JP2016203436A - Synthetic resin skin material and method for producing the same, and molding using synthetic resin skin material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a synthetic resin skin material capable of forming a molding which suppresses deformation due to heating and drying in production of a synthetic resin skin material, enables preheating molding performed by bonding to a molding in a mold, and is excellent in appearance and a simple method for producing the same; and a molding having good appearance and a method for producing the same.SOLUTION: There is provided a synthetic resin skin material which has an adhesive layer, a base material layer containing a colorant and a synthetic resin, and a skin layer that contains at least one resin selected from an acrylic resin and a fluororesin and has irregularities formed on a surface on the side which does not contact with the base material layer on an adhesive layer protective sheet having a synthetic resin base material in this order, where the synthetic resin base material of the adhesive layer protective sheet has a softening point of 80°C or higher and 150°C or lower, and stretchability measured according to JIS K6734 using a tension/compression tester on conditions of a temperature of 150°C and a tensile speed of 500 mm/min is 150% or more.SELECTED DRAWING: Figure 1

Description

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

In recent years, automotive interior / exterior parts (instrument panels, door trims, seats, ceilings, etc.), railway vehicle interior parts, aircraft interior parts (trims, seats, ceilings, etc.), furniture, shoes, footwear, bags, interior / exterior components for construction, Synthetic resin skin materials having excellent durability are frequently used for clothing covering materials, clothing linings, wall covering materials, etc., 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. For example, in order to produce an automotive interior part using such a skin material, a method is generally used in which a skin material is disposed on the surface of a molded resin and is heat-molded or vacuum-laminated in a molding die. It is.

An acrylic resin film formed by the extrusion method has advantages such as excellent transparency, solvent resistance, stain resistance, and weather resistance, and can be molded at a relatively low temperature. Attempts are made to use it for exterior skin materials. However, since the heat resistance of the acrylic resin is not sufficient, when used as a skin material, even if irregularities such as a handle are formed on the surface, the irregular shape cannot be maintained at the time of heat molding, and is produced by heat molding. There is a problem that it is difficult to use as a skin material of a three-dimensional molded body member.
In order to form a skin layer that takes advantage of the properties of acrylic resin, a skin material is proposed that uses a skin layer containing an inorganic filler in an acrylic resin on the surface of a specific polyester resin layer (for example, (See Patent Document 1). However, even when this skin material is used, there is still room for improvement in the retention of the drawn pattern on the surface layer.

In general, a synthetic resin skin material used for design imparting the surface of a plastic part is a sheet that protects the surface where the skin layer is formed, and a sheet that protects the adhesive layer in the synthetic resin skin material having the skin layer and the adhesive layer. Comprising at least one of the following. The protective sheet for protecting the adhesive layer protects the adhesive layer for bringing the synthetic resin skin material into close contact with the molded body, specifically, the surface of the molding substrate until the synthetic resin skin material is applied to the molded body. It is a sheet arranged for the purpose. Since the protective sheet for protecting the adhesive layer is a sheet that can be freely attached to and detached from the adhesive layer, it is usually a film that has been subjected to a release treatment on the side that contacts the adhesive layer, or a material having releasability. It is a formed film. Hereinafter, in this specification, an “adhesive layer protective sheet” provided to protect the adhesive layer may be referred to as a “separator”.
In order to produce a resin molded body using a synthetic resin skin material, the synthetic resin skin material is placed on the surface of a molding resin member, a molding substrate, etc. Heat and mold in mold. When having a separator on the surface of the adhesive layer of the synthetic resin skin material, the separator is peeled off and removed before the synthetic resin skin material is bonded to the molded body.
Currently, a separator used for a synthetic resin skin material that is generally used is made of a material having no heat moldability because it is peeled and removed before molding.

  When decorating the surface of a three-dimensional molded article with a sheet-shaped synthetic resin skin material, place the synthetic resin skin material in a three-dimensional molding die in advance, or three-dimensional molding substrate A sheet-shaped synthetic resin skin material is adhered to the surface, but depending on the shape of the molded body, wrinkles may be formed in the synthetic resin skin material, or some areas of the synthetic resin skin material may be significantly more than other areas during heat molding. The drawn pattern may be deformed due to stretching. For this reason, in order to suppress the generation of wrinkles while applying the appearance of the synthetic resin skin material sufficiently, in recent years, synthetic resin skin materials have been applied to the surface of the molding substrate or molding molds. In order to improve the adaptability to the shape of the molded body, it is desired to perform pre-heating molding before placing it on the surface.

JP 2009-166407 A

When the synthetic resin skin material is pre-heat-molded, the pre-heat-molding is performed with the separator protecting the adhesive layer for bonding to the molding substrate being laminated. Since conventional separators do not have heat deformability, if preheating is performed while the separators are stacked, the separators may be peeled off from the adhesive layer, or the adhesive layer may be deformed due to the effect of the separator that is not thermally deformed. It has been clarified by the present inventors that there is a fear. If the separator is peeled off from the synthetic resin skin material during preheating, the adhesion of the adhesive layer will be reduced, making it difficult for the synthetic resin skin material to adhere to the molded body substrate, which may affect the finish of the molded body. .
On the other hand, in consideration of thermal deformability, when a thermoplastic resin film having a low softening point suitable for pre-heating molding is used as the base film for the separator, in the manufacturing process of the synthetic resin skin material, There is a possibility that the base film itself is thermally deformed by heating when the adhesive layer is closely adhered to the substrate and the adhesive layer is cured.

The object of the present invention is to suppress deformation due to heating and drying during the production of a synthetic resin skin material, and can be pre-heat-molded before being bonded to a molding substrate in a mold, and has an excellent appearance. It is providing the synthetic resin skin material which can form a molded object, and its simple manufacturing method.
Another object of the present invention is to provide a synthetic resin molded article having a good appearance using the synthetic resin skin material of the present invention and a method for producing the same.

As a result of intensive studies, the present inventors have used a separator using a synthetic resin base material having specific thermal properties for a synthetic resin skin material having at least a fluorine-containing resin skin layer and an adhesive layer. The inventors have found that the problems can be solved and completed the present invention.
That is, the present invention includes the following embodiments.
The invention according to the first embodiment of the present invention includes an adhesive layer, a base material layer containing a colorant and a synthetic resin, an acrylic resin, and a fluororesin on an adhesive layer protective sheet having a synthetic resin base material. A skin layer containing at least one selected resin and having an uneven surface formed on the surface that does not come into contact with the base material layer in this order, and the synthetic resin base material of the adhesive layer protective sheet has a softening point Is a synthetic resin having a stretchability of 150% or more measured at a temperature of 150 ° C. and a tensile speed of 500 mm / min using a tensile and compression tester in accordance with JIS K6734. It is a synthetic resin skin material which is a base material.
The adhesive layer protective sheet synthetic resin base material has a softening point of 80 ° C. or higher and 150 ° C. or lower, and conforms to JIS K6734, using a tensile / compression tester at a temperature of 150 ° C. and a tensile speed of 500 mm / min. Since the measured stretchability is a synthetic resin base material of 150% or more, the adhesive layer protective sheet is not deformed by the heat treatment in the production process of the synthetic resin skin material, and the moldability by heating during the preheating molding is good. The pre-molding of the synthetic resin skin material can be easily performed, and even when the molded body is produced using the synthetic resin skin material, the surface drawing pattern is maintained well, and the colored base material layer A molded product having excellent hue visibility and a good appearance can be obtained.

The invention according to the second embodiment of the present invention is the synthetic resin skin material according to the first embodiment, wherein the synthetic resin substrate of the adhesive layer protective sheet is a synthetic resin substrate selected from olefin resins. is there.
By using a synthetic resin substrate selected from olefin resins as the synthetic resin substrate of the adhesive layer protective sheet, thermal shrinkage during pre-heating molding of the adhesive layer protective sheet is suppressed, and dimensional stability is further improved. And the shape followability of the synthetic resin skin material at the time of preheating molding is further improved.

In the invention according to the third embodiment of the present invention, the synthetic resin contained in the base material layer is the first resin selected from the group consisting of an acrylic resin, a polyvinyl chloride resin, and a polyurethane resin. It is a synthetic resin skin material as described in the embodiment or the second embodiment.
By using a resin selected from the group consisting of acrylic resin, polyvinyl chloride resin, and polyurethane resin as the synthetic resin contained in the base material layer, the colorability of the base material layer containing the colorant is further improved and transparent. A synthetic resin skin material having a better appearance due to the base material layer visually recognized through the outer skin layer, and has better workability when being heat-processed in close contact with the molded body.

The invention according to the fourth embodiment of the present invention is the synthetic resin skin material according to any one of the first to third embodiments, which is a skin material of a thermoformed product.
In the synthetic resin skin material according to any one of the first to third embodiments of the present invention, deformation in application and curing treatment of the adhesive layer is suppressed, and preheating molding can be easily performed. Therefore, it can be suitably used as a skin material of a heat-molded product typified by a resin molded body, and an excellent appearance can be imparted to the heat-molded product.

The invention according to the fifth embodiment of the present invention includes a base material layer forming step of forming a base material layer containing a colorant and a synthetic resin using a colored resin composition containing a colorant and a synthetic resin. The base material layer is laminated on one surface of the base material layer with a material for forming a skin layer containing at least one resin selected from an acrylic resin and a fluororesin, and is laminated and embossed using a squeeze roll. And forming the skin layer by bonding the surface layer forming material and the surface layer forming material surface containing at least one resin selected from the acrylic resin and the fluororesin. Forming an adhesive layer forming composition layer by applying an adhesive layer forming composition to a surface of the base material layer opposite to the side on which the skin layer is formed, and forming the adhesive layer forming composition. On the surface of the layer, the softening point is 80 ° C or higher and 150 ° C An adhesive layer having a synthetic resin base material having a stretchability of 150% or more measured under conditions of a temperature of 150 ° C. and a tensile speed of 500 mm / min using a tensile and compression tester in accordance with JIS K6734 A protective sheet is laminated, and the laminate of the adhesive layer forming composition layer and the adhesive layer protective sheet is below the softening point of the synthetic resin substrate and is heated to 30 ° C. or higher and lower than 150 ° C. to adhere An adhesive layer forming step of forming a layer, and a method for producing a synthetic resin skin material.
After forming the adhesive layer-forming composition layer and laminating the adhesive layer protective sheet, it is below the softening point of the synthetic resin substrate and is in the temperature range of 30 ° C. or higher and lower than 150 ° C., preferably 40 ° C. to 60 ° C. When the composition layer for forming an adhesive layer is cured by heating to an adhesive layer, an adhesive layer having good adhesiveness, uniform layer thickness, and better dimensional stability is formed. Since the synthetic resin base material of the adhesive layer protective sheet has a softening point of 80 ° C. or higher and 150 ° C. or lower and has good stretchability, the adhesive layer is protected by heating when the adhesive layer is cured. The obtained synthetic resin skin material can be easily pre-heat-molded without thermal deformation of the sheet.

The invention according to a sixth embodiment of the present invention is the synthetic resin skin material according to any one of the first to fourth embodiments, wherein the synthetic resin skin material is 90 ° C to 140 ° C, and A pre-molding step of pre-heating molding under a temperature condition equal to or higher than the softening point of the synthetic resin forming the synthetic resin base material of the adhesive layer protective sheet, and peeling the adhesive layer protective sheet of the pre-molded synthetic resin skin material, And a molding step that is arranged on the surface of the molding substrate and heat-molded under a temperature condition of 90 ° C. to 140 ° C.
By pre-heating the synthetic resin skin material, the sheet-shaped synthetic resin skin material is pre-shaped into a shape suitable for the molding substrate, and the synthetic resin skin material is in close contact with the molding substrate having a curved surface. Compared to the case where wrinkles are suppressed and pre-heating is not performed, the generation of wrinkles in the synthetic resin skin material is suppressed, the adhesion between the synthetic resin skin material and the molding substrate is excellent, and the appearance is good. Can be easily manufactured.

In the invention according to the seventh embodiment of the present invention, the molding step peels off the adhesive layer protective sheet of the synthetic resin skin material that has been pre-heated and arranged in a mold for forming a molded body, It is a manufacturing method of the molded object as described in the said 6th Embodiment including arrange | positioning a shaping | molding base material in the said metal mold | die, and heat-molding on the temperature conditions of 90 to 140 degreeC.
Remove the pre-heat-molded synthetic resin skin material adhesive layer protective sheet, place it in the mold in advance, place the molding substrate in the mold and heat-mold it to make the appearance more efficient. An excellent molded body can be obtained.

The invention according to the eighth embodiment of the present invention is a molded body obtained by the method for manufacturing a molded body according to the sixth embodiment or the seventh embodiment.
Since the molded body of the present invention is pre-heat-molded with a synthetic resin skin material having good heat processability and used for the production of the molded body, it has excellent adhesion between the synthetic resin skin material and the molding substrate, and the synthetic resin skin material. It becomes a molded article excellent in appearance with suppressed generation of wrinkles.

  In the present invention, the skin layer has an acrylic resin excellent in adhesiveness with a base material layer containing a synthetic resin and a colorant (hereinafter, appropriately referred to as a colored base material layer), and excellent durability, Even when heated, it is provided with a skin layer containing at least one resin selected from fluororesins excellent in retention of the formed uneven pattern, and is formed on the outermost surface even when used for heat molding It is considered that a synthetic resin skin material that can maintain a drawn pattern well, has a high degree of freedom in coloring, and can form a molded article having an excellent appearance can be obtained. Moreover, according to the preferable aspect of the said structure, by using an acrylic resin for a colored base material layer and a skin layer, the content rate of the acrylic resin in a synthetic resin skin material increases, and vacuum laminate molding is carried out on the resin base material. There is an advantage that the developability of the case becomes good.

Further, on the side of the colored base material layer where the skin layer is not formed (hereinafter, the surface opposite to the side of the colored base material layer on which the skin layer is formed may be referred to as the back surface), the molded base material and the synthetic resin For the purpose of bonding the skin material, an adhesive layer is provided by laminating an adhesive or an adhesive. In addition, you may form between the coloring base material layer and the said contact bonding layer the resin layer (henceforth a primer layer) consisting of resin which functions as a primer between these layers.
Moreover, in other preferable embodiment of this invention, the base material layer containing various coloring agents can be easily manufactured by forming a coloring base material layer by a calendar method, In order to easily clean the inside of the apparatus necessary when changing the type and amount of addition, the method for producing a synthetic resin skin material of the present invention has a desired hue and a desired drawn pattern. Since various variations can be easily manufactured, it is suitable for small lot production of synthetic resin skin materials with abundant variations in hue and drawing pattern and excellent durability.
As described above, the skin material of the present invention is excellent in solvent resistance, contamination resistance, and weather resistance of the surface, and the drawn pattern is maintained well after being applied to a molded body. It is suitably used not only as a material but also as a vehicle exterior material.

According to the present invention, the deformation due to heating and drying during the production of the synthetic resin skin material is suppressed, and pre-heat molding performed before bonding in the molding substrate and the mold is possible, and the appearance is excellent. A synthetic resin skin material capable of forming a molded body and a simple manufacturing method thereof can be provided.
According to the present invention, by using the synthetic resin skin material of the present invention, a synthetic resin molded article having a good appearance and a method for producing the same can be provided.

It is a schematic sectional drawing which shows the synthetic resin skin material of 1 aspect of this invention. It is a schematic sectional drawing which shows the one aspect | mode of the molded object of 1 aspect of this invention.

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 illustrating an example of a layer configuration of a synthetic resin skin material 10 according to one embodiment of the present invention.
The synthetic resin skin material 10 of the present embodiment has a base material layer (colored base material layer) 12 containing a synthetic resin and a colorant, and is in contact with the colored base material layer on one surface of the colored base material layer 12. A surface layer 18 containing at least one resin selected from an acrylic resin and a fluororesin, on which unevenness is formed on the surface not to be formed, on the surface of the colored substrate layer 12 opposite to the side on which the skin layer 18 is formed The adhesive layer 22 has an adhesive layer protective sheet (separator) 24 on the surface of the adhesive layer 22.
The synthetic resin skin material 10 of this embodiment includes a colored base material layer 12 and a skin layer 18 containing at least one resin selected from an acrylic resin and a fluororesin. The outermost surface is, for example, natural leather-like. It has an arbitrary drawn pattern typified by unevenness.

Moreover, the adhesive layer 22 for making it adhere to the shaping | molding base material for forming a molded object is protected by the adhesive layer protective sheet 24, and when making it adhere | attach to a shaping | molding base material, the adhesive layer protective sheet 24 is peeled off. Glue. That is, the synthetic resin skin material 10 of the present invention includes an adhesive layer 22, a colored base material layer 12 containing a colorant and a synthetic resin, and a colored base material on an adhesive layer protective sheet 24 having a synthetic resin base material. A surface layer 18 containing at least one resin selected from an acrylic resin and a fluororesin in which irregularities are formed on the surface not in contact with the layer, in this order, and the synthetic resin base material of the adhesive layer protective sheet 24 The softening point is 80 ° C. or higher and 150 ° C. or lower, and the extensibility measured using a tensile / compression tester at a temperature of 150 ° C. and a tensile speed of 500 mm / min is 150% or higher in accordance with JIS K6734. It is a synthetic resin base material.
As shown in FIG. 1, the synthetic resin skin material 10 of the present invention has a molding base, which will be described later, on the surface of the colored base material layer 12 on which the skin layer 18 is not formed (the back surface of the colored base material layer). An adhesive layer 22 for adhering to the material 26 is provided. The adhesive layer 22 can be formed by applying an adhesive layer forming composition to the back surface of the adhesive base layer 12 to provide an adhesive layer forming composition layer, and drying and curing. Application of the adhesive layer forming composition layer to the colored substrate layer 12 may be performed by a transfer method or a coating method, but from the viewpoint of uniform lamination, the transfer method is preferred.
In order to further improve the adhesion between the colored base material layer 12 and the adhesive layer 22, it is also preferable to further include a primer layer 20 made of a resin having a function as a primer between both layers.
The synthetic resin skin material 10 of the present invention is used as a skin material of a molding base material 26 formed by thermoforming as will be described later. After forming the adhesive layer 22 on the back surface, the adhesive base material 22 is interposed on the molding base material 26. To obtain a molded body whose surface is decorated with a synthetic resin skin material 10, preferably by heat molding by a vacuum laminate molding method.

Hereinafter, the synthetic resin skin material of the present invention will be sequentially described together with materials constituting the same and a manufacturing method thereof.
(1. Base material layer containing synthetic resin and colorant)
(1-1. Synthetic resin)
The synthetic resin used for the colored base material layer 12 of the synthetic resin skin material 10 of the present invention is not particularly limited as long as it is a resin that can form a film or sheet by a known molding method such as a calender method or a melt extrusion method. . Examples of the synthetic resin that can be used for forming the colored substrate layer 12 include vinyl chloride resin, acrylic resin, polyurethane resin, and olefin resin.
Of these, a synthetic resin selected from the group consisting of a vinyl chloride resin, an acrylic resin, and a polyurethane resin is preferable from the viewpoint of ease of processing and flexibility of the obtained synthetic resin skin material.

As the vinyl chloride resin that can be used for the colored substrate layer 12, any vinyl chloride resin that has been conventionally used for vinyl chloride leather can be used without particular limitation. Specifically, in addition to polyvinyl chloride having an average degree of polymerization of 800 to 2000, preferably about 800 to 1500, a copolymer resin with ethylene chloride, vinyl acetate, methacrylic acid ester or the like mainly composed of vinyl chloride, or these Examples thereof include mixed resins of resin and polyester resin, epoxy resin, acrylic resin, vinyl acetate resin, urethane resin, acrylonitrile, styrene-butadiene copolymer resin, partially saponified vinyl alcohol, and the like.
When using a vinyl chloride resin for the colored base material layer 12, the colored base material layer 12 may be a foamed layer containing bubbles. When the colored substrate layer 12 is a vinyl chloride foam layer, a composition for forming a colored substrate layer is prepared by adding a plasticizer, a foaming agent, and the like to the vinyl chloride resin in addition to the colorant. The colored base layer 12 can be formed by forming the colored base layer forming composition into a sheet by a known molding method such as a calendar method or a casting method. Foaming may be performed either before forming into a sheet shape or after forming into a sheet shape.

  Examples of the acrylic resin that can be used for the colored base layer 12 include a polymer or copolymer of methacrylic acid or methacrylic ester represented by polymethyl methacrylate (PMMA), and a copolymer of alkyl methacrylate, alkyl acrylate, and styrene. From the viewpoint of moldability, a copolymer of alkyl methacrylate, alkyl acrylate, and styrene, a mixture of a copolymer of methyl methacrylate and methyl acrylate, and the like can be given.

Examples of the urethane resin that can be used for the colored substrate layer 12 include polycarbonate-based polyurethane, polyether-based polyurethane, polyester-based polyurethane, and modified products thereof. Of these, polycarbonate-based polyurethane and the like are preferable when long-term durability is required, such as automobile interior materials.
Examples of the olefin resin that can be used for the colored substrate layer 12 include polyethylene and polypropylene.

(1-2. Colorant)
Examples of the colorant contained in the base material layer include dyes, pigments, pearl particles, metal powders such as aluminum powder, and the like. Among these, pigments are preferably used from the viewpoints of durability and weather resistance.
Examples of the pigment that can be used in the present invention include inorganic pigments such as carbon black and titanium dioxide, and organic pigments exemplified below.
There is no restriction | limiting in particular in a pigment, In order to achieve a desired hue, 1 type, or 2 or more types of conventionally well-known various inorganic pigments, organic pigments, etc. can be selected suitably and can be used.
As the particle diameter of organic pigments, inorganic pigments, pearl particles, etc., from the viewpoint of color developability and handling properties, the average primary particle diameter is preferably in the range of 0.5 μm to 100 μm, more preferably 3 μm to 50 μm. Range.
The average primary particle diameter of the pigment is obtained by observing with a scanning microscope (SEM) or a transmission microscope (TEM), measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating an average value. be able to.

Examples of organic pigments that can be used in the present invention include, but are not limited to, the following.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment orange 36, 71,
C. I. Pigment Red 122,150,171,175,177,209,224,242,254,255,264
C. I. Pigment violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Brown 25, 28,
C. I. Pigment Green 7, 36, 37,
C. I. Pigment Black 1,

  In the case of using a pigment as the colorant, in the colored base material layer 12, in order to make the dispersibility in the synthetic resin contained in the colored base material layer 12 serving as the pigment dispersion medium better, It is preferable to use a dispersant suitable for a certain synthetic resin. For example, when carbon black is used as the pigment, it is preferable from the viewpoint of uniform dispersibility of the pigment that the colored base material layer 12 is formed using a mixture in which carbon black, an ester-based dispersant, and a synthetic resin are mixed in advance.

If an example of the usage aspect of a pigment is given, about 100 mass parts of synthetic resins used as the base material of the colored base material layer 12 will be charged about 3 mass parts to 5 mass parts of a pigment as a colorant, and a heat mixing roll By heating and mixing, the colorant is uniformly dispersed in the synthetic resin, and the synthetic resin is colored.
The colored substrate layer 12 may contain only one kind of colorant, or may contain two or more kinds for the purpose of toning. There is no restriction | limiting in particular in content of the pigment as a coloring agent, According to the hue of the target synthetic resin skin material 10, it selects suitably. Generally, it is preferable to contain in 3 to 20 mass% in the total solid content which comprises the colored base material layer 12. FIG. In addition, solid content means the component except the solvent in all the components which comprise the colored base material layer 12 here.

  In addition to the synthetic resin and the colorant, the colored substrate layer 12 may contain various compounds depending on the purpose. Examples of compounds that can be used in combination include plasticizers, lubricants, processing aids, flame retardants, light-resistant stabilizers, heat stabilizers, and the like.

The thickness of the colored substrate layer 12 is preferably in the range of 50 μm to 400 μm, and more preferably in the range of 180 μm to 220 μm.
There is no restriction | limiting in particular in the formation method of the colored base material layer 12, What is necessary is just to apply a well-known sheet shaping | molding method, and any of a calender method, a melt extrusion method, a solution method, etc. may be used. Of these, the calendar method is preferable from the viewpoint of ease of production and maintainability of the apparatus.
When forming the colored base material layer 12 by a calendar method, it may be formed under conditions of 200 ° C. to 210 ° C. using an apparatus such as a rolling roll manufactured by Nippon Roll.

(2. Skin layer)
The skin layer 18 of the synthetic resin skin material 10 of the present invention is a skin layer having irregularities formed on the surface, and contains at least one resin selected from an acrylic resin and a fluororesin. The skin layer may be a fluororesin-containing skin layer, an acrylic resin-containing layer, or a skin layer containing an acrylic resin and a fluororesin.

(2-1. Acrylic resin)
As the acrylic resin that can be used for the skin layer 18, the same acrylic resin that is described in the colored base layer 12 and that can be used for the colored base layer 12 can be used.

(2-2. Fluororesin)
The fluororesin that can be used for the skin layer 18 is a resin containing one or more fluorine atoms in the molecule, and examples thereof include a resin obtained by polymerizing an olefin containing a fluorine atom.

Examples of the fluororesin include tetrafluoroethylene resin, trifluorochloroethylene resin, hexafluoroethylenepropylene resin, ethylene-tetrafluoroethylene copolymer, and vinylidene fluoride resin.
The thickness of the skin layer 18 containing a fluororesin is preferably in the range of 10 μm to 100 μm, and more preferably in the range of 20 μm to 80 μm.

There is no restriction | limiting in particular in the formation method of the skin layer 18, What is necessary is just to form by applying a well-known layer formation method.
As a method of forming irregularities on the surface of the skin layer 18, a known method can be used as appropriate.

For example, natural leather-like unevenness is formed in advance on the squeeze roll, and the skin layer 18 is laminated and embossed using the squeeze roll on which the unevenness is formed. The unevenness is transferred.
Regardless of the method for forming the skin layer 18 and the method for forming irregularities on the surface of the skin layer 18, the heating temperature in the laminate embossing is preferably 100 ° C. to 190 ° C.
The synthetic resin skin material 10 of the present invention has a skin layer 18 on the outermost surface that is excellent in transparency and durability, and has a good ruggedness retention property during heating, and is a lower colored base material layer. Since the degree of freedom of coloring of No. 12 is high, it is suitably used as a skin material for a molded body that requires heat molding, and the obtained processed product has excellent appearance, surface durability, and solvent resistance. Become.

The thickness of the skin layer 18 containing at least one resin selected from an acrylic resin and a fluororesin is preferably in the range of 10 μm to 400 μm, and more preferably in the range of 20 μm to 200 μm.
The skin layer 18 is preferably transparent in order to reflect the hue of the colored base material layer 12 in the appearance. Here, “transparent” means that the transmittance of light having a wavelength in the visible region is 80% or more, and preferably 90% or more.

(3. Adhesive layer)
The synthetic resin skin material 10 of the present invention has an adhesive layer 22 on the surface of the colored base material layer 12 opposite to the side having the skin layer 18 for the purpose of bonding the molded base material 26 and the synthetic resin skin material 10. Prepare. There is no restriction | limiting in particular in the adhesive agent and adhesive used for formation of the contact bonding layer 22, According to the kind of the shaping | molding base material 26, it selects suitably. Examples of adhesives and pressure-sensitive adhesives that can be used for forming the adhesive layer include (1) two-component curable polyester adhesive, (2) two-component curable urethane adhesive, and (3) two-component curable acrylic adhesive. Are preferably used.
The adhesive used for forming the adhesive layer is also available as a commercial product. 3660 [Two-component curable polyurethane adhesive: No Tape Industry Co., Ltd.], Daikarak 7250NT [Two-component curable polyester adhesive: Daido Kasei Co., Ltd.] and the like are suitable.

The thickness of the adhesive layer 22 formed of an adhesive or a pressure-sensitive adhesive is preferably in the range of 20 μm to 100 μm in terms of dry film thickness.
As a method of forming the adhesive 22 on the colored substrate layer 12 or the resin layer 20 provided as desired, which will be described in detail below, any known method such as a transfer method or a coating method can be used. Among these, from the viewpoint that an adhesive layer having a uniform thickness can be easily formed, it is preferable to use a transfer method.
The adhesive layer 22 is provided with an adhesive layer-forming composition containing an adhesive or a pressure-sensitive adhesive on the colored substrate layer 12 or the resin layer 20 to provide an adhesive layer-forming composition layer, and then dried and bonded. The adhesive layer 22 is formed by curing the layer forming composition layer.
When forming the adhesive layer, in order to remove the solvent contained in the composition for forming the adhesive layer or to promote the curing reaction of the adhesive, the softening point of the synthetic resin base material used for the separator described later is below And it is preferable to heat and dry in a temperature range of 30 ° C. or higher and lower than 150 ° C. The heating temperature is preferably in the range of 40 ° C. or higher and 120 ° C. or lower, and more preferably in the range of 40 ° C. or higher and 60 ° C. or lower. Heating and drying are preferably performed in a non-contact manner, and examples thereof include drying with warm air and drying by transporting through a heating zone set to a predetermined temperature.

(Resin layer: Primer layer)
The synthetic resin skin material 10 of the present invention includes an adhesive layer 22 and a colored base material provided on the surface opposite to the surface on which the skin layer 18 of the colored base material layer 12 is provided (also referred to as the back surface of the colored base material layer 12). For the purpose of improving adhesion to the layer 12, it is preferable to further have a resin layer 20 as a primer layer between the adhesive layer 22 and the colored substrate layer 12.
The resin layer 20 can be formed by a coating method. That is, the resin for forming the resin layer can be dissolved in an appropriate solvent, applied to the back surface of the colored base material layer 12 opposite to the surface having the skin layer 18, and dried.
The resin layer 20 as the primer layer is preferably formed including a polyester resin or the like from the viewpoint of affinity with the synthetic resin constituting the colored base layer 12 and the resin contained in the adhesive layer 22.
There is no particular limitation on the coating amount of the resin layer, it is appropriately selected according to the purpose, in general, from the viewpoint of adhesiveness improvement in the range of 1g ^/ m ² ~5g / m 2 ^preferably, and more preferably in the range of ^{2g / m 2 ~3g / m 2} .

(4. Adhesive layer protective sheet: separator)
The synthetic resin skin material 10 of the present invention has an adhesive layer protective sheet (separator) 24 on the surface of the adhesive layer 22 in order to protect the surface of the adhesive layer 22.
As the separator 24, a synthetic resin film (synthetic resin substrate) and a synthetic resin film subjected to a release treatment can be used.
The synthetic resin substrate used for the separator 24 according to the present invention has a softening point of 80 ° C. or higher and 150 ° C. or lower, and conforms to JIS K6734, using a tensile / compression tester, at a temperature of 150 ° C. and a tensile speed of 500 mm. This is a synthetic resin base material having a stretchability of 150% or more measured under the conditions of / min.
If the softening point of the resin constituting the synthetic resin base material used for the separator is less than 80 ° C., the separator may be deformed when the adhesive layer 22 is heated and dried. In addition, when the softening point exceeds 150 ° C., pre-heating molding becomes difficult, energy required for pre-heating molding becomes large, and by pre-heating molding at a high temperature, it becomes a constituent component of other layers such as an adhesive layer. This is not preferable because there are concerns such as adverse effects.
Since the softening point of the synthetic resin base material used for the separator 24 is in the above range, the separator 24 is not deformed by the heat treatment in the manufacturing process of the synthetic resin skin material 10, and is easily deformed by heating at the time of pre-heating molding. Preheating molding of the synthetic resin skin material 10 can be easily performed, and the applicability to the molded body substrate is improved by the preheating molding.

The softening point can be measured according to the measuring method of JIS K6785 Vicat softening point.
The softening point correlates with the glass transition temperature (Tg) when the synthetic resin is an amorphous resin and with the melting point when it is a crystalline resin. When a commercially available synthetic resin film is used as the synthetic resin base material of the separator, the catalog value may be referred to for the softening point of the synthetic resin film.

  The synthetic resin base material has a stretchability of 150% or more measured under conditions of a temperature of 150 ° C. and a tensile speed of 500 mm / min using a tensile and compression tester in accordance with JIS K6734. The stretchability is preferably 180% or more, and more preferably 200% or more from the viewpoint of ease of preheating molding.

Examples of the synthetic resin that can be used for the synthetic resin base material of the separator 24 include olefin resins such as polyethylene and polypropylene. Polypropylene is preferable from the viewpoint of dimensional stability and suitability for preheating molding. Examples of the synthetic resin base material using polypropylene include uniaxially stretched polypropylene, biaxially stretched polypropylene, and unstretched polypropylene.
The thickness of the separator 24 is preferably 20 μm to 150 μm, and preferably 30 μm to 100 μm, from the viewpoint of ease of preheating molding.

As long as the separator 24 is a synthetic resin base material having stable adhesion to the adhesive layer 22 and easy peelability, the separator 24 may be composed of only the synthetic resin base material, and is bonded to the adhesive layer 22 of the synthetic resin base material. The surface on the side to be processed may be subjected to a mold release treatment.
As the release treatment, a known release treatment method such as a method of applying a fluorine-containing resin, a silicone resin or the like can be applied.
An adhesive layer may be further provided on the surface of the separator 24 opposite to the side in contact with the adhesive layer 22 for temporarily fixing the synthetic resin base material 10 when pre-heating molding is performed.

(Method for producing synthetic resin skin material)
The method for producing a synthetic resin skin material of the present invention includes a base material layer forming step of forming a base material layer containing a colorant and a synthetic resin using a colored resin composition containing a colorant and a synthetic resin. A surface layer forming material containing at least one resin selected from an acrylic resin and a fluororesin is laminated on one surface of the base material layer, and laminating and embossing using a squeezing roll, and the base material layer and A skin layer forming step of bonding the material for forming the skin layer and forming an unevenness on the surface of the skin layer to obtain a skin layer, and a surface opposite to the side on which the skin layer is formed of the base material layer An adhesive layer forming composition is applied to the adhesive layer forming composition layer, and the softening point is 80 ° C. or higher and 150 ° C. or lower on the surface of the adhesive layer forming composition layer, and JIS K6734. In accordance with the temperature of 150 ° C using a tensile and compression tester And an adhesive layer protective sheet having a synthetic resin substrate having a stretchability of 150% or more measured under a tensile speed of 500 mm / min, and a laminate of the adhesive layer forming composition layer and the adhesive layer protective sheet And an adhesive layer forming step of forming an adhesive layer by heating to 40 ° C to 60 ° C.
As a method for forming each layer, a known layer forming method can be applied as described above.

(Method for producing molded body)
The manufacturing method of the molded body 28 of the present invention is the softening point of the synthetic resin that forms the synthetic resin base material of the adhesive layer protective sheet in the synthetic resin skin material 10 of the present invention at 90 ° C to 140 ° C. A preforming step in which preheating is performed under the above temperature conditions, and the adhesive layer protective sheet 24 of the pre-molded synthetic resin skin material 10 is peeled off so that the adhesive layer 22 is in contact with the molding substrate 26. A molding step that is arranged on the surface of the material 26 and is heat-molded under a temperature condition of 80 ° C to 140 ° C.
When the adhesive layer protective sheet 24 of the pre-molded synthetic resin skin material 10 is peeled and placed on the surface of the molding substrate 26, the pre-molded synthetic resin skin material 10 is used for forming a molded body. Then, the molding base material 26 may be placed in the mold and heat-molded, and a synthetic resin skin material is adhered to the surface of the molding base material 26 via the adhesive layer 22. Then, you may heat-mold in a metal mold | die.

The resin constituting the molding substrate 26 used in the production process of the molded body is not particularly limited as long as it is a resin generally used for molding, but acrylonitrile / butadiene / styrene copolymer (ABS), polypropylene It is preferable to use (PP), a mixture of PC and ABS resin (PC / ABS), or the like.
The molded body 28 of the present invention is preferably molded by a vacuum laminate molding method in the above temperature range using the molding base material 26 formed of the resin and the synthetic resin skin material 10.

(Molded body)
The synthetic resin skin material 10 of the present invention is suitably used as the skin material of the molded body 28.
FIG. 2 is a schematic cross-sectional view showing the molded body 28 of the present invention.
The synthetic resin skin material 10 of the present invention preferably has a primer layer 20 and an adhesive layer 22 formed on the back surface of the colored base material layer 12, and the adhesive layer 22 is protected by a separator 24 as shown in FIG. Yes.
The molded body 28 of the present invention is a molded body 28 that is formed by bringing the adhesive layer 22 of the synthetic resin skin material from which the separator 24 has been peeled off and the molding base material 26 into close contact, and heat molding in a temperature range of 90 ° C to 140 ° C. .
The molded article of the present invention is a molded article having good adhesion to the synthetic resin skin material and excellent in appearance decorated with the synthetic resin skin material.

The synthetic resin skin material of the present invention is formed by a simple method, is excellent in appearance and durability, and is suitably used as a skin material for thermoforming. Therefore, the interior material for automobiles, interior parts for railway vehicles, aircraft It can be suitably used in various fields such as interior parts, furniture, shoes, footwear, bags, building interior / exterior members, clothing covering materials, clothing linings, and the like.
Moreover, the molded object formed using the synthetic resin skin material of this invention is manufactured by a simple method, and is excellent in an external appearance.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not restrict | limited to these.
[Example 1]
First, 2 kg of pigment (carbon black) is added to 100 kg of polyvinyl chloride resin [S1001N (trade name) Kaneka Co., Ltd.], and the thickness after drying is 150 μm by calendering while heating to 200 ° C. The colored base material layer 12 was obtained by forming into a sheet shape.
Then, the acrylic resin layer side was obtained above using a laminate of a fluororesin-containing layer and an acrylic resin-containing layer [KFC film FT-50Y (trade name), Kureha Chemical Industry Co., Ltd .: thickness of about 50 μm]. Laminated embossing using a squeezing roll (sheet surface temperature 170 ° C., speed 10 m / min) is made in contact with the colored substrate layer 12 to form a drawn pattern on the surface of the fluororesin-containing layer, and the colored substrate A laminated body of the layer 12 and the skin layer 18 on which the drawn pattern was formed was formed.
Thereafter, a polyester-based primer is applied to the back surface of the colored substrate layer 12 so that the thickness after drying is 3 μm, and dried to form a resin layer (primer layer) 20. Curable acrylic adhesive] is applied so that the film thickness after drying is 40 μm, the separator 24 is adhered to the surface, and heated and dried at 50 ° C. for 1 minute to form the adhesive layer 22. The synthetic resin skin material 10 of Example 1 having the skin layer 18 on the surface of the material layer 12 and the resin layer (primer layer) 20, the adhesive layer 22, and the separator 24 on the back surface of the colored base material layer 12 was produced.
As the separator 24, a stretched polypropylene film having a thickness of 60 μm (softening point: 100 ° C., stretchability: 500% or more) was used.

(Preliminary molding of synthetic resin skin material)
The obtained synthetic resin skin material 10 of Example 1 was placed in a preforming mold, and preheated by a vacuum molding method at a temperature condition of 150 ° C.
When the synthetic resin skin material 10 after the preheating molding was observed, the separator 24 was preliminarily molded into a shape as designed without peeling off from the adhesive layer 22.

(Production of molded body)
The separator 24 was peeled off from the preformed synthetic resin skin material 10 of Example 1, and the exposed adhesive layer 22 was formed into a molded base material (molded base resin: acrylonitrile / butadiene / styrene copolymer ( (ABS)) 26 and placed on the surface of the molding substrate 26. Adhesion of the synthetic resin skin material 10 to the molding base material 26 is generally performed by a manual pasting method. In the manual pasting method, the synthetic resin skin material 10 is adhered without wrinkles along the shape of the molding base material. Although it was difficult, the pre-molded synthetic resin skin material 10 of Example 1 was able to be bonded to the molding substrate 26 without wrinkles.
Thereafter, the molded substrate 26 and the synthetic resin skin material from which the separator 24 was peeled were molded by vacuum lamination molding at a temperature of 80 ° C. to 140 ° C. to obtain a molded body 28. The molded body 28 was a molded body 28 having a configuration as shown in FIG. 2, in which the preformed synthetic resin skin material 10 was in close contact with the surface of the molded base 26.

(Evaluation of synthetic resin skin material and molded product)
When the obtained molded body 28 was visually observed, the drawing pattern formed on the skin layer 18 had good retentivity, and no wrinkles of the synthetic resin skin material 10 were observed. A molded body 28 excellent in appearance and having an outer surface decorated with the synthetic resin skin material 10 was obtained.

[Comparative Example 1]
A synthetic resin skin material of Comparative Example 1 was obtained in the same manner as in Example 1 except that the separator in the synthetic resin skin material 10 was replaced with polyethylene terephthalate having a thickness of 60 μm (softening point: 80 ° C., stretchability: 115%). .
Thereafter, the obtained synthetic resin skin material was placed in a preforming mold and pre-heat-molded by a vacuum molding method at a temperature of 150 ° C.
When the synthetic resin skin material of Comparative Example 1 after the preliminary molding was observed, it was found that the separator 24 did not stretch and did not follow the mold.

  Thereafter, the molding substrate 26 and the synthetic resin skin material of Comparative Example 1 from which the separator 24 was peeled were molded by vacuum lamination molding at a temperature condition of 90 ° C. to 140 ° C. to obtain a molded body 28.

(Evaluation of synthetic resin skin material and molded product)
When the molded body using the synthetic resin skin material of Comparative Example 1 obtained was visually observed, it was difficult for the synthetic resin skin material of Comparative Example 1 to adhere to the molded body base material, resulting in floating, and the finished appearance. Declined.

  From the comparison between Example 1 and Comparative Example 1, the synthetic resin skin material of the present invention is excellent in the retention of the drawn pattern on the surface even under the preheating molding and the heating conditions in the thermoforming of the molded body. It is excellent in compatibility with the molding substrate 26, and the molded article of the present invention using this is excellent in retention of the drawn pattern formed on the surface of the skin material even after heat molding, and is caused by the synthetic resin skin material. It can be seen that the molded product 28 has a good appearance with suppressed generation of wrinkles.

10 Synthetic resin skin material 12 Colored substrate layer 18 Skin layer 20 Resin layer (primer layer)
22 Adhesive layer 24 Adhesive layer protective sheet (separator)
26 Molding Base Material 28 Molded Body

Claims (8)

On the adhesive layer protective sheet having a synthetic resin base material, the adhesive layer, a base material layer containing a colorant and a synthetic resin, and at least one resin selected from an acrylic resin and a fluororesin, A skin layer with irregularities formed on the surface on the side not in contact with the material layer, and in this order,
The synthetic resin substrate of the adhesive layer protective sheet has a softening point of 80 ° C. or higher and 150 ° C. or lower, and conforms to JIS K6734, using a tensile / compression tester at a temperature of 150 ° C. and a tensile speed of 500 mm / min. A synthetic resin skin material, which is a synthetic resin base material having a stretchability of 150% or more measured under conditions.   The synthetic resin skin material of Claim 1 whose synthetic resin base material of the said contact bonding layer protection sheet is a synthetic resin base material chosen from an olefin resin.   The synthetic resin skin material of Claim 1 or Claim 2 whose synthetic resin contained in the said base material layer is a synthetic resin selected from the group which consists of a polyvinyl chloride resin, an acrylic resin, and a polyurethane resin.   The synthetic resin skin material according to any one of claims 1 to 3, which is a skin material of a thermoformed product. A base material layer forming step of forming a base material layer containing a colorant and a synthetic resin using a colored resin composition containing a colorant and a synthetic resin;
A surface layer forming material containing at least one resin selected from an acrylic resin and a fluororesin is laminated on one surface of the base material layer, and laminating and embossing using a squeezing roll, and the base material layer and A skin layer forming step for obtaining a skin layer by bonding the material for forming the skin layer and forming irregularities on the surface of the material for forming the skin layer containing at least one resin selected from the acrylic resin and the fluororesin When,
An adhesive layer forming composition is applied to the surface of the base material layer opposite to the side on which the skin layer is formed, an adhesive layer forming composition layer is formed, and the adhesive layer forming composition layer surface is formed. The softening point is 80 ° C. or higher and 150 ° C. or lower, and the extensibility measured using a tensile / compression tester at a temperature of 150 ° C. and a tensile speed of 500 mm / min is 150% or higher in accordance with JIS K6734. An adhesive layer protective sheet having a synthetic resin base material is laminated, and the laminate of the adhesive layer forming composition layer and the adhesive layer protective sheet is below the softening point of the synthetic resin base material and is 30 ° C. or higher. An adhesive layer forming step of heating to less than 150 ° C. to form an adhesive layer;
A method for producing a synthetic resin skin material having The synthetic resin skin material according to any one of claims 1 to 4, wherein the synthetic resin skin material is 90 ° C to 140 ° C and is equal to or higher than a softening point of a synthetic resin that forms a synthetic resin substrate of the adhesive layer protective sheet. A pre-molding step for pre-heating molding under the temperature conditions of
The pre-heat-molded synthetic resin skin material adhesive layer protective sheet is peeled, placed on the surface of the molding substrate, and molded by heating under a temperature condition of 90 ° C to 140 ° C. Method.   The molding step peels off the adhesive layer protective sheet of the synthetic resin skin material that has been pre-heated, and is placed in a mold for forming a molded body, and a molding substrate is placed in the mold, The manufacturing method of the molded object of Claim 6 including heat-molding on the temperature conditions of 90 to 140 degreeC.   The molded object obtained by the manufacturing method of the molded object of Claim 6 or Claim 7.

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