JP5236896B2 - Manufacturing method of resin molded products - Google Patents

Description

  The present invention relates to a method for manufacturing a decorative molded resin product such as a home appliance exterior part, a mobile phone exterior part, a mobile device exterior part, a building material exterior part, or a vehicle interior part.

Exterior members used for home appliances, mobile phones, mobile devices, building materials, vehicle interior parts, etc. are generally produced by a molding method that can be produced in large quantities at a low cost and in a simple manner. Technology has also evolved as its applications expand.
Originally, simple, low cost, mass production is a feature of molded products, but due to the diversification of consumer demand in recent years, molded products are also excellent in design and can be differentiated in terms of functionality such as design and touch. The demand for has increased.

In terms of appearance, leather-like crests are engraved on the mold for molding in advance, the technology that gives the design to the appearance with the molding resin alone, the technology that insert-molds the leather-like film, and the leather-like film is laminated on the molded resin plate in advance. A vacuum forming method is generally used. Patent Document 1 discloses a technique for imparting designability and volume feeling by insert molding synthetic leather or leather.
However, the one molded by the former method certainly has a leather-like design on the appearance, but when you actually touch the molded product, you can feel the hardness and coldness of the molding resin and film, The so-called plastic product does not go out, and the one molded by the latter method is certainly different from the plastic product, but before molding, the shape after leather or synthetic There is a problem that the process becomes complicated, such as the need to process leather.

For this reason, it is conceivable to form a three-dimensional shaped molded product by using a continuously molded sheet and disposing the sheet on the surface of the molded product.
In the case of adopting a method of three-dimensional processing later using such continuously formed sheets, it can be performed using a method as shown in Patent Document 2.
JP 2006-175639 A JP 2006-1078 A

By the way, in the case of using a continuously formed sheet material on the surface of a molded product that has been subjected to three-dimensional processing, the surface of the molded product should be made to follow the shape of the mold without causing wrinkles due to the sheet material to have a desired shape. It was difficult to achieve both continuous molding of the sheet material.
That is, when the sheet material is continuously formed, tension is generated in the sheet material. However, if the strength of the sheet material is weak at the forming stage, deformation or the like occurs, and the sheet material cannot be accurately formed. Further, when the strength of the sheet material is high, the elongation at the time of pulling becomes small, and when the continuously formed sheet material is deformed into a three-dimensional shape, it is difficult to deform into a desired shape and also causes wrinkles. End up.

  On the other hand, by using a porous sheet material as the sheet material used for the surface of the molded product, the elongation at the time of pulling becomes larger, and the deformation at the time of compression becomes easy. Therefore, it becomes easy to follow a curved surface having a three-dimensional shape, and a molded product having a soft feeling and a volume feeling can be obtained. However, if a sheet material that has been foamed using a foaming agent during continuous molding, such as a sheet material that has been used conventionally, foaming is caused by the foaming agent remaining during reheating during three-dimensional processing. However, the surface condition of the molded product may be lowered.

  Therefore, it is desirable to use a porous sheet material without using a foaming agent. And as such a sheet material, there is a synthetic leather manufactured on a base material using a wet coagulation method, but there is a limit of elongation in a nonwoven fabric, a woven fabric, a knitted fabric, etc. used as a base material, and the whole sheet As a result, the elongation during pulling becomes small.

  Therefore, the present invention provides a decorative molding sheet for performing decorative molding that is arranged and molded so as to be the surface of a three-dimensionally processed molded product. It is an object of the present invention to provide a material that can achieve both surface properties.

And in order to achieve the above-mentioned object, the method for producing a resin molded product of the present invention is to apply a predetermined material on a release substrate and continuously make it porous by a wet coagulation method. pressurizing the decorative molding sheet, arranged so that the molded article on the surface of the three-dimensional shape, which is molded decorative, porous having to porous layer formed by peeling the release substrate after the The layer is formed by using a polyurethane material .

  In the method for producing a resin molded product of the present invention, a decorative molding sheet that has been continuously made porous by a wet coagulation method is used. Therefore, the sheet can be continuously molded, and this sheet is used. Therefore, when molding a three-dimensionally processed molded product, re-foaming does not occur, so that the moldability is good.

  Invention of Claim 2 is a manufacturing method of the resin molded product of Claim 1 characterized by using the textile fabric or the nonwoven fabric for the peeling base material.

  According to the invention described in claim 2, since a woven fabric or a non-woven fabric is used for the peeling substrate, extraction can be performed from the peeling substrate side during the wet coagulation method, and a well-balanced porous material Layer formation is possible.

In the invention according to claim 3 , the decorative molding sheet has a skin layer laminated on a porous layer, and the decorative molding sheet is formed of a molded product having a three-dimensional shape. It arrange | positions so that it may become the surface, and decorate-molding, It is a manufacturing method of the resin molded product of Claim 1 or 2 characterized by the above-mentioned.

According to the invention described in claim 3 , since the decorative molding sheet has a skin layer laminated on the porous layer, it is easy to impart designability and surface strength of a three-dimensional shaped molded product. It can be carried out.

Further, the skin layer can impart a shape to impart a leather-like appearance (claim 4).

In the invention described in claim 5 , the porous layer has a transfer surface formed by transferring the release surface of the release substrate, and the skin layer is laminated on the surface opposite to the transfer surface. It is a manufacturing method of the resin molded product of Claim 3 or 4 characterized by the above-mentioned.

According to the invention described in claim 5 , since the skin layer is laminated on the surface opposite to the transfer surface, it is also manufactured by a method of peeling the peeling substrate after laminating the skin layer. Can do. In addition, when a woven fabric or non-woven fabric is used as the release substrate, the surface shape of the release substrate can be transferred to the transfer surface, and when a three-dimensional molded product is formed, the decorative molding sheet is transferred. Adhesion between the surface and the resin sheet or the like that becomes the main body portion of the molded product can be improved.

The invention according to claim 6 is the method for producing a resin molded product according to claim 1 or 2 , characterized in that the surface of the porous layer is scraped to make a suede tone.

According to the invention described in claim 6 , since the surface of the porous layer is scraped to make a suede tone, it is possible to easily impart designability to a three-dimensional shaped molded product.

In the invention according to claim 7 , the porous layer has a transfer surface formed by transferring the release surface of the release substrate, and the surface opposite to the transfer surface is scraped to make a suede tone. It is a manufacturing method of the resin molded product of Claim 6 characterized by these.

According to the seventh aspect of the present invention, since the surface opposite to the transfer surface is scraped to make a suede tone, it can also be manufactured by a method of peeling the peeling substrate after shaving. In addition, when a woven fabric or non-woven fabric is used as the release substrate, the surface shape of the release substrate can be transferred to the transfer surface, and when a three-dimensional molded product is formed, the decorative molding sheet is transferred. Adhesion between the surface and the resin sheet or the like that becomes the main body portion of the molded product can be improved.

The related invention is a method for manufacturing a decorative molding sheet for manufacturing the decorative molding sheet according to any one of claims 1 to 7 , wherein a predetermined material is coated on the release substrate and wet. A step of continuously forming a porous layer by a coagulation method, a step of peeling the porous layer from the release substrate, and a step of laminating a skin layer on the porous layer. It is a method for producing a decorative molding sheet, characterized by producing a decorative molding sheet for performing decorative molding that is arranged and molded so as to be on the surface of a molded product.

  According to the present invention, a step of applying a predetermined material on the release substrate and making it continuously porous by a wet coagulation method, a step of peeling the porous porous layer from the release substrate, Since the decorative molding sheet is manufactured by the process of laminating the skin layer on the porous layer, the molding can be easily performed continuously, and a molded product of three-dimensional processing is molded using such a sheet. In some cases, the moldability is good.

  ADVANTAGE OF THE INVENTION According to this invention, the continuous formability of the sheet | seat for decorative shaping | molding can be performed favorably, and the surface property of the molded article of a three-dimensional process can be made favorable.

  The decorative molding sheet 1 used in the present invention has a layer configuration as shown in FIG. 1 and has a porous layer 10 and a skin layer 11. And as shown in FIG. 3, it can use for the decorative shaping | molding which arrange | positions the sheet | seat 1 for decorative shaping | molding on the surface of the molded article 5, and shape | molds.

As described later, the porous layer 10 is a layer formed by a wet coagulation method, and has a porous shape.
Although the thickness of the porous layer 10 is not specifically limited, 0.20-1.00 mm is preferable. This thickness can be adjusted by adjusting the coating amount of the raw material of the porous layer 10.

The skin layer 11 is a layer laminated on the porous layer 10. And as will be described later, when the decorative molding sheet 1 is arranged on the surface of the molded product 5 and the decorative molding sheet 1 becomes a part of the molded product 5, the skin layer 11 becomes the outermost layer of the molded product 5. Be placed.
The skin layer 11 is not porous and has a higher strength than the porous layer 10. Therefore, when the molded product 5 is used, the decorative molding sheet 1 is less likely to be damaged due to friction or the like.
Although the thickness of the skin layer 11 is not specifically limited, 1-50 micrometers is preferable. And this thickness can be adjusted by adjusting the coating amount of the raw material of the skin layer 11. FIG.

  In addition, the skin layer 11 is provided with a shape for giving a leather-like appearance, and specifically, has a certain pattern of irregularities.

As shown in FIG. 2, the porous layer 10 is formed by applying a predetermined material to be the porous layer 10 on the peeling substrate 50 and by wet coagulation.
Specifically, first, a release material 50 whose surface has been subjected to a mold release treatment is used, and a predetermined material that becomes the porous layer 10 is coated thereon.
The peeling substrate 50 is a long sheet material, and a material having strength and flexibility is used so that tension or winding can be performed in the process of forming the porous layer 10. The release substrate 50 can be made of a fabric material such as a woven fabric or a non-woven fabric. And by using the thing of such a material, when extracting the solvent of the raw material used for the porous layer 10, it can be extracted also from the peeling base material 50 side, and can extract from both surfaces.

  Specific examples of the material that can be used for the release substrate 50 include polyethylene terephthalate film, polyester oxford, polyester taffeta, polyester pongy, nylon film, nylon taffeta, woven fabric using natural fibers, and the above-mentioned synthetic fibers. Nonwoven fabrics and the like can be mentioned, and further, composites of these can be combined.

  Further, a release treatment can be performed on the release surface 50a on which the raw material of the porous layer 10 of the release substrate 50 is placed. As the mold release treatment, a silicone treatment, a fluorine-based water repellent treatment, an acrylic resin treatment, and a combination of the above treatments can be used. Further, when a fabric material such as a woven fabric or a nonwoven fabric is used for the release substrate 50, when the raw material for forming the porous layer 10 is applied, the release substrate 50 passes through the release substrate 50 and the back surface of the release substrate. There is concern over the breakthrough. In such a case, such processing can be prevented by performing calendar processing or the like after the processing.

The peel strength between the peeling substrate 50 and the porous layer 10 is desirably within a predetermined range. Specifically, the peel strength is preferably 20 to 200 g / inch, and more preferably 30 to 150 g / inch. If the peel strength is below, the peeling substrate 50 and the porous layer 10 are peeled off in the step of forming the porous layer 10 (particularly the wet coagulation step), causing troubles such as poor appearance and wrinkles. Further, if the peeling strength is exceeded, the peeling process of peeling the peeling substrate 50 and the porous layer 10 may cause a problem that peeling cannot be performed, and even if peeling can be performed, the porous layer 10 contracts or curls. There is a possibility that the porous layer 10 itself may be torn or fallen incapable of peeling.
In order to make this peeling strength fall within a predetermined range, it is carried out by selecting or combining the type of the peeling substrate 50, the processing method, and the like.

And the raw material used as the porous layer 10 is apply | coated to the peeling base material 50, and it wet-coagulates, and the porous layer 10 is formed.
The raw material used for forming the porous layer 10 in the present embodiment is obtained by dissolving polyurethane in the organic solvent A.

Polyurethane is a resin having a urethane bond, and specifically, conventionally known ones such as polyester-type polyurethane, polyether-type polyurethane, polycarbonate-type polyurethane, and composite polyurethane combining these can be used.
Furthermore, polycarbonate-type polyurethane and polyether-polycarbonate-type polyurethane are suitable for use in applications requiring high durability such as home appliances, mobile devices, building materials, and exterior members of interior parts for vehicles. On the other hand, for mobile phone exterior members, the life cycle of the product is short, so it seems that durability need not be very important, but because it is used for touching human skin, durability against sweat is required. Again, polycarbonate type polyurethane and polyether polycarbonate type polyurethane are suitable. Furthermore, since a temperature of 150 ° C. or higher is applied at the time of molding, a polycarbonate type polyurethane having excellent heat resistance is more preferable because of relatively high crystallinity.
These polyurethanes may be modified with other polymers having different skeletons, and examples include various types such as silicone-modified, fluorine-based polymer-modified, and polyacrylate-based polymer-modified polyurethane.

  The hardness of the polyurethane used as the raw material of the porous layer 10 can be arbitrarily selected. Since this hardness is affected by the soft feeling, volume feeling, and physical properties required for applications and molded products, in consideration of this, the range in which the 100% modulus is 2.94 to 29.3 MPa is preferable. Is particularly preferably 3.92 to 15.3 MPa.

And since the elongation at break of this polyurethane needs to correspond to deep drawing at the time of molding or to follow a three-dimensional curved surface, it is preferably 100 to 500%. Below this range, the sheet does not follow the deep drawing at the time of molding, and sheet breakage occurs, or a molded product with a sharp shape cannot be obtained without following the three-dimensional curved surface. On the other hand, if it exceeds this range, the followability of the deep drawing and the three-dimensional curved surface is good, but the porous structure is fully extended, resulting in lack of volume and softness.
In addition, the polyurethane used for the porous layer 10 may be used alone, or may be mixed with a plurality of types, and can be used according to the use and required characteristics of the molded product.
The measurement of 100% modulus and elongation at break is measured according to JIS K 6251.

Since the raw material for the porous 10 is made by dissolving polyurethane in the organic solvent A, the organic solvent A is one that can dissolve the polyurethane.
And the organic solvent A can use the organic solvent used for a conventionally well-known wet coagulation method, for example, aprotic polar solvents, such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone, dichloromethane, chloroform, Examples thereof include halogen solvents such as carbon tetrachloride, ketone solvents such as dimethyl ketone and methyl ethyl ketone, cyclic ether solvents such as tetrahydrofuran and dioxane, and aromatic organic solvents such as toluene and xylene.

In particular, among the above solvents used for the organic solvent A, an aprotic polar solvent is preferable in consideration of the influence on the environment, workability in the wet coagulation method, simplicity, and the like. Moreover, you may mix and use 2 or more types of these solvents as needed. Furthermore, the concentration at which the polyurethane is dissolved in the organic solvent A can be selected arbitrarily depending on the solvent, but is preferably 10 to 30% by mass, particularly preferably 15 to 25% by mass.
When the concentration is lower than these ranges, a ratio of pores to the volume in the porous layer 10, that is, a porous layer having a high porosity is obtained. In this case, the strength of the porous layer becomes remarkably weak and not only difficult to handle as a sheet, but also the porous layer is crushed at the time of molding, making it impossible to impart functionality such as volume and softness.
When the concentration is higher than these ranges, the strength of the porous layer 10 is improved, but the viscosity of the raw material for the porous layer 10 is remarkably increased, so that coating is difficult or desolvation is remarkable. This makes it difficult to obtain the porous layer 10.

  In addition, if necessary, additives such as modification of film physical properties of the polyurethane porous layer 10 in the present invention, exterior parts for home appliances, exterior parts for building materials, imparting flame retardancy required for interior parts for vehicles, etc. , Pore modifiers, fillers, flame retardants and the like may be added to the raw material for the porous layer.

For example, as an additive for the purpose of improving film physical properties, acrylic beads, ceramic beads, those in which these are dispersed in polyurethane, isocyanate-based crosslinking agents for imparting heat resistance, etc. can be mentioned. . Examples of pore regulators include nonionic, cationic, anionic surfactants, alcoholic solvents, hydrophilic polymer additives such as polyethylene oxide, and hydrophobic additives such as paraffinic oil and aromatic solvents. . The addition amount of these pore modifiers may be a commonly used amount, preferably about 0.1 to 10 parts by weight, and two or more types of the above regulators may be used in combination.
As the filler, there are inorganic and organic fillers, which are preferably added in accordance with the purpose of modification.
Examples of flame retardants include magnesium hydroxide, aluminum hydroxide, phosphorous nitrogen flame retardant, phosphate ester flame retardant, halogen flame retardant, etc., while balancing the deterioration of mechanical properties and imparting flame retardancy. It is preferable to add. Other additives include colorants for imparting design properties. As the colorant, it is preferable to select a colorant suitable for a conventionally known wet coagulation method, and a particularly preferable one is a vehicle having high durability.

In the step of applying the raw material for the porous layer 10 to the release substrate 50, a commonly used method can be employed. For example, a clearance coating method, a doctor knife coating method, a reverse roll coating method, a gravure coating method, Various things such as a bar coating method can be mentioned.
Although it is the quantity which applies the raw material for porous layer 10, it can change arbitrarily with the thickness of a base material, weight, and the kind of porous layer 10, 500-2000g per square meter is preferable. If it is less than this range, the self-supporting property of the porous layer 10 will be lost, and when peeling from the substrate, not only will there be problems of wrinkles and width shrinkage, but a volume feeling after molding may also be obtained. It becomes difficult. On the other hand, if it exceeds this range, the porous layer 1 shrinks during wet film formation, so that the base material is easily wrinkled, and if this becomes worse, the porous layer 10 will be peeled off during the process. A problem occurs.

And what coated the raw material for the porous layer 10 to a base material is immersed in the organic solvent B, is wet-coagulated, and is dried.
When immersed in the organic solvent B, the organic solvent A elutes in the organic solvent B. On the other hand, since the polyurethane itself does not dissolve in the organic solvent B, the porous layer 10 is formed by the polyurethane contained in the raw material for the porous layer 10. It is formed.
Further, as shown in FIG. 2, the porous layer 10 is formed by being peeled off from the peeling substrate 50. When the peeling step is performed, the porous layer 10 is completely dried. Or may be peeled off in an incomplete dry state.

The porous layer 10 is formed by peeling from the peeling surface 50a of the peeling substrate 50 after the wet coagulation method. Therefore, when a fabric material such as a woven fabric or a nonwoven fabric is used for the peeling substrate 50 as in this embodiment, fine irregularities on the peeling surface 50 a are transferred to the transfer surface 10 a of the porous layer 10.
And when the molded product 5 is shape | molded using the sheet | seat 1 for decorative shaping | molding, as FIG. 3 shows, it can carry out by making the transfer surface 10a of the porous layer 10 into a back surface. That is, the adhesiveness with the resin plate 20 can be improved by arranging the transfer surface 10a on the resin plate 20 or the adhesive 21 side.

The skin layer 11 is a layer for imparting design properties and surface strength, and is a layer laminated on the porous layer 10.
The lamination of the skin layer 11 may be performed before or after the porous layer 10 is peeled from the peeling substrate 50. In addition, the skin layer 11 can be formed on the porous layer 10. Alternatively, the skin layer 11 may be separately formed in a sheet shape and laminated by adhering it.
When it is difficult to handle the porous layer 10, a method of laminating the skin layer 11 before peeling the porous layer 10 from the peeling substrate 50 and then peeling the peeling substrate 50 can be employed.
As a method of forming the skin layer 11, a conventionally known method such as a dry transfer method of polyurethane, gravure coating, embossing, buffing or the like can be used.

As the resin used for the skin layer 11, a resin exhibiting a breaking elongation substantially equivalent to that of the porous layer 10 is preferable. This is because, when the fracture elongation between the porous layer 10 and the skin layer 11 is large during molding, the elongation characteristics are different in the thickness direction of the sheet. This is because when the sheet is bent or stretched, there is a problem that the sheet is cut or does not follow the three-dimensional curved surface.
Therefore, it is desirable to adjust the elongation at break between the resin for the porous layer 10 and the resin for the skin layer 11. However, considering the adhesion between the porous layer 10 and the skin layer 11, it is desirable to use the same type of resin. When polyurethane is used for the porous layer 10, the resin for the skin layer 11 is used. Is also preferably a polyurethane-based resin.
Moreover, what laminated | stacked the skin layer 11 combining the some layer according to the design and physical property which are requested | required is employable.

  In the decorative molding sheet 1 of the present embodiment, the skin layer 11 is disposed on the side opposite to the transfer surface 10a of the porous layer 10, and the transfer surface 10a of the porous layer 10 is used for decorative molding. It becomes the back surface of the sheet 1. The skin layer 11 can be disposed on the opposite side, and can also be disposed on the transfer surface 10a side.

And the molded product 5 can be manufactured as follows using the sheet | seat 1 for decorative shaping | molding as mentioned above.
When the molded product 5 is manufactured, the decorative molding sheet 1 is disposed in the mold, and the pressure on the front side of the decorative molding sheet 1 is smaller than the pressure on the back side due to injection pressure, reduced pressure in the mold, or the like. In this manner, the front side of the decorative molding sheet 1 is pressed against the mold. Then, the back side of the decorative molding sheet 1 is brought into close contact with the resin that is the main body portion of the molded product 5.
As a specific method, in a state where the decorative molding sheet 1 is disposed in the mold, the decorative molding sheet 1 can be molded by injection molding from the back side. A resin sheet or a resin plate serving as a main body portion of the molded product 5 can be laminated and molded by vacuum molding in which the decorative molding sheet 1 side is decompressed to a substantially vacuum state.

For the above-described injection molding or vacuum molding, a known method can be employed, and a conventionally known resin such as polyethylene terephthalate, polycarbonate, ABS or the like can be employed as the resin to be used.
Moreover, when using vacuum forming, although it can also adhere | attach by laminating | stacking the decorative molding sheet | seat 1 on the above-mentioned resin sheet or resin plate, it arrange | positions and shape | molds by arrange | positioning an adhesive agent among these. You can also. And the sheet | seat 1 for decorative molding can be stuck more firmly by arrange | positioning an adhesive agent.

  In this embodiment, as shown in FIG. 1 and FIG. 3, the molded product 5 is formed by stacking the decorative molding sheet 1 and the resin plate 20 and molding by vacuum molding using a mold 60. is there. As shown in FIG. 3, the decorative molding sheet 1 is arranged on the surface of the molded product 5 such that the skin layer 11 is the front side and the transfer surface 10 a side of the porous layer 10 is the back side. Further, an adhesive 21 is arranged between the decorative molding sheet 1 and the resin plate 20, and the decorative molding sheet 1 and the resin plate 20 are closely adhered by the adhesive 21.

  As shown in FIG. 3, the skin layer 11 of the decorative molding sheet 1 is disposed on the surface of the molded product 5, and the porous layer 10 is disposed inside the skin layer 11. When using, it is possible to give a soft feeling and volume feeling while ensuring the strength such as friction.

  Moreover, since the foaming agent is not used for the porous layer 10, since it does not re-foam in the case of the decorative shaping | molding which shape | molds the molded article 5, the surface of the molded article 5 may be made into a clean state. it can.

Although the above-described decorative molding sheet 1 has the skin layer 11, a sheet without the skin layer 11 can be employed.
For example, in the decorative molding sheet 2 shown in FIG. 4, the skin layer 11 is not provided. And the resin plate 20 is laminated | stacked similarly to the thing of above-described embodiment, Furthermore, the sheet | seat 2 for decorative shaping | molding and the resin plate 20 are closely_contact | adhered with the adhesive agent 21, and shaping | molding of the molded article 6 is performed.

Further, the surface of the decorative molding sheet 2 is treated, and specifically, the surface of the porous layer 10 is scraped with sandpaper or the like, and buffing is performed so as to obtain a suede-like appearance. It has been broken. And it can be set as a buffing product using such a buffed thing.
This buffing is performed on the surface opposite to the transfer surface 10a, and the buffed surface can be the front surface and the transfer surface 10a can be the back surface.

  Hereinafter, the present invention will be described in more detail based on examples. However, the present invention is not limited to the following description examples as long as the gist thereof is not exceeded.

  By the method shown below, the decorative molding sheets of Examples 1, 2, and 3 and Comparative Examples 1 and 2 were manufactured, and (1) the elongation at break of these decorative molding sheets was confirmed. The resin molded product was molded by a vacuum molding method, and (2) followability and (3) re-foaming property were confirmed.

(1) About breaking elongation, it measured based on JISK6251.
(2) Regarding the followability, the case where the sheet follows the three-dimensional surface is “◯”, and the case where the sheet does not follow and does not follow the mold shape is “x”.
(3) Regarding re-foaming, a case where foaming was not observed on the sheet by heating during molding was indicated as “◯”, and a case where foaming due to heating during molding was observed was indicated as “X”.

Example 1
84 dtex × 102.5 / 84 dtex × 90 polyester taffeta is immersed in the following silicone water repellent, squeezed with 0.3 MPa mangle, and then dried at 150 ° C. for 3 minutes to create a release substrate did.
Water repellent formulation, silicone KM-768 (manufactured by Shin-Etsu Chemical) 3 parts, Cat. A (manufactured by Shin-Etsu Chemical) 0.04 part. Cat. B (manufactured by Shin-Etsu Chemical) 0.05 parts

And the raw material for porous layers is adjusted to the peeling base material with the following composition, 800 g per square meter is applied with a bar coater, then immersed in water at a temperature of 25 ° C. for 4 minutes, and further heated at 40 ° C. After being immersed in the film for 15 minutes, the sheet was squeezed with a mangle having a pressure of 0.4 MPa, dried in an oven at 140 ° C., and then peeled off from the release substrate to obtain a sheet serving as a porous layer.
Reusamine CU8614 (manufactured by Dainichi Seika, polyurethane) 100 parts ・ Dimethylformamide (manufactured by Dainichi Seika) 70 parts ・ Seika Seven BS780S (manufactured by Dainichi Seika, pigment) 15 parts

Next, the skin layer raw material for the skin layer was prepared as follows, 100 g per square meter was coated on the skin-like release paper, dried in an oven at 120 ° C. for 2 minutes, 0.3 MPa, 80 ° C., 20 Under the condition of seconds, the film was heat-transferred to the sheet to be a porous layer obtained above and peeled off from the release paper to obtain a decorative molding sheet having a leather-like appearance.
Formula for appearance treatment / Resamine ME8210 (manufactured by Dainichi Seika, polyurethane) 100 parts / Dilac PV-5824 (manufactured by Dainippon Ink and Chemicals, pigment) 7 parts / Dimethylformamide 20 parts / Methyl ethyl ketone 20 parts / Resamine NE crosslinking agent (large 2 parts made by Nissei Kasei Co., Ltd.)

(Example 2)
After the sheet | seat used as a porous layer was created with the prescription similar to Example 1, the raw material for skin layers was adjusted as follows, and the sheet | seat for decorative shaping | molding which has a leather-like external appearance was obtained.
Formula for appearance treatment, rack skin U-1834M (Seiko Kasei, polyurethane) 100 parts, rack skin U-1840G (Seiko Kasei, polyurethane) 30 parts, Dilack PV-5800 (Dainippon Ink and Chemicals, pigment) 5 Part

(Example 3)
After creating a porous sheet with the same formulation as in Example 1, as a surface treatment, the surface opposite to the transfer surface was buffed with # 180 sandpaper, and then dressed with # 240 sandpaper. A suede leather-like sheet was obtained.
In Example 3, no skin layer was provided.

(Comparative Example 1)
A 75-denier / 72-filament polyester multifilament yarn is supplied to the front heel of a warp knitting machine (28 gauge), and a 50-denier / 24-filament polyester multifilament yarn is supplied to the back heel to form a half structure. A tricot with raised hair was dipped in water and squeezed with a mangle with a pressure of 0.4 MPa to obtain a substrate. Thereafter, 800 g of the same composition as the raw material for the porous layer used in Example 1 was applied on the raised surface of the base material with a bar coater per square meter of coating amount, and then in water at a temperature of 25 ° C. for 4 minutes. After dipping and further dipping for 15 minutes in warm water at 40 ° C., drying in an oven at 140 ° C. yielded a decorative molding sheet having a porous layer laminated on a substrate.
Note that the decorative molding sheet of Comparative Example 1 has the same wet coagulation layer as Example 1, but the base material is not peeled off. The same synthetic leather was used.

(Comparative Example 2)
The resin composition shown below was kneaded for 5 minutes with a Banbury mixer, then kneaded for 6 minutes with a two-roll warm-up roll, and a reverse L-shaped four-roll calender to make a 1/2 twill fabric (weight per unit) (Amount: 180 g per square meter) was stuck to a thickness of 0.4 mm.
Resin blend / Acryt CM-2008 (Sumitomo Chemical, EMMA) 100 parts / AZ-H (Otsuka Chemical, foaming agent) 5 parts / LS-5 (Asahi Denka Kogyo, lubricant) 0.1 part / MBE- 10690 (special colorant industry, pigment) 5 parts

Then, 15 g of a primer (US-200CL-1, Seiko Kasei) is applied to the surface of the above sheet per square meter and dried, and then a modified acrylic resin type surface treatment agent (584-6, Seiko Kasei) is applied at 15 g per square meter. Coated and dried.
Further, the resin blend sheet was placed in an oven at a temperature of 210 ° C. for 2 minutes to obtain a foam sheet having a thickness of 0.9 mm. And the leather compound embossing was given to the resin compound side at 150 degreeC, and the sheet | seat for decoration shaping | molding was obtained.

And the vacuum molding was performed using the sheet | seat for decorative shaping | molding of Examples 1, 2, 3 and Comparative Examples 1, 2, and the three-dimensional-shaped resin molding was shape | molded.
Specifically, using an 8 cm long, 4 cm wide, 1 cm deep mold, an acrylic pressure-sensitive adhesive was applied to the decorative molding sheet and bonded to a 0.3 mm thick polycarbonate plate. Placed in the mold. Then, after heating under the conditions of a heater temperature of 270 ° C., a heating time of 20 seconds, and a heater-sheet distance of 15 mm, vacuum forming was performed.
In addition, this metal mold | die used the shape of the protrusion part of the three-dimensional shape by the side of the sheet | seat for decorative shaping | molding whose width is 48 mm, length is 86 mm, and depth is 10 mm.

Table 1 shows the evaluation results of Examples 1, 2, and 3 and Comparative Examples 1 and 2.

As shown in Table 1, the decorative molding sheets of Examples 1, 2, and 3 are good results in all test items, and since no fabric is used, The horizontal difference is small.
On the other hand, the decorative molding sheet of Comparative Example 1 is inferior in followability as compared with Examples 1, 2, and 3, and the decorative molding sheet of Comparative Example 2 is compared with Examples 1, 2, and 3. The followability and re-foamability are inferior.

It is sectional drawing which showed the process of performing decoration shaping | molding using the sheet | seat for decoration shaping | molding. It is sectional drawing which showed the process of forming the porous layer of the sheet | seat for decorating shaping | molding shown in FIG. It is sectional drawing which showed the process of performing decoration shaping | molding using the sheet | seat for decoration shaping | molding shown in FIG. It is sectional drawing which showed the molded article decorated and molded using the sheet | seat for decoration shaping | molding of a modification.

DESCRIPTION OF SYMBOLS 1, 2 Sheets for decorative molding 5, 6 Molded article 10 Porous layer 11 Skin layer 20 Resin plate 21 Adhesive 50 Peeling substrate

Claims (7)

Decorative molding having a porous layer formed by applying a predetermined material on a release substrate and making it porous continuously by a wet coagulation method, and then removing the release substrate after making it porous the use sheets, arranged so that the molded article on the surface of the three-dimensional shape, which is molded decorative, the molding of the porous layer, the resin molded article wherein the polyurethane material is used Manufacturing method.   The method for producing a resin molded product according to claim 1, wherein a woven fabric or a non-woven fabric is used for the release substrate. The decorative molding sheet has a skin layer laminated on the porous layer,
The method for producing a resin molded product according to claim 1 or 2 , wherein the decorative molding sheet is arranged and decorated so that the skin layer is a surface of a molded product having a three-dimensional shape. . The method for producing a resin molded product according to claim 3 , wherein a shape for imparting a leather-like appearance is imparted to the skin layer. The porous layer has a transfer surface formed by transferring a release surface of a release substrate, and the skin layer is laminated on a surface opposite to the transfer surface. A method for producing a resin molded product according to 3 or 4 . Method for producing a resin molded article according to claim 1 or 2, characterized in that the suede by cutting the surface of the porous layer. The porous layer has a transfer surface which can be by transferring the release surface of the release substrate, according to claim 6, characterized in that the suede by cutting the surface opposite to the transfer surface Manufacturing method for resin molded products.

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