JP5823324B2 - Manufacturing method and manufacturing apparatus for synthetic resin skin material - Google Patents

Description

  The present invention relates to a method for producing a synthetic resin skin material and a production apparatus used in the production method.

  In recent years, automotive interior parts (instrument panels, door trims, seats, ceilings, etc.), railcar / aircraft interior parts (trims, seats, ceilings, etc.), furniture, shoes / footwear / bags, interior / exterior components for building, 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 is manufactured by a transfer method. When a synthetic resin skin material is manufactured by a transfer method, a textured shape is formed on one surface, and a release agent layer is formed on this surface. The surface layer forming composition, the intermediate layer forming composition, and the adhesive are sequentially applied to the surface of the release agent layer of the temporary support, and dried to form the surface layer, the intermediate layer, and the adhesive layer. It laminates with a base material and peels a temporary support body (patent document 1).

Japanese Patent Laid-Open No. 6-199978

However, when manufacturing a skin material having a fine, deep-drawn shape, a composition for forming a surface layer is used to prevent unnatural glossiness when faithfully reproducing the embossed shape formed on the temporary support. It is necessary to spread the object and the intermediate layer forming composition to the depths of the irregularities of the temporary support.
Therefore, in the case of forming either the surface layer or the intermediate layer, it is necessary to increase the coating thickness of the surface layer forming composition and the intermediate layer forming composition.

  However, although gravure rolls and microchamber doctors that have been generally used in the past can be applied at high speed, the composition for forming the surface layer and the composition for forming the intermediate layer are spread to the depths of the irregularities of the temporary support. Is difficult. In addition, since the coating amount per one time is small, when forming the surface layer or the intermediate layer, it was necessary to repeat the application and drying of the surface layer forming composition or the intermediate layer forming composition a plurality of times. .

  Moreover, when it was going to apply thickly the composition for surface layer formation, and the composition for intermediate | middle layer formation by one application | coating, it had to slow down the application | coating speed.

  The present invention is capable of thickly coating a skin layer forming composition such as a surface layer forming composition and an intermediate layer forming composition at a high speed, and is a composition for forming a skin layer up to the depth of irregularities on the surface of a temporary support. An object of the present invention is to provide a manufacturing method and a manufacturing apparatus for a synthetic resin skin material capable of spreading the above.

The invention of claim 1 relates to a method for producing a synthetic resin skin material, and is applied to the surface of the release agent layer of the temporary support having a release agent layer by discharging the composition for forming the skin layer from a slit-like outlet, then drying the temporary support by heating from both sides said skin layer forming composition, and a skin layer forming step for forming a skin layer, formed on the surface of the skin layer, the adhesive from the slit-like discharge port agent pressure, discharged was applied with, then the temporary support is dried the adhesive is heated from both sides, and having a adhesive layer forming step of forming an adhesive layer.

  In the method for producing the synthetic resin skin material, the coating liquid such as the composition for forming the skin layer is pumped toward the slit-like discharge port and discharged from the discharge port, and applied to an object such as a temporary support. Yes. Accordingly, since the coating liquid is pressurized inside the discharge type coating apparatus, bubbles are prevented from being mixed into the coating liquid, and appearance defects due to the mixing of bubbles can be prevented. Further, since the coating liquid is discharged in a state of being pressurized from the discharge port, it is pressed into the depth of the unevenness formed on the surface of the temporary support. Therefore, since the coating liquid spreads to the depths of the irregularities of the temporary support, the embossed shape formed on the surface of the temporary support is faithfully reproduced. As a result, the occurrence of unnatural gloss due to insufficient reproduction of the embossed shape and the appearance defect due to bumping of the solvent in the skin layer are effectively suppressed. Furthermore, in the skin layer forming step and the adhesive layer forming step, the temporary support is heated from both the surface on which the composition for forming the skin layer or the adhesive is applied and the surface opposite to this surface. Therefore, although the skin layer forming composition and the adhesive are thickly applied, the drying can be performed quickly, and the occurrence of drying unevenness can be prevented.

The invention according to claim 2 is the method for producing a synthetic resin skin material according to claim 1, wherein the skin layer is formed on the surface of the release agent layer of the temporary support having the release agent layer from the slit-like discharge port. The composition for forming a surface layer is applied by applying pressure and discharge as a composition, and then the temporary support is heated from both sides to dry the composition for forming the surface layer, forming a surface layer, and further forming a slit. The intermediate layer forming composition is applied as a skin layer forming composition by pressurizing and discharging the surface layer to the surface of the surface layer from the discharge port, and then the temporary support is heated from both sides to form the intermediate layer. The composition is dried to form an intermediate layer.

  Since the synthetic resin skin material obtained by the method for producing the synthetic resin skin material has a skin layer separated into a surface layer and an intermediate layer, for example, by forming the intermediate layer as a foamed layer, a synthetic resin suitable for lightweight applications As a skin material, a synthetic resin skin material corresponding to various requirements that cannot be satisfied by a synthetic resin skin material having a single skin layer can be produced.

  Invention of Claim 3 is the manufacturing method of the synthetic resin skin material of Claim 1 or 2, In the composition for skin layer formation, the composition for surface layer formation, intermediate | middle layer formation from the said slit-shaped discharge port A closed die coater is characterized in that the composition and the adhesive are discharged and applied.

  Since the closed die coater used in the method for manufacturing the synthetic resin skin material does not have a liquid reservoir near the discharge port, it is difficult for foreign matter to enter the coating liquid. In addition, since the coating liquid is discharged from the discharge port at a pressure that remains pressurized inside the closed die coater, it is possible to more effectively prevent air bubbles from being mixed into the coating liquid and to be formed on the surface of the temporary support. The wrinkled shape can be reproduced more faithfully.

According to a fourth aspect of the present invention, in the method for producing a synthetic resin skin material according to the second aspect, the intermediate layer forming composition comprises a two-component polycarbonate polyurethane resin composition, a colorant, and thermal expansion. It contains beads and a solvent that dissolves the two-component polycarbonate polyurethane resin composition but does not dissolve the resin constituting the thermally expanded beads.

  In the method for producing the synthetic resin skin material, since the intermediate layer forming composition contains a two-component polycarbonate polyurethane resin composition and thermally expandable beads, the intermediate layer forming composition is dried. Sometimes the two-component polycarbonate polyurethane resin composition in the intermediate layer forming composition is cured to form a high-strength film, and the thermally expanded beads are expanded to form voids. Therefore, an intermediate layer having high strength and having appropriate voids is formed. Furthermore, by controlling the blending amount of the thermally expanded beads and the heating temperature of the thermally expanded beads, there is an advantage that an intermediate layer (urethane foam layer) having a thickness and elasticity as designed is formed.

  The invention according to claim 5 is the method for producing a synthetic resin skin material according to claim 4, wherein the intermediate layer forming composition further contains a diamine chain extender.

  In the method for producing the synthetic resin skin material, since a composition containing a diamine chain extender in addition to the two-component polycarbonate polyurethane resin composition and the thermally expanded beads is used as the intermediate layer forming composition, By heating to 130 ° C. or higher in the drying after coating, the blocking agent of the isocyanate moiety in the two-component polycarbonate polyurethane resin composition is dissociated and polymerized with the diamine structure of the chain extender to form a chain structure. Extended. Therefore, since a higher molecular weight polymer structure is formed in the intermediate layer, an intermediate layer having higher strength and higher flexibility is formed.

The invention according to claim 6 relates to a synthetic resin skin material manufacturing apparatus, a temporary support transporting device for transporting a temporary support having a release agent layer formed on one surface in a certain direction, and a composition for forming a skin layer. Is applied to the surface of the release agent layer of the temporary support by applying pressure and discharge from a slit-like discharge port, and downstream of the discharge-type coating apparatus along the transport direction of the temporary support. A skin layer forming apparatus provided with a double-sided dryer for drying the skin layer forming composition by heating the temporary support on which the skin layer forming composition is positioned and drying the surface, and the transport direction of the temporary support On the surface of the skin layer in the temporary support formed by the skin layer forming device by being pressed and discharged from the slit-shaped discharge port, and located on the downstream side of the skin layer forming device. Discharge-type coating apparatus for coating, and the temporary support An adhesive layer forming apparatus provided with a double-sided dryer that is located downstream of the discharge-type coating apparatus along the transport direction and heats the temporary support coated with the adhesive from both sides to dry the adhesive; A base material laminate which is positioned on the downstream side of the adhesive layer forming device along the transport direction of the temporary support and is laminated by pressing and adhering the base material to the adhesive layer formed by the adhesive layer forming device And a temporary support peeling device that is located downstream of the substrate laminating device along the transport direction of the temporary support and peels the temporary support to form a synthetic resin skin material. And

  In the synthetic resin skin material manufacturing apparatus, the discharge type coating apparatus provided in the skin layer forming apparatus and the adhesive layer forming apparatus pumps a coating liquid such as a skin layer forming composition toward the slit-shaped discharge port. It is a coating device that discharges from a discharge port and applies to a target such as a temporary support. Accordingly, since the coating liquid is pressurized inside the discharge type coating apparatus, bubbles are prevented from being mixed into the coating liquid, and appearance defects due to the mixing of bubbles can be prevented. Further, since the coating liquid is discharged in a state of being pressurized from the discharge port, it is pressed into the depth of the unevenness formed on the surface of the temporary support. Therefore, the embossed shape formed on the surface of the temporary support is faithfully reproduced, and the appearance of unnatural gloss due to insufficient reproduction of the embossed shape and the appearance defect due to bumping of the solvent in the coating liquid are effective. Deterred.

  In addition, since the double-sided dryers provided in the surface layer forming apparatus and the adhesive layer forming apparatus both heat the temporary support from both sides, the drying is quickly performed even though the coating solution is thickly applied. And the occurrence of uneven drying can be prevented.

The invention according to claim 7 is the synthetic resin skin material manufacturing apparatus according to claim 6, wherein the skin layer forming apparatus peels the surface layer forming composition as the skin layer forming composition from the temporary support. A surface layer forming apparatus that forms a surface layer by coating and drying on the surface of the agent layer, and is located on the downstream side of the surface layer forming apparatus along the transport direction of the temporary support, and is formed by the surface layer forming apparatus. An intermediate layer forming device that forms an intermediate layer by applying and drying the intermediate layer forming composition as the skin layer forming composition on the surface layer surface,
Each of the surface layer forming apparatus and the intermediate layer forming apparatus includes a discharge type coating apparatus that pressurizes and discharges a coating liquid from a slit-shaped discharge port and applies the liquid onto an object, and a transport direction of the temporary support. And a double-sided drier that heats the temporary support from both sides and dries the coating liquid .

  According to the synthetic resin skin material manufacturing apparatus, it is possible to manufacture a synthetic resin skin material in which the skin layer is divided into a surface layer and an intermediate layer therebelow. Therefore, for example, by using a foam layer as the intermediate layer, a synthetic resin skin material suitable for light weight applications can be used, and a variety of requirements that cannot be met by a synthetic resin skin material with a single skin layer can be met. A synthetic resin skin material can be produced.

  The invention according to claim 8 is the synthetic resin skin material manufacturing apparatus according to claim 6 or 7, wherein each of the discharge-type coating apparatuses is a closed die coater.

  Since the closed die coater used in the synthetic resin skin material manufacturing apparatus does not have a liquid reservoir in the vicinity of the discharge port, foreign matter is unlikely to enter the coating liquid. In addition, since the coating liquid is discharged from the discharge port at a pressure that remains pressurized inside the closed die coater, it is possible to more effectively prevent air bubbles from being mixed into the coating liquid and to be formed on the surface of the temporary support. The wrinkled shape can be reproduced more faithfully.

  The invention according to claim 9 is the synthetic resin skin material manufacturing apparatus according to claim 8, wherein each of the double-sided dryers is a double-sided hot-air nozzle type dryer that blows hot air on both sides of the temporary support to dry it. It is characterized by being.

  The double-sided hot air nozzle type dryer used as a double-sided dryer in the synthetic resin skin material manufacturing device realizes a subtle drying temperature gradient by controlling the air volume, wind speed, and direction of the hot air. The temperature gradient can be optimized.

  A tenth aspect of the present invention is the synthetic resin skin material manufacturing apparatus according to the sixth aspect, wherein the skin layer forming device and the adhesive layer forming device are disposed between the discharge type coating device and the double-sided dryer. A coating amount measuring device that measures the coating amount of the layer forming composition or adhesive; and the coating amount of the skin layer forming composition or adhesive in the discharge type coating device is the measurement result in the coating amount measuring device. It is controlled based on this.

  In the synthetic resin skin material manufacturing apparatus, the coating amount of the coating solution such as the composition for forming the skin layer is measured with a coating amount measuring device, and the coating solution is applied in the discharge type coating device based on the obtained measurement result. Since the amount is feedback controlled, the coating amount of the coating liquid can be controlled in real time.

The invention according to claim 11, in the apparatus for manufacturing a synthetic resin skin material according to claim 10, wherein the coating amount meter measuring device is characterized in that the β-ray weighing scale.

  In the synthetic resin skin material manufacturing apparatus, since the β-ray weight meter is used as the coating amount measuring device, the coating amount of the coating liquid can be measured in real time and in a non-contact manner.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method and manufacturing apparatus of a synthetic resin skin material which can be thickly coated with the composition for skin layer formation at high speed, and can be spread to the back of the unevenness | corrugation of the surface of a temporary support are provided. .

FIG. 1 is a schematic diagram showing a configuration of an example of a manufacturing apparatus according to the present invention. FIG. 2 is an enlarged view showing the configuration of the coating unit provided in the surface layer forming apparatus constituting the manufacturing apparatus shown in FIG. FIG. 3 is an enlarged view showing a configuration of a double-sided drier provided in the surface layer forming apparatus constituting the manufacturing apparatus shown in FIG. FIG. 4 (A) is a schematic cross-sectional view showing the structure of one embodiment of a laminate having a surface layer and a coating solution layer on a temporary support in the production method of the present invention, and FIG. FIG. 4C is a schematic cross-sectional view showing a state of the laminated body after the process, FIG. 4C is a schematic cross-sectional view showing a state where the temporary support is peeled from the laminated body, and FIG. It is a schematic sectional drawing which shows the structure of the synthetic leather obtained by the manufacturing method.

1. Method for Producing Synthetic Resin Skin Material First, a method for producing a synthetic resin skin material will be sequentially described with reference to FIG.
In the method for producing the synthetic resin skin material 10 of the present invention, the surface layer formation is performed by applying the surface layer forming composition to the surface of the release agent layer of the temporary support 12 having the release agent layer 14 and drying it. And a solvent that does not dissolve the resin constituting the two-component polycarbonate polyurethane resin composition, the colorant, the thermal expansion beads 15 and the thermal expansion beads on the formed surface layer 16, and a viscosity at 25 ° C. There a composition for forming an intermediate layer is ^{5000mPa · s~20000mPa · s, 50g /} m 2 ~500g / m 2 and drying the coating with the coating liquid layer forming step of forming a coating solution layer 18 was formed The coating liquid layer 18 is heated and dried to foam the thermally expandable beads 15, and an intermediate layer forming step for forming the intermediate layer 22 containing the bubbles 20, and an adhesive is applied to the surface of the formed intermediate layer 22. Adhesive layer 2 The laminate forming step of forming the skin material forming laminate 26, and laminating the surface having the adhesive layer 24 of the obtained skin material forming laminate 26 and the base material (base fabric) 28 are laminated. Then, the manufacturing method of the synthetic resin skin material 10 which has the transfer process which peels the temporary support body 12 after that. The thermally expandable beads 15 can be foamed at the same time as the coating liquid layer 18 is dried.

[Surface layer forming step]
In the surface layer forming step, the surface layer forming composition is applied to the surface of the release agent layer 14 of the temporary support 12 having the release agent layer 14 and dried to provide the surface layer 16. In the surface layer forming step, the intermediate layer forming step, and the adhesive layer forming step, which will be described later, a discharge type coating device is used in the coating step, and a double-sided dryer is used in the drying step. The method will be described in “Method for producing synthetic resin skin material”.
The temporary support 12 has a release agent layer 14 on the surface, and a desired embossed pattern (uneven pattern) is formed on the surface. For example, when the synthetic resin skin material 10 is a skin material having a natural leather-like appearance, a leather-like uneven pattern may be formed in advance on the surface of the temporary support 12 on which the release agent layer 14 is formed. . At this time, a leather-like uneven pattern is transferred to the surface layer 16 to be formed by applying the surface layer forming composition to the surface of the temporary support 12 on which the release agent layer 14 is formed.

(Resin for surface layer)
The resin used for forming the surface layer 16 is appropriately selected according to the purpose of use of the synthetic resin skin material 10, but polycarbonate resin, water-based polyurethane resin, silicon-modified polyurethane resin, polyether-modified polyester resin, etc. are used, and heat resistance From the viewpoint of good property and chemical resistance, a polycarbonate resin is preferred.

(Other components contained in the surface layer)
The surface layer contains a colorant in addition to the base resin.
Examples of the colorant include colored organic resin particles in which a colorant is contained in organic resin fine particles selected from urethane resin particles, acrylic resin particles, silicone resin particles, and the like. From the viewpoints of affinity and uniform dispersibility with respect to the polyurethane-based resin, it is preferable to contain polycarbonate-based colored resin particles.
In general, the average particle diameter of such organic resin fine particles is preferably in the range of 0.5 μm to 100 μm, more preferably in the range of 3 μm to 50 μm.

  A known method is appropriately used for applying the surface layer. As a coating method, for example, the above-mentioned components are dissolved in an appropriate solvent on a sheet serving as a base material to prepare a composition for forming a surface layer, and applied to the base material surface using a known coating apparatus. Examples thereof include a method of forming a coating film, and drying the obtained coating film by a drying means of a direct drying method.

(Surface layer solvent)
The solvent used for the preparation of the composition for forming the surface layer is not particularly limited as long as it can uniformly dissolve and disperse the polyurethane resin and the like. Specifically, for example, methyl ethyl ketone (MEK), toluene, tetrahydrofuran (THF), dimethylacetamide (DMAC), N, N-dimethylformamide (DMF), isopropyl alcohol (IPA), N-methyl-2-pyrrolidone (NMP) and the like.

(Coating amount of surface layer)
There is no restriction | limiting in particular in the application quantity of a surface layer, and a film thickness, Although it selects suitably according to the objective, Generally, as an application quantity before drying from a viewpoint of intensity | strength and an external appearance, 50g / m < ² >- is preferably in the range of 300 g / ^{m 2,} more preferably in the range of ^{150g / m 2 ~300g / m 2} . Further, the film thickness after drying is preferably about 10 μm to 70 μm, more preferably about 20 μm to 50 μm.

[Coating liquid layer forming step]
On the surface layer 16 formed in the surface layer forming step, a two-component polycarbonate polyurethane resin composition, a colorant, a thermally expandable bead 15, and a solvent that does not dissolve the resin constituting the thermally expandable bead, 25 the viscosity at ℃ is 5000mPa · s~20000mPa · s composition for forming an intermediate ^{layer, 50g / m 2 ~500g / m} 2 was applied and dried to form a coating liquid layer 18. FIG. 4A is a schematic cross-sectional view showing a state in which the surface layer 16 and the coating liquid layer 18 are formed on the surface of the temporary support 12 having the release agent layer 14 on the release agent layer 14 forming side. The formed coating liquid layer 18 is heated in an intermediate layer forming process, which is the next process, so that the thermally expanded beads 15 in which the coating liquid layer 18 is present are expanded to form an intermediate layer 22 in which the voids 20 are inherent. Is done. In this embodiment, the thermal expansion beads are included in the intermediate layer, but the intermediate layer does not need cushioning properties, for example, in the case of being provided for the purpose of adjusting the thickness, strength, hue, etc. of synthetic leather However, it is not always necessary to include thermally expanded beads. When the thermal expansion beads are not contained, an intermediate layer that does not contain the bubbles 20 is formed.
Hereinafter, the embodiment will be described in detail with reference to an embodiment in which the intermediate layer contains thermally expanded beads, but the present invention is not limited to the embodiment described below.

(Interlayer resin)
As the two-pack type polycarbonate-based polyurethane resin composition used for forming the intermediate layer 22, at least a block type isocyanate and a diol are stored in two liquids and mixed when blending the intermediate layer forming composition. It is preferable to use a resin composition as a raw material. Here, the block type isocyanate refers to a compound in which an isocyanate group is protected with a blocking agent, and the blocking agent is dissociated by heating to regenerate an active isocyanate group. Such a two-component type polycarbonate-based polyurethane resin containing a block type isocyanate is also available as a commercial product. Specifically, for example, Crisbon series manufactured by DIC Corporation, Daiichi Kogyo Seiyaku Co., Ltd. Each product such as Elastron series and Elastron BN series manufactured by the present invention can be used in the present invention.
In a general one-pack type polycarbonate-based polyurethane resin, when the intermediate layer coating solution is dried and heated to expand the thermally expanded beads to form bubbles, the intermediate layer itself is thermally deformed by heating, or Since there exists a possibility that the intensity | strength of the formed intermediate | middle layer may fall, it is not preferable.

(Thermal expansion beads)
The composition for forming an intermediate layer may contain thermally expanded beads 15. The thermally expanded beads 15 are particles in which an organic solvent such as a hydrocarbon solvent is encapsulated in hollow thermoplastic tree particles, and the volume of the particles increases due to the volume expansion of the organic solvent due to heating. Bubbles 20 are inherent in the resin matrix (dispersion medium).
As the thermal expansion beads used in the present invention, any thermal expansion beads can be used as long as they can expand by heating to form hollow bubbles in the specific urethane resin matrix and maintain the state of the formed bubbles. May be.
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 to 10 parts by mass, more preferably 1 to 7 parts by mass with respect to 100 parts by mass of the two-component polycarbonate polyurethane resin. preferable.
In addition, when the content is sequentially changed from 3 parts by mass to 6 parts by mass, when the heating and foaming temperatures in the intermediate layer forming step described later are made constant, the film thickness of the intermediate layer is increased as the addition amount increases. Can do. That is, by controlling the amount of the thermally expanded beads 15 added, the amount and density of voids contained in the intermediate layer can be controlled, and the thickness of the intermediate layer itself containing such bubbles is also controlled. be able to.

(Solvent for intermediate layer)
The intermediate layer forming composition of the present invention uses an organic solvent instead of water as a solvent from the viewpoint of efficiently drying. As a solvent used for the preparation of the coating liquid layer, it is necessary to select a solvent that does not dissolve the resin constituting the thermally expanded beads. This is because when the resin constituting the thermally expanded beads is dissolved by an organic solvent, the hollow portion cannot be maintained, and an intermediate layer having desired elasticity is not formed.
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 thereof include glycol, n-hexane, cyclohexane, methyl ethyl ketone (MEK), and propylene glycol monomethyl ether (PGME), and these solvents may be appropriately selected and used. Of these, ethyl acetate, methyl ethyl ketone, isopropyl alcohol, and propylene glycol monomethyl ether are preferable from the viewpoint of processability. A preferable combination of solvents includes a combination of propylene glycol monomethyl ether and ethyl acetate.
Note that N, N-dimethylformamide (DMF), which is widely used in the field as a solvent, easily dissolves the resin of the thermally expanded beads, so that formation of voids due to foaming is hindered. However, when a solvent that does not dissolve the above-mentioned thermally expandable beads is used as a main solvent (for example, 80% by mass or more in all solvents), an amount that does not damage the thermally expanded beads (for example, all solvents) DMF may be used in combination as long as it is 20% by mass or less.
The content of the solvent in the intermediate layer forming composition is preferably 10 parts by mass to 500 parts by mass, and 30 parts by mass to 70 parts by mass with respect to 100 parts by mass of the two-component polycarbonate polyurethane resin. Is more preferable.

(Coloring agent)
The composition for forming an intermediate layer contains a colorant for the purpose of adjusting the appearance of the intermediate layer. As the colorant used in the intermediate layer, colored organic fine particles including various pigments and dyes can be selected and used according to the purpose. From the viewpoint of design and durability, organic pigments and inorganic pigments can be used. One or more selected or colored organic fine particles containing these pigments are preferred. The surface layer may also contain a colorant, and the colorant in the surface layer and the colorant in the intermediate layer may be the same or different.
As the colorant, colored organic fine particles such as Daicarac series manufactured by DIC Corporation are preferably used. Moreover, although content of a coloring agent is suitably selected according to the intended purpose of using a skin material, it may contain in 1 mass part-100 mass parts with respect to 100 mass parts of polycarbonate-type polyurethane resins which are the main ingredients. preferable. When a plurality of colorants are contained, the content indicates the total amount of the plurality of colorants.
In addition, you may use together another additive for the composition for intermediate | middle layer in the range which does not impair the effect of this invention. Examples of additives that can be used in combination include flame retardants, chain extenders, thixotropy imparting agents, antifoaming agents, leveling agents, and surfactants.

(Chain extender)
The intermediate layer coating solution according to the present invention preferably contains a chain extender from the viewpoint of improving the strength of the resulting skin material. There are no particular restrictions on the chain extender that can be used in the present invention, but since a polycarbonate-based polyurethane resin is used as the main component of the intermediate layer coating solution, it can be obtained by interacting with an isocyanate compound that is a raw material of the polyurethane resin. An amine chain extender that easily exhibits effects such as increasing the molecular weight of the urethane resin and improving flexibility is preferred. Specifically, for example, CLH-1 manufactured by DIC Corporation can be given as a commercial product.
The addition amount of the chain extender is preferably in the range of 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the polycarbonate-based polyurethane resin as the main agent. Within the range of this addition amount, the flexibility and strength of the formed intermediate layer can be compatible.

(Flame retardants)
The intermediate layer coating solution according to the present invention may contain a flame retardant. In particular, when the synthetic resin skin material obtained by the production method of the present invention is used for a vehicle interior material or the like, it is preferable to contain a flame retardant because the flame retardancy becomes important as well as the strength.
A well-known thing can be used suitably for the flame retardant which can be used for this invention, For example, you may use a metal hydroxide, a phosphorus flame retardant, a nitrogen-phosphorus flame retardant, etc. The flame retardant is also available as a commercial product, and examples thereof include STC powder manufactured by Clariant Japan Co., Ltd.
The flame retardant content is preferably in the range of 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the polycarbonate-based polyurethane resin as the main agent.

(Thixotropic agent)
Examples of the thixotropy-imparting agent that can be used for the intermediate layer include those obtained by hydrophilizing a chain viscosity mineral selected from sepiolite, attapulgite, and smectite.
(Leveling agent)
Examples of the leveling agent that can be used for the intermediate layer include organic polymer leveling agents, and examples of commercially available products include DIC Corporation, Crisbon Assister SD-56, and the like.
When the leveling agent is used, the content is preferably 0.01 parts by mass to 3 parts by mass with respect to 100 parts by mass of the polyurethane resin. In the range of this content, a leveling effect is sufficiently obtained, and a decrease in adhesiveness due to the addition of a leveling agent is suppressed.

In addition, since the intermediate layer can form an intermediate layer having a desired film thickness in one step by thickly applying an appropriate amount in one step if desired, the viscosity at 25 ° C. of the intermediate layer forming composition is It is preferable to adjust to 5000 mPa · s to 20000 mPa · s. The preparation of the coating solution viscosity is controlled by the amount of solvent added. In addition, the viscosity in this specification uses the average value measured 3 times on 25 degreeC and 10 rpm conditions using the BM type | mold viscometer.
The concentration of the intermediate layer forming composition is not particularly limited as long as the viscosity is in the above-mentioned preferable range, but from the viewpoint of coating suitability, the solid content concentration is preferably about 20% by mass to 50% by mass. .

Coating weight before drying of the intermediate layer forming ^composition, required to be a ^{50g / m 2 ~500g / m 2} , is preferably ^{100g / m 2 ~200g / m 2} . When the coating amount of the intermediate layer forming composition is within the above range, a synthetic resin skin material having sufficient elasticity and strength is formed.

(Intermediate layer forming process)
In this step, the coating liquid layer 18 of the intermediate layer forming composition formed in the above step is heated to foam the thermally expanded beads 15 to form the intermediate layer 22 containing the bubbles 20. FIG. 4B is a schematic cross-sectional view showing a state in which an intermediate layer 22 containing bubbles 20 formed after heating is laminated on the surface layer 16.
The coating liquid layer 18 is preferably dried at a temperature in the range of 90 ° C to 130 ° C, more preferably 100 ° C to 120 ° C.
Moreover, in the said intermediate | middle layer formation process, it is preferable that the heating temperature for expanding the thermal expansion bead 15 is the range of 130 to 200 degreeC, and it is more preferable that it is the range of 150 to 180 degreeC.
In addition, when the addition amount of the thermal expansion beads 15 is constant, the volume of the bubbles 20 formed by increasing the volume of the thermal expansion beads increases as the heating temperature increases in the range of 130 ° C. to 200 ° C. It was confirmed that the film thickness of the intermediate layer 22 also increased accordingly.
Therefore, by adjusting the heating conditions to control the volume of the bubbles 20, even when the same intermediate layer forming composition is used, the voids (bubbles) 20 having a preferable size can be formed. The thickness of the intermediate layer 22 itself containing such bubbles 20 can also be controlled. At this time, if the volume of the bubbles 20 is increased, the film thickness of the intermediate layer 22 is increased, and the density of the intermediate layer is reduced.

Due to the expansion of the thermally expanded beads in the intermediate layer 22, the intermediate layer 22 contains the bubbles 20.
In the intermediate layer forming step in the present invention, an organic solvent which is rich in volatility and does not adversely affect the resin constituting the thermally expanded beads is selected as the solvent contained in the intermediate layer. And, the expansion of the thermally expanded beads by heating is rapidly performed, and the workability is excellent.
In a preferred embodiment of the present invention, the two-component polycarbonate polyurethane resin composition used for the intermediate layer forming composition contains at least a block isocyanate and a diol, and further contains a diamine chain extender. It is preferable to include. By containing a diamine chain extender, the chain extender and the blocking agent of the isocyanate part of the block type isocyanate which is the urethane resin raw material are dissociated by heating for expansion of the thermally expandable beads, and the chain extender has a diamine The polymerization reaction with the structure forms a high molecular weight polymer structure in the intermediate layer, improving the film strength, and improving the flexibility of the resin by extending the chain structure.
For this reason, since the obtained intermediate layer has appropriate thickness and elasticity by including bubbles, and the film strength and flexibility are improved by polymerization, the skin material is excellent in strength and elasticity. Can be obtained.
The thickness of the intermediate layer on the substrate is appropriately adjusted according to the purpose of use of the synthetic resin skin material, but the thickness of the intermediate layer after drying is preferably in the range of 50 μm to 1000 μm, preferably 100 μm to 700 μm. More preferably, it is in the range.

[Laminated body formation process]
In this step, an adhesive is applied to the surface of the formed intermediate layer 22 and dried to form the adhesive layer 24 to obtain the skin material-forming laminate 26. The obtained laminate 26 for forming a skin material may be stored as a synthetic resin skin material forming material by covering the surface of the adhesive layer 24 with a protective sheet, and subsequently synthesizing by laminating the base material 28 in the next step. The resin skin material 10 may be formed.

[Transfer process]
The surface having the adhesive layer 24 of the obtained skin material forming laminate 26 and the base material 28 are adhered to each other and laminated, so that the skin material forming laminate 26 is in close contact with the base material 28 via the adhesive layer 24. To do. Lamination can be performed by a conventional method. In order to make the air bubbles 20 existing in the intermediate layer 22 not damaged and to be in close contact with the base material 28 while maintaining the thickness of the intermediate layer 22, the laminating is performed by a roll nip apparatus at a heating temperature in the range of 100 ° C. to 150 ° C. preferable.
After that, as shown in FIG. 4C, the temporary support 12 having the release agent layer 14 is peeled off, so that the surface layer 16 has a leather-like uneven pattern and has elasticity and strength. Material 10 is obtained.

<Base material>
There is no restriction | limiting in particular in the base material 28 used for the base of the synthetic resin skin material of this invention, A well-known thing can be used according to the objective.
Specifically, for example, a base fabric such as a knitted fabric or a non-woven fabric made of fibers such as tricot, a thermoplastic elastomer such as a styrene elastomer, an olefin elastomer, and a polyester elastomer or a thermoplastic resin molded into a sheet shape, etc. Is mentioned.
When a base fabric is used as the base material 28, the laminate for forming the skin material may be laminated without any particular processing. In addition, when using a sheet made of thermoplastic elastomer or thermoplastic resin as a base material, an easy adhesion treatment such as a corona discharge treatment or an adhesion assistant layer (primer layer) is applied to improve adhesion. It may be provided.
Even if a base material is a single | mono layer, it may have a multilayer structure which laminated | stacked the sheet | seat which has a physical property according to the objective.

If necessary, a first surface treatment layer 29 containing a colorant such as carbon black is formed on the surface of the surface layer 16 as shown in FIG. 4D, and a matting agent or the like is further formed thereon. You may form the 2nd surface treatment layer 30 to contain.
According to the production method of the present invention, a synthetic resin skin material provided with an intermediate layer having a desired film thickness, elasticity, and strength can be easily produced by a simple production method.

2. Synthetic resin skin material manufacturing equipment <Configuration>
Hereinafter, the configuration of an example of a synthetic resin skin material manufacturing apparatus according to the present invention will be described with reference to the drawings.
As shown in FIG. 1, the synthetic resin skin material manufacturing apparatus 1 includes a temporary support body delivery unit 3 that unwinds a web-like temporary support body 12 wound in a roll shape and sends out the web-like temporary support body 12 along the longitudinal direction a. Surface layer forming apparatus 5 for applying surface layer forming composition to release agent layer 14 of temporary support 12 delivered from temporary support delivery unit 3 and drying to form surface layer 16, and temporary support delivery unit 3 is located on the downstream side of the surface layer forming apparatus 3 along the feeding direction a of the temporary support 12 from 3, in other words, the conveying direction a, and the intermediate layer forming composition is applied to the surface of the surface layer 16 and applied. The liquid layer 18 is formed and dried to form the intermediate layer 22. The intermediate layer forming apparatus 7 is positioned on the downstream side of the intermediate layer forming apparatus 7 along the transport direction a and is bonded to the surface of the intermediate layer 22. A coating material is applied and dried to form an adhesive layer 24 to form a skin material laminate 26. Includes an adhesive layer forming device 9 which, a.

  On the downstream side of the adhesive layer forming apparatus 9 along the transport direction a, the base material laminating apparatus 11 for laminating the base material 28 by pressurizing and adhering to the adhesive layer 24 of the skin material forming laminate 26, and the base material The temporary support 12 is peeled off from the laminate 26 for forming the skin material 28 and the synthetic support 31 is peeled off, and the temporary support 12 peeled off by the temporary support 13 is wound up. And a temporary support winding unit 17. And the product winding part 19 which winds up the completed synthetic resin skin material 10 or the synthetic leather 31 is provided in the most downstream side along the conveyance direction a. In the synthetic resin skin material manufacturing apparatus 1, the temporary support feeding part 3 and the temporary support winding part 17 correspond to the temporary support conveying apparatus of the present invention.

  The surface layer forming device 5 detects a coating part 50 for applying the surface layer forming composition to the release agent layer 14 of the temporary support 12 and a coating weight of the surface layer forming composition applied by the coating part 50. A β-ray weight meter 51 for determining the coating amount per unit area, and both surfaces for drying the surface layer forming composition applied at the coating unit 50 and located downstream of the β-ray weight meter 51 along the conveying direction a. A dryer 52.

  The intermediate layer forming apparatus 7 includes an application unit 70 for applying the intermediate layer forming composition to the surface of the surface layer 16 formed by the surface layer forming apparatus 5, and a coating weight of the intermediate layer forming liquid applied by the application unit 7. The β-ray weight meter 71 for detecting the coating amount per unit area and the downstream of the β-ray weight meter 71 along the transport direction a, and drying the intermediate layer forming composition to apply the coating liquid layer 18. And then a double-sided dryer 72 that is heated and foamed to form the intermediate layer 22.

  The adhesive layer forming apparatus 9 includes an application unit 90 that forms an adhesive layer 24 by applying an adhesive to the surface of the intermediate layer 22 formed by the intermediate layer forming apparatus 7, and the weight of the adhesive formed by the application unit 90. A β-ray weight meter 91 that detects the amount of coating per unit area and detects the coating amount, and double-sided drying that dries the adhesive applied by the coating unit 90 and located downstream of the β-ray weight meter 91 along the transport direction a. Machine 92.

  Hereinafter, the application unit 50 of the surface layer forming apparatus 5 will be described. As shown in FIGS. 1 and 2, the coating unit 50 is used for forming a surface layer on the backup roller 50B around which the temporary support 12 is wound and the release agent layer 14 of the temporary support 12 wound around the backup roller 50B. A closed die coater 50A for applying the composition by pressurizing and discharging.

  As shown in FIG. 2, the closed die coater 50A includes a back plate 50C positioned upstream with respect to the conveyance direction a of the temporary support 12, that is, the rotation direction a of the backup roller 50B, and the rotation direction a of the backup roller 50B. And a discharge plate 50E formed between the back plate 50C and the front plate 50D. The upper end of the discharge channel 50E is a slit-shaped discharge port 50F. The closed die coater 50 </ b> A is disposed such that the discharge port 50 </ b> F is orthogonal to the transport direction a of the temporary support 12.

  Side plates are provided at both ends of the back plate 50C and the front plate 50D, but the side plates are omitted in FIG.

  The lower end of the discharge flow path 50E is a coating liquid supply flow path 50G to which the surface layer forming composition is supplied. A pump 50H for pumping the composition for forming a surface layer is connected to the coating liquid supply channel 50G via a pipe 50I.

  The rotation speed of the pump 50H is controlled so that the coating amount of the surface layer forming composition from the discharge port 50F is constant based on the measurement result of the coating weight of the surface layer forming composition in the β-ray weight meter 51. Is done.

  Since the application part 70 of the intermediate layer forming apparatus 7 and the application part 90 of the adhesive layer forming apparatus 9 have the same configuration as the application part 50 of the surface layer forming apparatus 5, description thereof is omitted.

Next, the double-sided dryer 52 will be described.
As shown in FIG. 3, the double-sided dryer 52 is a double-sided hot air nozzle type dryer, and has a casing 52A in which an inlet 52B and an outlet 52C of the temporary support 12 are formed. The inside of the housing 52A has a front side heating chamber 52D for heating and drying the surface on the side of the temporary support 12 on which the surface layer forming composition is applied, that is, the front side, with the path of the temporary support 12 as a boundary, and a temporary support The back side heating chamber 52E for heating and drying the back side surface of the body 12 is divided.

  In the front side heating chamber 52D, hot air nozzles 52F provided with slit-like hot air outlets 52L protrude from the ceiling surface 52G toward the conveyance path of the temporary support 12 at regular intervals. The direction of the hot air outlet 52L is a direction orthogonal to the transport direction a of the temporary support 12. Further, a portion near the inlet 52B of the front side heating chamber 52D is a temperature raising zone 52J, and a portion near the outlet 52C is a drying zone 52K. In the temperature raising zone 52J, the wind speed of the hot air ejected from the hot air nozzle 52F is set lower than that in the drying zone 52K.

  In the back side heating chamber 52E, hot air nozzles 52H having the same configuration as the hot air nozzle 52F protrude from the floor surface 52I toward the conveyance path of the temporary support 12 at a constant interval. However, the interval between the hot air nozzles 52H is set larger than the interval between the hot air nozzles 52F. In the example shown in FIG. 3, the interval between the hot air nozzles 52H is twice the interval between the hot air nozzles 52F, but is not limited to twice. In the hot air nozzle 52H, compared with the temperature raising zone 52J and the drying zone 52K, the wind speed of hot air is low, and the air volume is set large. The back side heating chamber 52E is also provided with support rollers 52M for supporting the temporary support 12 from below at regular intervals.

  The double-sided dryer 72 of the intermediate layer forming device 7 and the double-sided dryer 92 of the adhesive layer forming device 9 have the same configuration as the double-sided dryer 52 of the surface layer forming device 5 and are measured by the β-ray weight meters 71 and 91. Since the control is based on the result, the description is omitted.

  The substrate laminating apparatus 11 includes a nip roller 11A for niping the substrate 28 on the surface of the skin material forming laminate 26 on which the adhesive layer 24 is formed.

  The temporary support peeling apparatus 13 includes a support roller 13A that supports the skin material forming laminate 26 on which the base material 28 is laminated on the surface of the temporary support 12 in other words, that is, the lower surface.

<Action>
Hereinafter, the operation of the synthetic resin skin material manufacturing apparatus 1 will be described.
The temporary support 12 delivered from the temporary support delivery unit 3 first passes through the surface layer forming apparatus 5. Here, in the surface layer forming apparatus 5, the intermediate layer forming apparatus 7, and the adhesive layer forming apparatus 9, the temporary support 12 is placed on the backup rollers 50 </ b> B, 70 </ b> B, and 90 </ b> B in the application units 50, 70, and 90 with the release agent layer 14. It is wound so that the surface on the side where no is formed contacts.

  Therefore, as shown in FIG. 2, in the coating unit 50 of the surface layer forming apparatus 5, the surface layer forming composition is applied to the surface of the release agent layer 14 by the closed die coater 50A.

  The temporary support 12 coated with the surface layer forming composition passes through the double-sided dryer 52. The composition for forming a surface layer thus applied is heated and dried, and a surface layer 16 is formed on the surface of the release agent layer 14 as shown in FIG.

  Next, the temporary support 12 on which the surface layer 16 is formed passes through the intermediate layer forming apparatus 7. In the intermediate layer forming apparatus 7, the intermediate layer forming composition is applied to the surface of the surface layer 16 by the closed die coater 70 </ b> A. The temporary support 12 coated with the intermediate layer forming composition then passes through the double-sided dryer 72. In the double-sided dryer 72, the intermediate layer forming composition is dried in the temperature raising zone 72J to form the coating liquid layer 18 as shown in FIG. 4A, and then the coating liquid layer 18 is further formed in the drying zone 72K. By heating, the foam beads in the coating liquid layer 18 are foamed, and an intermediate layer 22 containing bubbles 20 is formed as shown in FIG.

  The temporary support 12 on which the intermediate layer 22 is formed passes through the adhesive layer forming apparatus 9, and the adhesive layer 24 is formed on the surface of the intermediate layer 22 as shown in FIG. 26.

  The skin material forming laminate 26 then passes through the substrate laminating apparatus 11 and then passes through the temporary support peeling apparatus 13. Thereby, as shown in FIG. 4C, the base material 28 is laminated on the surface on which the adhesive layer 24 is formed, and the temporary support 12 is peeled off from the surface layer 16, so that the synthetic resin skin material 10 and Is done.

  The temporary support 12 peeled off by the temporary support peeling device 13 is wound up in a roll shape by the temporary support winding portion 17.

  On the other hand, the synthetic resin skin material 10 is wound up in a roll shape by the product winding portion 19.

  In the manufacturing apparatus 1, the surface layer forming apparatus 5 applies the surface layer forming composition using the closed die coater 50A. Here, in the closed die coater 50 </ b> A, the surface layer forming composition is pumped by the pump 50 </ b> H and discharged from the discharge port 50 </ b> F, so that it is press-fitted into the irregularities formed on the surface of the temporary support 12. The same applies to the intermediate layer forming apparatuses 7 and 9.

  Therefore, although the surface layer forming device 5, the intermediate layer forming device 7, and the adhesive layer forming device 9 are thickly coated with the surface layer forming composition, the intermediate layer forming composition, and the adhesive, respectively. Application at high speed is possible.

  In addition, bubbles are prevented from being mixed into the surface layer forming composition, the intermediate layer forming composition, and the adhesive, so that appearance defects due to the mixing of bubbles can be prevented. Further, since the surface layer forming composition and the intermediate layer forming composition are press-fitted to the back of the irregularities formed on the surface of the temporary support 12, the embossed shape formed on the surface of the temporary support 12 is faithful. Is reproduced. Therefore, the occurrence of unnatural gloss due to insufficient reproduction of the embossed shape and the appearance defect due to bumping of the solvent in the coating liquid are effectively suppressed.

  Furthermore, in the surface layer forming device 5, the intermediate layer forming device 7, and the adhesive layer forming device 9, the temporary support 12 is heated and dried from both sides, so that the surface layer forming composition and the intermediate layer forming composition are used. Despite being thickly coated with an article and an adhesive, drying can be performed quickly, and drying unevenness can be prevented.

  In addition, in the double-sided dryers 52, 72, 92, the front side drying chambers 52D, 72D, 92D are divided into an inlet side heating zone 52J, 72J, 92J and an outlet side drying zone 52K, 72K, 92K. The wind speed is low in the temperature raising zones 52J, 72J, and 92J, and the wind speed is set high in the drying zones 52K, 72K, and 92K. For this reason, the applied surface layer forming composition, intermediate layer forming composition, and adhesive are gradually heated in the temperature rising zones 52J, 72J, and 92J. The drying zones 52K, 72K, and 92K are heated more strongly than the temperature raising zones 52J, 72J, and 92J. Therefore, in the temperature raising zones 52J, 72J, and 92J, the surface layer forming composition, the intermediate layer forming composition, and the solvent in the adhesive are gradually evaporated and removed, and in the drying zones 52K, 72K, and 92K, Dry to almost no solvent.

  On the other hand, in the back side drying chambers 52E, 72E, and 92E, the hot air velocity is lower than the front side drying chambers 52D, 72D, and 92D, and the air volume is set to be large. Therefore, the surface layer applied to the temporary support 12 It is possible to prevent appearance defects such as swelling due to abrupt heating of the forming composition, the intermediate layer forming composition, and the adhesive from the back side.

(Example 1)

(Base material)
A tricot fabric (knitted 40 denier yarn) base fabric was used as the substrate 28.

(Temporary support)
As the temporary support body 12, what was produced in the following procedures was used.
A prototype of natural leather was made by computer graphics, and the surface of the silicone rubber roller was infrared laser engraved based on the digital data to obtain a squeezing roll (embossing roll) having a fine wrinkle shape.
Using this embossing roll and a sheet for forming a release material having a resin layer having a thickness of 200 μm made of a resin composition containing 4-methyl-1-pentene resin on a nonwoven fabric, a leather wrinkle having a fine wrinkle shape A temporary support 12 having a shape was produced.
Further, a surface release treatment was performed on the embossed surface side of the temporary support 12 to form a release agent layer 14.

(Surface layer forming composition)
・ 100 parts by mass of one-component ether-modified polycarbonate polyurethane resin (DIC Corporation, Crisbon series)
-Colored organic resin fine particles (DIC Corporation, Daikarak series) 38 parts by mass-Solvent (toluene) 14 parts by mass-Solvent (DMF) 36 parts by mass

The above surface layer forming composition was sufficiently mixed to obtain a surface layer forming composition having a solid content of about 15% by mass.
On the surface of the temporary support 12 provided with the release agent layer 14 on the release agent layer 14 formation side, the surface layer forming composition is applied to a wet coating amount of 260 g / m ² using a closed die coater. Applied. After the coating film is formed, the coating film is dried using a double-sided hot air nozzle dryer at 100 ° C. for 2 minutes, and the surface layer 16 (film thickness after drying: about 40 μm) is formed on the temporary support 12. Formed.

(Composition for intermediate layer formation)
・ 100 parts by weight of a two-component polycarbonate polyurethane resin composition (DIC Corporation, Crisbon TK1015T)
・ 4 parts by mass of thermal expansion beads (made by Nippon Ferrite Co., Ltd., Expandel DU120)
Amine chain extender 4.6 parts by mass (manufactured by DIC Corporation, Crisbon CLH-1)
・ Colored organic resin fine particles 5.0 parts by mass (manufactured by DIC Corporation, Daikarak series)
・ Phosphate flame retardant 32 parts by mass (Clariant Japan, Peco Frame STC powder)
-Leveling agent 0.2 parts by mass (manufactured by DIC Corporation, Crisbon Assister SD-56)
・ Solvent (PGME) 26 parts by mass ・ Solvent (ethyl acetate) 26 parts by mass

The above intermediate layer forming composition was sufficiently mixed to obtain an intermediate layer forming composition having a solid content of about 50% by mass.
On the surface layer 16, the intermediate layer forming composition was applied using a closed die coater so that the wet coating amount was 150 g / m ² . After the coating film is formed, the coating film is dried using a double-sided hot air nozzle dryer at 100 ° C. for 2 minutes, and the coating liquid layer 18 (dried) is formed on the surface layer 16 as shown in FIG. The subsequent coating amount: 79 g / m ² ) was formed.
The formed laminate having the coating liquid layer 18 is heated at 170 ° C. for 2 minutes using a double-sided hot air nozzle type dryer to expand the thermally expanded beads, and as shown in FIG. The intermediate layer 22 having a thickness of about 360 μm was formed.

The surface of the formed intermediate layer 22 was coated with about 130 g / m ² of adhesive (manufactured by DIC Corporation, Crisbon TA-205) and dried at 100 ° C. for 2 minutes to form an adhesive layer 24. A laminate 26 for formation was obtained.
Next, the adhesive layer 24 of the laminate 26 and the tricot base fabric (base material) 28 were brought into contact with each other and laminated by a roll nip apparatus. The heating temperature was 135 ° C.
The temporary support 12 is peeled off, and as shown in FIG. 4C, the synthetic resin skin material having the adhesive layer 24, the intermediate layer 22 containing the bubbles 20 and the surface layer 16 in this order on the surface of the substrate 28. 10 was obtained.

(First surface treatment forming composition)
On the obtained laminate, 1% by mass of a carbon black pigment as a colorant is added to a non-yellowing polycarbonate polyurethane surface treatment agent (Star: WF-13-139) having a 100% modulus of 784 N / cm 2, and a lubricant. 10% by weight of a silicone emulsion (manufactured by Nissin Chemical Industry Co., Ltd .: Charine 170EM) and 5% by weight of carbodiimide as a cross-linking agent are coated with a gravure reverse coating apparatus so that the dry thickness is 8 μm. The first surface treatment layer 29 having excellent flat surface wearability was formed by drying at 2 ° C. for 2 minutes. A direct reverse gravure coater or the like may be used.

(Second surface treatment forming composition)
Further, a non-yellowing polycarbonate polyurethane having a 100% modulus of 735 N / cm 2 on the first surface treatment layer 29 (manufactured by Dainichi Seika Kogyo Co., Ltd .: Resamine LU-503SP) as a matting agent has an average particle size of 10 The surface treatment agent to which -20μm urethane beads and organic substance with moisture absorption / release function (manufactured by Kaneka Corporation: collagen powder (average particle size 3-5μm)) is added directly so that the dry thickness becomes 3μm. Applying with a gravure coater and drying at 140 ° C. for 2 minutes to form a moist, high-tactile second surface treatment layer 30, as shown in FIG. Of synthetic leather 31 was obtained. A gravure reverse coating apparatus may be used.

(Evaluation of the obtained synthetic resin skin material)
〔appearance〕
As for the so-called glossy, the appearance is visually observed, and there is no gloss that is not found in natural leather. Was evaluated as “◯”. At the same time, abnormalities in external shapes such as pinholes were also evaluated.
[Thickness]
The tactile sensation test conditions relating to the thickness feeling are as follows.
As a tester, a KES-G5 handy compression tester manufactured by Kato Tech Co., Ltd. was used.
<Test conditions>
Speed: 0.2mm / sec
Load: 50 gf / cm ²
<Evaluation method>
Thickness and thinness are obtained and determined from the value of To-Tm obtained under the above conditions. It can be said that as the value of To-Tm is larger, the paint is applied to the deep part of the temporary support 12 having abundant unevenness, so that there is a sense of volume. The results are shown in Table 1.

  As shown in Table 1, the synthetic leather 31 obtained in Example 1 showed no appearance abnormality such as glossy or pinhole. In addition, the wrinkle pattern was faithfully reproduced and there was a sense of volume.

(Example 2)
A synthetic resin skin material 10 shown in FIG. 4C was obtained in the same manner as in Example 1 except that the first surface treatment layer 29 and the second surface treatment layer 30 were not provided. About the obtained synthetic resin skin material 10, the external appearance and thickness feeling were evaluated in the same procedure as Example 1. The results are shown in Table 1.

  As shown in Table 1, the synthetic resin skin material 10 obtained in Example 2 did not show any appearance abnormality such as glossy or pinhole. In addition, the wrinkle pattern was faithfully reproduced and there was a sense of volume.

(Comparative Example 1)
In the formation of the three layers of the surface layer 16, the intermediate layer 18, and the adhesive layer 24, the surface layer forming composition, the intermediate layer forming composition, and the adhesive are applied by a liquid dam type knife instead of the closed die coater. A synthetic leather was produced in the same manner as in Example 1 except that the coater was used and the coating film was dried using a one-side hot air nozzle dryer instead of the double-side hot air nozzle dryer. About the obtained synthetic leather, the external appearance and thickness feeling were evaluated in the same procedure as Example 1. The results are shown in Table 1.

  As shown in Table 1, abnormal appearance such as glossy pinholes was clearly recognized in the synthetic leather obtained in Comparative Example 1. Moreover, since the wrinkle pattern was not reproduced faithfully, the volume feeling was poor.

(Comparative Example 2)
In the formation of the three layers of the surface layer 16, the intermediate layer 18, and the adhesive layer 24, the surface layer forming composition, the intermediate layer forming composition, and the adhesive are applied by a liquid dam type knife instead of the closed die coater. A synthetic resin skin material was produced in the same manner as in Example 2 except that the coating was performed using a one-side hot air nozzle dryer instead of the double-side hot air nozzle dryer. did. About the obtained synthetic resin skin material, the external appearance and thickness feeling were evaluated in the same procedure as Example 1. The results are shown in Table 1.

  As shown in Table 1, appearance abnormalities such as glossy and pinholes were also clearly recognized in the synthetic resin skin material obtained in Comparative Example 2. Moreover, since the wrinkle pattern was not reproduced faithfully, the volume feeling was poor.

DESCRIPTION OF SYMBOLS 1 Manufacturing apparatus 3 Temporary support body delivery part 5 Surface layer forming apparatus 7 Intermediate layer forming apparatus 9 Adhesive layer forming apparatus 10 Synthetic resin skin material 11 Base material laminating apparatus 11A Nip roller 12 Temporary support body 13 Temporary support body peeling apparatus 13A Support roller 14 Release agent layer 15 Thermal expansion bead 16 Surface layer 17 Temporary support winding part 18 Coating liquid layer 19 Product winding part 20 Air bubble 22 Intermediate layer 24 Adhesive layer 26 Laminate for skin material formation 28 Base material 29 First surface treatment Layer 30 Second surface treatment layer 31 Synthetic leather 50, 70, 90 Application part 50A, 70A, 90A Closed die coater 50B, 70B, 90B Backup roller 51, 71, 91 β-ray weight meter 52, 72, 92 Double-side dryer

Claims (11)

On the surface of the release agent layer of the temporary support having the release agent layer, the composition for forming the skin layer is discharged and applied from the slit-shaped discharge port, and then the temporary support is heated from both sides for forming the skin layer. A skin layer forming step of drying the composition to form a skin layer;
The formed surface of the skin layer, an adhesive pressure, discharged was applied to and then drying the adhesive by heating the temporary support from both sides of the slit-shaped discharge port, forming an adhesive layer Forming an adhesive layer;
A method for producing a synthetic resin skin material having In the skin layer forming step,
The surface layer forming composition is applied as a skin layer forming composition by applying pressure and discharge to the surface of the release agent layer of the temporary support having a release agent layer from a slit-shaped discharge port, and then the temporary support. Is heated from both sides to dry the composition for forming a surface layer, to form a surface layer,
Furthermore, the composition for forming an intermediate layer pressure, discharged was applied to as the skin layer forming composition to the surface of the surface layer from the slit-shaped discharge opening, then the heating said temporary support from both The method for producing a synthetic resin skin material according to claim 1, wherein the intermediate layer is formed by drying the intermediate layer forming composition .   The closed-die coater discharges and applies the skin layer forming composition, the surface layer forming composition, the intermediate layer forming composition, and the adhesive from the slit-shaped discharge port. Of manufacturing synthetic resin skin material. The intermediate layer forming composition dissolves the two-component polycarbonate polyurethane resin composition, the colorant, the thermally expanded beads, and the two-component polycarbonate polyurethane resin composition, but constitutes the thermally expanded beads. The method for producing a synthetic resin skin material according to claim 2, wherein the resin contains a solvent that does not dissolve. The method for producing a synthetic resin skin material according to claim 4, wherein the intermediate layer forming composition further contains a diamine chain extender . A temporary support transporting device for transporting a temporary support having a release agent layer formed on one surface in a certain direction;
A discharge-type coating apparatus that applies the composition for forming the skin layer to the surface of the release agent layer of the temporary support by applying pressure and discharge from the slit-shaped discharge port, and the discharge mold along the transport direction of the temporary support. A skin layer forming apparatus provided with a double-sided dryer located on the downstream side of the coating apparatus and heating the temporary support coated with the skin layer forming composition from both sides to dry the skin layer forming composition;
Along said conveying direction of the temporary support positioned on the downstream side of the skin layer forming apparatus, and the pressure of the adhesive from the slit-shaped discharge opening, discharging was in the temporary support formed by the skin layer forming apparatus A discharge-type coating device that is applied to the surface of the skin layer in the body, and a temporary support body, which is located downstream of the discharge-type coating device along the transport direction of the temporary support, and is coated with the adhesive from both sides An adhesive layer forming apparatus comprising a double-sided dryer for heating and drying the adhesive;
A base material laminating apparatus which is positioned downstream of the adhesive layer forming device along the transport direction of the temporary support and laminates the base material by pressing and adhering to the adhesive layer formed by the adhesive layer forming device When,
A temporary support peeling device located on the downstream side of the substrate laminating apparatus along the transport direction of the temporary support, and peeling the temporary support to make a synthetic resin skin material;
An apparatus for manufacturing a synthetic resin skin material. The skin layer forming apparatus is
A surface layer forming apparatus for forming a surface layer by applying and drying the surface layer forming composition on the surface of the release agent layer of the temporary support as the skin layer forming composition;
The intermediate layer forming composition is located on the surface layer surface formed by the surface layer forming device as the skin layer forming composition on the downstream side of the surface layer forming device along the transport direction of the temporary support. An intermediate layer forming apparatus for forming an intermediate layer by coating and drying;
With
Each of the surface layer forming apparatus and the intermediate layer forming apparatus includes a discharge type coating apparatus that pressurizes and discharges a coating liquid from a slit-shaped discharge port and applies the liquid onto an object, and a transport direction of the temporary support. An apparatus for producing a synthetic resin skin material according to claim 6, further comprising: a double-sided dryer that is positioned downstream of the discharge-type coating device and heats the temporary support from both sides to dry the coating solution . The synthetic resin skin material manufacturing apparatus according to claim 6 or 7 , wherein each of the discharge type coating apparatuses is a closed die coater.   The synthetic resin skin material manufacturing apparatus according to claim 8, wherein each of the double-sided dryers is a double-sided hot-air nozzle type dryer that blows hot air on both sides of the temporary support to dry. The skin layer forming device and the adhesive layer forming device have a coating amount measuring device for measuring the coating amount of the skin layer forming composition or the adhesive between the discharge type coating device and the double-sided dryer,
The synthetic resin skin material manufacturing apparatus according to claim 6, wherein the coating amount of the skin layer forming composition or the adhesive in the discharge type coating device is controlled based on a measurement result in the coating amount measuring device. Synthetic resin skin material production apparatus according to claim 10 wherein the coating amount meter measuring device is a β-ray weighing scale.

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