost surface, and a cross-linked layer 20 that is excellent in wear resistance adjacent thereto, It is suitably used as a skin material for a molded article having a complicated shape.

  The synthetic resin skin material of the present invention is formed by a simple method, is excellent in appearance, durability, and flexibility, is added to automobile interior materials, railway vehicle / aircraft interior parts, furniture, shoes, footwear, bags, It can be suitably used in various fields such as building interior / exterior members, clothing covering materials and linings.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not restrict | limited to these.
[Example 1]
As the vinyl chloride resin layer forming resin, polyvinyl chloride having an average polymerization degree of 1300 was used.
The prescription of the resin composition for forming a vinyl chloride resin layer is as follows.
Polyvinyl chloride resin (average degree of polymerization 1300) 100 parts by mass Plasticizer (dialkyl phthalate) 95 parts by mass Stabilizer (Ba-Zn composite stabilizer) 2 parts by mass Filler (calcium bicarbonate) 10 parts by mass Parts, colorant (pigment) 5 parts by mass

The prescription of the composition for forming a vinyl chloride foam layer is as follows.
(Composition for forming a vinyl chloride foam layer)
-Polyvinyl chloride resin (average polymerization degree 1300) 100 parts by mass-Foaming agent (ADCA) 4 parts by mass-Plasticizer (dialkyl phthalate) 95 parts by mass-Stabilizer (Ba-Zn composite stabilizer) 2 parts by mass- 10 parts by mass of filler (calcium bicarbonate), 2 parts by mass of colorant (pigment)

Using a calendar device, a laminate in which the vinyl chloride resin layer 18 and the vinyl chloride foam layer forming composition layer are laminated is formed. The thickness of the vinyl chloride resin layer 18 of the laminate was 0.17 mm, and the thickness of the foam layer forming composition layer (before foaming) was 0.22 mm.
About 10 g / m ^{2 of} an adhesive (manufactured by DIC Corporation, urethane emulsion adhesive) was applied to the surface of the obtained laminate on the foam layer forming composition side, and the base fabric 12 was bonded.
As the base fabric 12, a knitted fabric with improved knitting (fiber: polyester rayon blend yarn 30th count, basis weight 250 g / m ² , thickness 0.40 mm) was used. The elongation ratio between the length and the width of the synthetic resin skin material 10 obtained by using the base fabric 12 measured in accordance with JIS K6772 is about 1: 1, and the volume feeling is also excellent.

Thereafter, the following composition for forming a cross-linked layer is applied to the surface of the vinyl chloride resin layer 18 of the laminate bonded to the base fabric 12 by a gravure printing method and dried at 120 ° C. to form a water-based cross-linked polyurethane layer having a thickness of 8 μm. 20 was formed.
(Composition for forming a crosslinked layer)
-100 parts by weight of an aqueous two-component polycarbonate polyurethane resin composition-4 parts by weight of a crosslinking agent (kaibodiimide type crosslinking agent)-15 parts by weight of a silicone compound (manufactured by Stahl, water-dispersed silicone)

Furthermore, in order to improve the tactile sensation, a surface treatment layer forming composition having the following formulation was applied by gravure printing and dried to form a surface treatment layer 22 having a thickness of 2 μm.
(Surface treatment layer forming composition)
-Polyurethane resin composition with urethane beads 100 parts by mass-Solvent (methyl ethyl ketone: MEK) 17 parts by mass

After forming the cross-linked layer 20 and the surface treatment layer 22, the obtained laminate is passed through a heating furnace having a temperature condition of 190 ° C. to 230 ° C. to foam the foaming agent, and the vinyl chloride foam layer in which bubbles are present 16 was formed.
The embossing roll engraved with the squeezed shape was pressed on the surface of the laminate on which the vinyl chloride foam layer 16 was formed, while the surface was heated to 130 ° C. to perform embossing, and a squeezed pattern was formed on the surface. The synthetic resin skin material 10 of Example 1 was obtained.

(Comparative Example 1)
As the vinyl chloride resin layer forming resin, polyvinyl chloride having an average polymerization degree of 1300 was used.
(Resin composition for forming a vinyl chloride resin layer)
-Polyvinyl chloride resin (average polymerization degree 1300) 100 parts by mass-Plasticizer (dialkyl phthalate) 75 parts by mass-Stabilizer (Ba-Zn composite stabilizer) 2 parts by mass-Filler (calcium bicarbonate) 10 parts by mass Parts, colorant (pigment) 5 parts by mass

(Composition for forming a vinyl chloride foam layer)
-Polyvinyl chloride resin (average polymerization degree 1300) 100 parts by mass-Foaming agent (ADCA) 4 parts by mass-Plasticizer (dialkyl phthalate) 75 parts by mass-Stabilizer (Ba-Zn composite stabilizer) 2 parts by mass- 10 parts by mass of filler (calcium bicarbonate), 2 parts by mass of colorant (pigment)

Lamination obtained by laminating a vinyl chloride resin layer 18 and a vinyl chloride foam layer forming composition layer using the above-mentioned composition for forming a vinyl chloride resin layer and a composition layer for forming a vinyl chloride foam layer in a calendar device. Form the body.
The thickness of the vinyl chloride resin layer 18 in the laminate was 0.30 mm, and the thickness of the foam layer forming composition layer (before foaming) was 0.65 mm.
About 10 g / m ^{2 of} an adhesive (manufactured by DIC Corporation, urethane emulsion adhesive) was applied to the surface of the obtained laminate on the foam layer forming composition side, and the base fabric 12 was bonded.
As the base fabric 12, a general double-sided knitted knitted fabric (fiber: polyester rayon blended yarn 30th used, basis weight 150 g / m ² , thickness 0.30 mm) was used. The elongation ratio between the vertical and horizontal dimensions of the synthetic resin skin material obtained using this base fabric 12 in accordance with JIS K6772 is about 1: 6, and the elongation balance is poor and the volume feeling is poor.
Thereafter, the following skin layer forming composition was applied to the surface of the vinyl chloride resin layer 18 of the laminate bonded to the base fabric 12 by a gravure printing method, dried at 120 ° C., and a polyurethane layer having a thickness of 2.5 μm ( (Skin layer) 24 was formed.

(Skin layer forming composition)
・ 100 parts by mass of solvent-type polycarbonate polyurethane resin composition

By passing the obtained laminate through a heating furnace having a temperature condition of 190 ° C. to 230 ° C., the foaming agent was foamed to form a vinyl chloride foam layer 16 containing bubbles.
The embossing roll engraved with the squeezed shape was pressed on the surface of the laminate on which the vinyl chloride foam layer 16 was formed, while the surface was heated to 130 ° C. to perform embossing, and a squeezed pattern was formed on the surface. The synthetic resin skin material 30 of the comparative example 1 of the structure shown in FIG. 2 was obtained.

(Evaluation of synthetic resin skin material)
The obtained synthetic resin skin material 10 of Example 1 and the synthetic resin skin material 30 of Comparative Example 1 were evaluated according to the following criteria. The results are shown in Table 1 below.
(Abrasion resistance: Plane wear resistance test)
The test was conducted with reference to a plane abrasion tester (Method B) of JASO M 403/88 / sheet skin material.
As described below, the test conditions were stricter than those of the JASO method.
(Test conditions)
Standard conditions in JASO method → Conditions of this test Press load: 9.81N → 19.6N
Number of tests: 10,000 times → 40,000 times

The judgment criteria are as shown below.
Grade Criterion 5 No change 4 Change is slightly observed 3 Change is clearly recognized 2 Change is slightly significant 1 Change is significant

(Elongation test)
The synthetic resin skin material of Example 1 and Comparative Example 1 was measured for vertical and horizontal elongation according to the method described in JIS K6772, and the vertical to horizontal elongation ratio was measured.
In the synthetic resin skin material of Example 1, the vertical: horizontal elongation was 90%: 95%. On the other hand, in the synthetic resin skin material of Comparative Example 1, the vertical / horizontal elongation was 45%: 230%. From the comparison between Example 1 and Comparative Example 1, it can be seen that the synthetic resin skin material 10 of Example 1 has a better balance of vertical and horizontal elongation than the conventional product.

(Tactile evaluation)
(1) Dry / wet feeling The touch test conditions are as follows.
As a testing machine, a KES-SE friction tester manufactured by Kato Tech Co., Ltd. was used.
(Test conditions)
Friction: Fingerprint type Sensor speed: 1.0 m / sec
Load: 25g
(Evaluation method)
The wet and dry sensation is obtained from the MIU (average coefficient of friction) / MMD (friction coefficient displacement) value obtained under the above conditions, and determined according to the following criteria. The MIU / MMD is judged to be good (◯) in the range of 10 to 40,
○: MIU / MMD is in the range of 10 to 40 ×: MIU / MMD is less than 10 or more than 40

(2) Rough feeling The tactile sensation test conditions for rough feeling are as follows.
As a testing machine, Ra: centerline average roughness (μm) was determined using a surface roughness / contour shape measuring machine manufactured by Tokyo Seimitsu Co., Ltd., and manufactured by Kato Tech Co., Ltd., KES-SE. Using a friction tester, MMD: Change in average dynamic friction coefficient is obtained.

Surface roughness / contour shape measuring machine test condition speed: 0.3 mm / sec

Friction tester test conditions Friction: Fingerprint type Sensor speed: 1.0 m / sec
Load: 25g

(Evaluation method)
From the value of Ra (centerline average roughness (μm)) × MMD (variation of average dynamic friction coefficient) obtained under the above conditions, the rough feeling is obtained and objectively determined. When Ra × MMD is 0.20 or less, it is judged that the feel is good, and when it exceeds 0.20, it is a level that causes a practical problem.

(Evaluation criteria)
○: Ra × MMD is 0.20 or less ×: Ra × MMD exceeds 0.20

  From the results of Table 1, the synthetic resin skin material of Example 1 showed only slight changes even in severe conditions of wear resistance tests, and showed a level of wear resistance with no practical problems. It can be seen that the wear resistance, excellent feel, and flexibility are compatible, and that it can be suitably used for a molded article having complicated irregularities.

10 Synthetic resin skin material 12 Base fabric 14 Adhesive layer 16 Vinyl chloride foam layer (foam layer)
18 Vinyl chloride resin layer 20 Water-based crosslinked polyurethane layer (crosslinked layer)
22 Surface treatment layer 30 Conventional synthetic resin skin material

Claims (10)

  A synthetic resin skin material comprising a vinyl chloride foam layer, a vinyl chloride resin layer, a water-based crosslinked polyurethane layer, and a surface treatment layer containing a resin and organic particles in this order on a base fabric.   The synthetic resin skin material according to claim 1, wherein the water-based crosslinked polyurethane layer is a layer having a thickness of 2 μm to 15 μm formed by crosslinking water-based polyurethane with a carbodiimide-based crosslinking agent.   The synthetic resin skin material according to claim 1 or 2, wherein the organic particles are organic particles having an average particle diameter of 1 µm to 10 µm selected from the group consisting of urethane resin particles, protein particles, and acrylic beads.   The synthetic resin skin material according to any one of claims 1 to 3, wherein the water-based crosslinked polyurethane layer further contains a silicone compound.   The synthetic resin skin material of any one of Claims 1-4 which has an adhesive bond layer between the said base fabric and the said vinyl chloride foam layer.   The ratio of the vertical and horizontal elongation measured in accordance with JIS K6772 is in the range of vertical elongation: horizontal elongation = 1: 1 to 1: 2, and any one of claims 1 to 5. Synthetic resin skin material. A laminate forming step of forming a laminate of a vinyl chloride resin layer and a composition layer for forming a vinyl chloride foam layer comprising a composition containing a foaming agent and a resin;
A base fabric bonding step of bonding a base fabric to the vinyl chloride foam layer forming composition layer side of the laminate;
A crosslinked layer forming step of forming an aqueous crosslinked polyurethane layer by applying a composition containing an aqueous polyurethane resin and a crosslinking agent to the surface of the laminate on the vinyl chloride resin layer side and drying,
A surface treatment layer forming step of forming a surface treatment layer by applying a composition containing a resin and organic particles to the surface of the water-based crosslinked polyurethane layer;
A foaming step of foaming the foaming agent in the composition for forming a vinyl chloride foam layer by heating to form a vinyl chloride foam layer, and a method for producing a synthetic resin skin material.   The method for producing a synthetic resin skin material according to claim 7, wherein the foaming step is performed after the cross-linked layer forming step and the surface treatment layer forming step.   The method for producing a synthetic resin skin material according to claim 7, wherein the foaming step is performed prior to the cross-linked layer forming step and the surface treatment layer forming step after the base fabric adhering step.   The said base fabric adhesion process includes the process of providing an adhesive bond layer between the composition layer for vinyl chloride foam layer formation of the said laminated body, and a base fabric, The any one of Claims 7-9. Of manufacturing synthetic resin skin material.