JP2010255151A - Method for manufacturing embossed release paper - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing an embossed release paper capable of improving releasing properties with a synthetic leather and improving the shaping ratio of emboss processing. <P>SOLUTION: The embossed release paper includes: an embossed release substrate 1 with an unevenness on the surface; and a releasing layer 2 formed on the surface of the release substrate 1 by a CVD method. In the method for manufacturing the embossed release paper, the unevenness is formed by a chill roll embossing method in which an emboss roll 50 cooled at a predetermined temperature is brought into contact with a hot melt resin 13 and the hot melt resin 13 is cooled and solidified. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an embossed release paper and a method for producing an embossed release paper.

  Synthetic leather consists of a substrate made of cloth or non-woven fabric and a leather surface layer made of a polymer material. The surface layer is made of polyvinyl alcohol, polyamide, polyurethane, etc. The surface of the surface layer is modified. A finishing layer made of polyamide, polyurethane, polyacrylic acid derivative or the like is formed, and a leather wrinkle pattern or the like is embossed on the finishing layer.

  For embossing, an embossed release paper having a reverse pattern such as a leather wrinkle pattern on the surface is used. The embossing release paper is formed by, for example, applying a coating material on a substrate and pressing an embossed plate heated to a predetermined temperature on the substrate on which the coating material is applied to melt the surface of the coating material. Done.

  The degree of achievement in embossing is expressed as, for example, the ratio of the depth from the reference surface of the corresponding part in the embossed product to the depth from the reference surface of the predetermined part in the plate roller for embossing, that is, "molding rate" There is. It is known that this shaping rate varies depending on various conditions in embossing and affects the quality of the object to be embossed.

  If the embossing pressure in embossing is small or the amount of resin to be melted is small, the amount of plastic deformation is reduced, so that the molding rate is lowered, and the formation of irregularities on the embossed object becomes shallow (there is a problem) For example, see Patent Document 1). Further, it is known that when embossing is performed by hot pressing, the forming rate can be improved only to about 80%.

  Embossing method by embossing using high energy of EB (electron beam) and extruding process in which molten resin is eluted from an extrusion machine and solidified while cooling the resin with a cooling roll to improve the forming rate It has been known. Examples of the resin used for these processes include resins such as polyethylene (PE), polypropylene (PP), polymethylpentene (TPX), polyester, and nylon.

  However, some resins such as polyethylene (PE), polypropylene (PP), and polymethylpentene (TPX) exhibit heat resistance only at about 110 to 180 ° C., and therefore need to be dried in a high temperature environment of 200 to 250 ° C. It cannot be used to manufacture PVC leather. Conversely, when a resin such as polyester or nylon is used, when a urethane resin is used as the surface film, it reacts with the isocyanate in the urethane resin, so that it is difficult to peel the synthetic leather from the release paper.

JP 2005-146467 A

  In view of the above problems, an object of the present invention is to provide a method for producing a release paper with embossing that can improve the releasability from synthetic leather and can improve the forming rate of embossing.

  In order to solve the above-mentioned object, an aspect of the present invention provides an embossed release paper provided with an embossed release substrate having irregularities on the surface and a release layer formed by a CVD method on the surface of the release substrate. The gist of the present invention is that the embossing roll cooled to a predetermined temperature is brought into contact with the hot melt resin, and the embossed release paper is formed by cooling and solidifying the hot melt resin.

  ADVANTAGE OF THE INVENTION According to this invention, this invention can provide the manufacturing method of the release paper with an embossing which can improve the peelability with a synthetic leather and can improve the shaping rate of embossing.

It is sectional drawing of the release paper with an embossing which concerns on embodiment of this invention. It is a graph which shows IR spectroscopy spectrum in case the flow ratio of the monomer gas of raw material gas at the time of film-forming is 100: 500 by a weight part. It is a graph which shows IR spectroscopy spectrum in case the flow rate ratio of the monomer of the raw material gas at the time of film-forming is 100: 1000 in a weight part. It is sectional drawing explaining the manufacturing method of the synthetic leather which concerns on embodiment of this invention. It is sectional drawing explaining the manufacturing method of the synthetic leather which concerns on embodiment of this invention. It is sectional drawing explaining the manufacturing method of the synthetic leather which concerns on embodiment of this invention. It is sectional drawing which shows the 1st example of the release paper with embossing which concerns on embodiment of this invention. It is the schematic which shows an example of the manufacturing apparatus of the release paper with an embossing which concerns on embodiment of this invention. It is a flowchart which shows the manufacturing method of the release paper with an embossing which concerns on embodiment of this invention. It is sectional drawing which shows the 2nd example of the release paper with an embossing which concerns on embodiment of this invention. It is the schematic which shows an example of the manufacturing apparatus of the release paper with an embossing which concerns on embodiment of this invention. It is a flowchart which shows the manufacturing method of the release paper with an embossing which concerns on embodiment of this invention. It is sectional drawing which shows the 3rd example of the release paper with embossing which concerns on embodiment of this invention. It is the schematic which shows an example of the manufacturing apparatus of the release paper with an embossing which concerns on embodiment of this invention. It is a flowchart which shows the manufacturing method of the release paper with an embossing which concerns on embodiment of this invention.

  Embodiments of the present invention will be described below with reference to the drawings. In the following description of the drawings, the same or similar parts are denoted by the same or similar reference numerals. However, the drawings are schematic. Therefore, specific dimensions and the like should be determined in light of the following description. Moreover, it is a matter of course that portions having different dimensional relationships and ratios are included between the drawings.

(Embossed release paper)
As shown in FIG. 1, the embossed release paper according to the embodiment of the present invention was formed on the surface of the release substrate 1 with the embossed surface and the surface of the release substrate 1 by the CVD method. And a release layer 2.

  As the release substrate 1, for example, PE, PP, TPX, polyester, nylon, acrylic resin on a sheet such as high-quality paper, kraft paper, glossy kraft paper, pure white roll paper, glassine paper, and cup base paper. A material coated with a resin such as is used.

As the release layer 2, for example, a silica film (SiO ₂ film) formed so as to leave at least one of a methyl (CH ₃ ) group and an ethyl (C ₂ H ₅ ) group on the surface is preferable. By forming at least one of the CH ₃ group and the C ₂ H ₅ group on the surface of the release layer 2, the peelability from the urethane resin is improved. The “silica film formed so as to leave at least one of a methyl group and an ethyl group on the surface” according to the present embodiment is formed by a CVD method using a material containing a methyl group directly bonded to an Si atom. Can be manufactured. The film forming conditions in the CVD method will be described later.

The presence of CH ₃ groups and C ₂ H ₅ groups remaining on the surface of the release layer 2 can be confirmed using an IR spectrometer. That is, the peak appearing in the vicinity of 1280 cm ^{−1 in the} IR spectroscopic spectrum is due to the Si—CH ₃ stretching vibration. Therefore, the presence of a methyl group can be confirmed by the presence of a peak appearing near 1280 cm ⁻¹ .

FIG. 2 shows that when the release layer 2 is formed using the CVD method, the ratio of the monomer material to oxygen in the source gas during film formation is set to 500 parts by weight of oxygen gas with respect to 100 parts by weight of monomer material. It is a graph showing the example of a case. FIG. 3 is a graph showing an example in which the oxygen gas is 1000 parts by weight with respect to 100 parts by weight of the monomer material. In the case of FIG. 2, since the peak near 1280 cm ⁻¹ is large, it can be seen that a methyl group is present on the surface. On the other hand, in the case of FIG. 3, since a peak near 1280 cm ⁻¹ cannot be confirmed, it is presumed that no methyl group remains on the surface.

  The thickness T of the release layer 2 is preferably 1 nm (10 cm) or more. If the film thickness T of the release layer 2 is thinner than 1 nm, the release layer 2 does not exist as a continuous film, so that release becomes difficult. On the other hand, if the film thickness is thicker than 100 nm, it is not preferable from the viewpoint of productivity, and the embossed shape may be damaged. In order to repeatedly use the embossed release paper, the film thickness T is preferably about 1 to 100 nm.

  It is preferable that the surface of the release layer 2 has a contact angle with diiodomethane of 60 ° or more, more preferably about 60 ° to 65 °. By setting the contact angle of the surface of the release layer 2 to 60 ° or more, a delicate pattern formed on the surface of the release substrate 1 can be imparted on the surface of the skin layer of the synthetic leather with good reproducibility. At the same time, the releasability when peeling the release paper from the synthetic leather is improved. For the evaluation of the contact angle, the contact angle was determined from the angle of the straight line connecting the left and right end points and the vertex of the droplet to the solid surface by the θ / 2 method.

(Method for producing release paper with emboss)
In order to manufacture the release paper with embossing according to the embodiment, for example, first, the release substrate 1 with embossing having irregularities on the surface is introduced into the vacuum chamber. Then, a monomer material containing at least one of Si atoms, CH ₃ groups and C ₂ H ₅ and a mixed gas containing oxygen gas are introduced into the vacuum chamber at a constant rate, and the release layer 2 is formed on the surface by the CVD method. Form.

Monomer materials used for forming the release layer 2 include monomer materials containing CH ₃ directly bonded to silicon (Si) atoms, such as hexamethyldisiloxane (HMDSO), tetramethyldisiloxane (TMDSO), and octamethylyl. Cyclotetrasiloxane, methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, ethylsilane and the like are preferably used.

The other monomer material may be any material as long as it is an organic compound, has an appropriate vapor pressure at room temperature, and can perform the CVD method. Therefore, for example, using a material having a functional group having 3 or more carbon atoms such as C ₃ H ₈ group, a silica film (peeling layer 2) containing at least one of CH ₃ group and C ₂ H ₅ is manufactured by CVD method. It is theoretically possible to do this. However, in reality, since these materials have very low vapor pressure, it is difficult to produce a silica film.

In the case of forming the release layer 2 according to this embodiment, it is preferable to use HMDSO, TMDSO, and octamethylcyclotetrasiloxane among monomer materials. These siloxane materials are stable in the film because the CH ₃ group exhibiting releasability is bonded directly to Si atoms, not through Si—O bonds or O—C bonds, which are easily broken. It is because it becomes easy to be taken in.

For example, oxygen gas is used as the mixed gas. Instead of oxygen gas, ozone gas or laughing gas (N ₂ O gas) can be used, but oxygen gas is most preferably used from the viewpoint of film formation efficiency and cost. It should be noted that, in the mixed gas, a gas (carrier gas) for efficiently introducing the monomer material into the vacuum chamber, or a target gas for generating plasma or enhancing the plasma can be introduced in an enhanced manner. You may perform as needed.

  There are several CVD methods such as thermal CVD and photo-CVD. In view of the peelability that is the object of the present invention, it is preferable to employ a plasma CVD method that enables low-temperature film formation and high material utilization efficiency.

The most common method as the plasma CVD method is a method in which an electric field of 13.56 MHz is applied between parallel plate electrodes. That is, a constant pressure (for example, 50 mTorr) is maintained by introducing a raw material gas into the vacuum chamber, and between the flat plate electrode installed in the vacuum chamber and the ground electrode installed in parallel with the flat plate electrode. An RF alternating voltage of 13.56 MHz is applied. For example, by applying 300 W of electric power to an electrode area of 500 cm ² , glow discharge plasma is generated, and a raw material gas is chemically reacted by using the plasma flow, thereby peeling off a silica film. Layer 2 can be formed. The release substrate 1 for forming the release layer 2 is usually installed on the surface of the ground electrode, but it may be installed on the plate electrode side to which RF power is applied.

  In this embodiment, it is possible to apply a lower frequency (such as 40 kHz or 50 kHz) or a higher frequency (such as 2.45 GHz) instead of applying an RF alternating voltage of 13.56 MHz. . Further, a DC voltage may be applied. Instead of the flat plate electrode, it is possible to use a hollow cathode electrode that generates a plasma flow by blowing a gas, or to generate induction plasma from an external coil. It is also possible to increase the plasma density by using a magnetic field or by using an ECR resonance phenomenon (a phenomenon in which electrons in plasma are subjected to cyclotron resonance by appropriately adjusting an electric field and a magnetic field).

In addition to the CVD method (input power frequency, electrode structure, etc.), there are various parameters such as input power, gas flow rate, film formation pressure, and distance between electrodes. It has an influence on the flow rate ratio of the monomer material and oxygen gas during film formation. That is, when a large amount of monomer material is supplied with respect to oxygen, CH ₃ groups that cannot be reacted remain in the release layer, so that high peelability is exhibited. On the other hand, when sufficient oxygen is supplied, all the CH ₃ groups are decomposed, so that no CH ₃ groups exist in the film. As a result, the contact angle with diiodomethane becomes small, and the peelability from the urethane resin becomes poor.

When HMDSO is used as a raw material, assuming an ideal state where all the raw materials are SiO ₂ , CO ₂ , and H ₂ O, a flow rate ratio of HMDSO of 100 parts by weight and oxygen gas of 1000 parts by weight is required. It is. However, even if the CVD method is performed at such a flow rate ratio, in reality, intermediate reactants such as methanol (CH ₃ OH) and formaldehyde (HCHO) may be generated, or the material itself may be exhausted. is there. Further, since oxygen that could not be reacted may be exhausted, the flow rate ratio between the monomer material and oxygen gas required for the CVD method does not conform to the chemical formula.

  As a result of intensive studies based on various experimental results, the present inventors have found that when the release layer 2 is formed on the mold release substrate 1 by the CVD method, oxygen gas is supplied to 100 parts by weight of the monomer material. It has been found that when the flow rate is 500 parts by weight, the release layer 2 is necessary to provide moisture resistance with a contact angle with diiodomethane of 60 °. It has been found that if the flow rate of oxygen gas is increased from 500 parts by weight, the value of the contact angle generally tends to decrease. It was found that if the flow rate of oxygen gas is decreased from 500 parts by weight, the value of the contact angle generally tends to increase.

Table 3 shows an example of the evaluation result of the contact angle of the silica film obtained with respect to the flow rate ratio of the monomer material and oxygen gas to diiodomethane. Evaluation of “peelability” in Table 3 is carried out on a release paper (release base material) having a release layer 2 formed on the surface by adjusting a polyester-based polyurethane resin composition having the composition shown in Table 1. The polyester-based polyurethane resin composition was applied with a knife coater so as to have a dry thickness of 20 μm, and dried with hot air at 160 ° C. for 1 minute to form a urethane skin layer. As an adhesive layer on this urethane skin layer, a two-component curable polyester polyurethane adhesive shown in Table 2 was applied with a knife coater so as to have a dry thickness of 40 μm, a base fabric was bonded, and dried at 130 ° C. for 5 minutes. Furthermore, after aging at 40 ° C. for 48 hours to cause the adhesive to react and solidify, the peel strength between the release paper and the urethane skin layer (measurement width 15 mm width, 90 ° peel) is measured, and when it is 100 g / 15 mm width or more , And the case of 50 g or more and less than 100 g / 15 mm width is evaluated as ◯. The contact angle was evaluated by the angle of the straight line connecting the left and right end points and the apex of the droplet to the solid surface by the θ / 2 method.

  As shown in Table 3, when the flow rate ratio of the monomer material and oxygen gas is 100: 500, the contact angle of diiodomethane is 60 ° or more, and the releasability from the urethane resin isocyanate used as the surface film is high. I understand that. It can also be seen that even when the contact angle of diiodomethane is 60 ° or more and oxygen gas is not flowed (flow rate ratio 100: 0), a favorable effect is obtained in peelability.

According to the method for producing an embossed release paper according to the embodiment, the release ratio of, for example, about 1 to 100 nm is formed on the surface of the release substrate 1 while controlling the flow ratio of the monomer material and oxygen gas within a certain range. Layer 2 is formed by a CVD method. Since the release layer 2 has CH ₃ groups and / or C ₂ H ₅ groups on the surface, the release paper can be easily released from the urethane resin used as the skin layer of the synthetic leather. Since the silica film as the release layer 2 formed by the CVD method has heat resistance even under a high temperature condition of 200 ° C. or higher, in addition to polyurethane leather, synthetic leather that requires treatment in a high temperature environment, for example, semi It can be applied to the production of various types of synthetic resins such as synthetic leather and PVC leather, and a highly versatile release paper with emboss can be produced.

  In addition, the vapor deposition method by PVD method other than the vapor deposition method by CVD method is also considered. However, the PVD method is not practical because it is difficult to introduce a methyl group (carbon) during vapor deposition.

(Method for producing synthetic leather)
When manufacturing synthetic leather using the release paper with embossing according to the embodiment, for example, as shown in FIG. 4, first, a molten resin paint containing a urethane resin, a colorant and the like is formed on the release layer 2. Coating is performed to form the skin layer 3 on the release layer 2. As shown in FIG. 5, after the skin sheet 3 such as a base fabric is bonded onto the skin layer 3, the skin layer 3 is cured. Thereafter, as shown in FIG. 6, the skin layer 3 is peeled off from the peeling layer 2, thereby obtaining the endothelial sheet 4 and the synthetic leather 5 having the skin layer 3 disposed on the endothelial sheet 4.

  According to the method for manufacturing synthetic leather according to the embodiment, the peelability between the urethane resin in the skin layer 3 and the release layer 2 can be increased, and therefore the same release paper is used repeatedly. Can do. As a result, the manufacturing cost can be kept low, and the productivity of synthetic leather can be increased.

(First example of release paper with emboss)
FIG. 7 shows a first example of an embossed release paper according to the embodiment. Note that FIG. 7 is an example, and there are of course various other modes. The release paper with embossing shown in FIG. 7 has a release substrate 1 with an emboss having an uneven surface, and a release layer 2 formed on the surface of the release substrate 1 by a CVD method. 1 includes a support sheet 11, an intermediate layer 12 on the support sheet 11, an embossed layer 13 on the intermediate layer 12, and a coat layer 14 on the embossed layer 13.

  As the support sheet 11, an inorganic pigment coating layer such as fine paper, kraft paper, glossy kraft paper, pure white roll paper, glassine paper, and cup base paper, art paper, coated paper, cast coated paper, etc. Coated paper coated with or synthetic paper not using natural pulp can be used.

  For example, when the embossed release paper shown in FIG. 7 is used in an environment of less than 200 ° C., as the support sheet 11, an acid paper made using a fixing agent such as aluminum sulfate and a rosin sizing agent is used. May be. When the embossed release paper shown in FIG. 7 is used in an environment of 200 ° C. or higher, a neutral rosin sizing agent that does not use aluminum sulfate as a fixing agent, or an alkyl ketene dimer (AKD) and an alkenyl succinic anhydride (ASA). Neutral paper made using a neutral sizing agent or the like can be used as the support sheet 11. Also, neutral paper made from aluminum sulfate and made at pH 6 to pH 9 can be used.

  Further, in the support sheet 11, fixing agents such as cationic polyacrylamide and cationic starch, various fillers for papermaking, yield improver, dry paper strength enhancer, wet paper strength enhancer, binder, dispersant, It may contain a flocculant, a plasticizer, and an adhesive. The support sheet 11 may have chemical resistance.

  The intermediate layer 12 includes acrylic resin, polyolefin resin such as polyethylene, polypropylene, and polymethylpentene, silicone resin, alkyd resin including amino alkyd, and the like. For example, when the release paper with embossing shown in FIG. 7 is used in an environment of less than 200 ° C., the intermediate layer 12 may include a polypropylene resin having excellent heat resistance. In this case, the intermediate layer 12 may contain propylene as a main component and a copolymer of propylene and an α-olefin such as ethylene, butene, pentene, hexene, octene, and 4-polymethylpentene-1. Good. When the release paper with embossing shown in FIG. 7 is used in an environment of less than 200 ° C., the intermediate layer 12 may include a polymethylpentene resin having a high melting point. Examples of the polymethylpentene resin include 4-methyl-1-pentene. Examples of polymethylpentene resins include 4-methyl-1-pentene as the main component, 4-methyl-1-pentene, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-octene, There are copolymers with α-olefins having 2 to 20 carbon atoms such as decene, 1-tetradecene, and 1-octadecene.

  The surface of the intermediate layer 12 may be subjected to a surface treatment for improving the adhesion density with the embossed layer 13. Examples of surface treatments include flame treatment, corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, atmospheric pressure plasma treatment, glow discharge treatment, and oxidation treatment using chemicals, etc. Etc. The film thickness of the intermediate layer 12 can be, for example, 3 μm to 40 μm, preferably 5 μm to 20 μm. By forming the intermediate layer 12 as a foamed layer, unevenness is easily formed on the upper embossed layer 13, and the thickness of the intermediate layer 12 can be controlled to be thick.

  The embossed layer 13 includes a resin that is cured by ionizing radiation or ultraviolet rays. A resin cured with ionizing radiation or ultraviolet rays is a resin such as polyurethane acrylate formed by irradiating a reaction product of an isocyanate compound and a methacrylic compound having a methacryloyl group and reacting with the isocyanate compound with ionizing radiation or ultraviolet rays. Point to. The resin cured with ionizing radiation or ultraviolet rays is a resin such as polyurethane acrylate formed by irradiating the reaction product of an isocyanate compound and an acrylic compound having an acryloyl group and reacting with the isocyanate compound with ionizing radiation or ultraviolet rays. Point to.

  On the coat layer 14, for example, a deep groove pattern 3a and a shallow groove pattern 3b are formed by hot embossing. When the coating layer 14 is disposed on the emboss layer 13, when the outermost surface of the release substrate is embossed using the manufacturing apparatus shown in FIG. 8 to be described later, the release substrate becomes an embossing device (embossing roll). ), It becomes easy to peel off. The coat layer 14 may not be formed as necessary.

  As the coating layer 14, for example, addition polymerization silicone having a film thickness of 0.01 μm to 20 μm and addition polymerization of an addition polymerization type silicone material can be used. The addition polymerization type silicone material includes at least an alkenyl group-containing organopolysiloxane and an organohydrogenpolysiloxane. Examples of alkenyl groups include vinyl, allyl, butenyl, pentenyl, hexenyl and the like. Examples of organopolysiloxanes include dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain, dimethylsiloxane / methylvinylsiloxane copolymer blocked with dimethylvinylsiloxy group at both ends of the molecular chain, and dimethylvinylsiloxy group-blocked dimethyl at both ends of the molecular chain. Siloxane / methylphenylsiloxane copolymer, trimethylsiloxy group-capped methylvinylpolysiloxane at both ends of molecular chain, trimethylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane copolymer at both ends of molecular chain, trimethylsiloxy group-capped dimethylsiloxane at both molecular chains・ Methyl (5-hexenyl) siloxane copolymer, both ends of molecular chain dimethylvinylsiloxy group-blocked dimethylsiloxane ・ Methylvinylsiloxane ・ Methylphenylsiloxane copolymer, both ends of molecular chain Methyl hydroxy group blocked methylvinylpolysiloxane, there is dimethylpolysiloxane with both molecular chain terminals hydroxy group-blocked dimethylsiloxane-methylvinylsiloxane copolymer. Each substance classified into the exemplified alkenyl group-containing organopolysiloxane may be contained alone in the coating layer 14 or may be contained in two or more kinds.

  According to the embossed release paper according to the first example, since the release layer 2 having a film thickness of about 1 to 100 nm is formed on the surface of the release substrate 1, the urethane resin used as the skin layer of the synthetic leather The release paper can be easily peeled off, and heat-resistant even under high temperature conditions of 200 ° C. or higher, and a highly versatile release paper with embossing can be produced. Moreover, since the mold release base material 1 of FIG. 7 is provided with the coat layer 14, the release base material 1 does not adhere to the embossing apparatus (embossing roll) at the time of embossing.

  An example of a manufacturing apparatus that can be used for manufacturing the release paper with embossing shown in FIG. 7 is shown in FIG. The manufacturing apparatus shown in FIG. 8 shows an example of an apparatus for forming surface irregularities (groove patterns 3a, 3b) formed on the release substrate 1 by hot embossing.

  The manufacturing apparatus shown in FIG. 8 includes an unwinding unit 20 that unwinds the sheet 17, a coating unit 21 that applies a coating material 22 mainly composed of a hot-melt resin film on one side of the sheet 17, and a coated sheet 17. A drying furnace 23 for drying the sheet, a first embossed portion 24a and a second embossed portion 25b for embossing the surface of the sheet 17, and an irradiation apparatus for irradiating the sheet 17 on which the embossed layer is formed with ultraviolet rays or an electron beam. 26, a CVD apparatus 28 for forming the release layer 2 according to the embodiment by a CVD method on the surface layer after irradiation with electron beams or ultraviolet rays, and a winding unit 29 for the sheet 17 on which the release layer 2 is formed. .

  In FIG. 8, the coating unit 21, the drying furnace 23, the embossing units 24 a and 24 b, the irradiation device 26, and the CVD device 28 are described as one continuous device, but each operation is not performed continuously. Of course, other devices may be used.

  When manufacturing the release paper with embossing of FIG. 7, for example, as shown in the flowchart of FIG. 9, first, the support sheet 11 is prepared in step S11. The support sheet 11 is unwound from the winding unit shown in FIG. 5, and the intermediate layer resin is applied onto the support sheet 11 in the coating unit 21 shown in FIG. 8 as shown in step S12. Thereafter, as shown in step S <b> 13, the solvent contained in the intermediate layer resin is evaporated in the drying furnace 23 of FIG. 8 to form the intermediate layer 12 on the support sheet 11. Next, an embossing layer resin including, for example, an acrylic ionizing radiation curable resin is applied onto the intermediate layer 12 by a coating portion, and the solvent contained in the embossing layer resin is dried in a drying furnace to form on the intermediate layer 12. An emboss layer 13 is disposed. Further, a coating material such as an addition polymerization type silicone material is applied on the embossing layer 13, and the solvent contained in the coating material is dried in a drying furnace to form the coating layer 14 on the embossing layer 13.

  In step S14, in the first embossed portion 24a of FIG. 8, the embossing roll heated to, for example, 50 to 150 ° C. and having a shallow groove pattern such as a texture pattern formed on the surface is pressed onto the coat layer 14, and the coat layer 14 A shallow groove pattern 3b shown in FIG. 7 is formed on the upper surface. Subsequently, in step S15, the second embossed portion 25b is heated to, for example, 50 to 150 ° C., and an embossing roll having a deep groove pattern formed on the surface is pressed onto the coat layer 14, and the surface on the coat layer 14 is pressed. A deep groove pattern 3a shown in FIG. Next, in step S15, the irradiation device 26 irradiates ionizing radiation such as an electron beam or ultraviolet rays from the coat layer 14 on the surface of which the shallow groove pattern 3b and the deep groove pattern 3a are formed. Is cured.

  Next, in step S <b> 16, the sheet on which the embossed layer 13 is formed is carried into the CVD apparatus 28. By introducing the mixed gas into the vacuum chamber of the CVD apparatus 28 at a flow rate ratio of 0 to 500 parts by weight with respect to 100 parts by weight of the monomer material, the pressure is maintained at 50 mTorr. An RF alternating voltage of 13.56 MHz is applied between a flat electrode placed inside and a ground electrode placed in parallel with the flat plate electrode to generate glow discharge plasma and form a release layer 2 made of a silica film As a result, the embossed release paper shown in FIG. 7 is obtained.

(Second example of release paper with emboss)
The 2nd example of the release paper with an embossing which concerns on embodiment is shown in FIG. The release paper with embossing shown in FIG. 10 includes an embossed release base material 1 having irregularities on the surface and a release layer 2 formed by a CVD method on the surface of the release base material. The support sheet 11, the intermediate layer 12 on the support sheet 11, and the embossed layer 13 on the intermediate layer 12 are hardened. Irregularities on the surface of the embossed layer 13 are cured by electron beam (EB) irradiation. This is different from the first example.

  As the embossing layer 13 in FIG. 10, for example, a resin containing an acrylic resin and a silicone resin is used. By using a material having a relatively high melting point such as polyester or nylon as the embossing layer 13, the release paper with embossing according to the second example can be used for PVC leather.

  The unevenness of the embossed layer 13 shown in FIG. 10 is hardened by EB irradiation, so that a molding rate close to 100% is obtained, compared with the hot embossing process in which the molding rate is only about 80%. The surface irregularities are reproduced more precisely. In the present embodiment, “molding rate” refers to the ratio of the depth from the reference surface of the corresponding part in the embossed product to the depth from the reference surface of the predetermined part in the embossing roller.

  Also in the release paper with embossing according to the second example, since the release layer 2 having a film thickness of about 1 to 100 nm is formed on the surface of the release substrate 1, the urethane resin used as the skin layer of the synthetic leather The release paper can be easily peeled off, and heat-resistant and highly versatile release paper with high versatility can be produced even under high temperature conditions of 200 ° C. or higher.

  FIG. 11 shows an example of a manufacturing apparatus that can be used for manufacturing the release paper with embossing shown in FIG. The manufacturing apparatus shown in FIG. 11 shows an example of an apparatus that forms unevenness on the surface of the emboss layer 13 formed on the release substrate 1 by EB irradiation.

  The manufacturing apparatus shown in FIG. 11 includes an unwinding unit 30 for unwinding the sheet 17, coating units 31 and 36 for coating the coating material 32 on one side of the sheet 17, a roller 35 having irregularities on the surface, and the sheet 17. Guide rollers 33 and 37 that are pressed against the roller 35; an electron beam irradiation device 34 that irradiates the sheet 17 with an electron beam to form irregularities on one side of the sheet 17; and a release layer formed on the surface of the sheet 17 after the irregularities are formed by a CVD method. 2 and a winding unit 39 that winds up the sheet 17 on which the release layer 2 is formed.

  When manufacturing the release paper with embossing of FIG. 10, for example, as shown in the flowchart of FIG. 12, first, the support sheet 11 is prepared in step S21. The support sheet 11 is unwound from the winding unit shown in FIG. 5, and the intermediate layer resin is applied onto the support sheet 11 in the coating unit 21 shown in FIG. 8 as shown in step S22. On the support sheet 11 coated with the intermediate layer resin, an emboss layer resin containing, for example, an acrylic ionizing radiation curable resin is applied by the coating unit 36, and an electron beam is irradiated on the surface by the electron beam irradiation device 34. The embossed layer 13 having irregularities is formed.

  Next, in step S <b> 24, the sheet on which the embossed layer 13 is formed is carried into the CVD apparatus 28. The mixed gas was introduced into the vacuum chamber of the CVD apparatus 28 at a flow rate ratio of 0 to 500 with respect to the flow rate 100 of the monomer material, so that the pressure was maintained at 50 mTorr and installed in the vacuum chamber. An RF alternating voltage of 13.56 MHz is applied between the flat electrode and a ground electrode installed in parallel with the flat plate electrode to generate glow discharge plasma, thereby forming a release layer 2 made of a silica film. A release paper with embossing as shown in FIG.

(Third example of release paper with emboss)
FIG. 13 shows a third example of the embossed release paper according to the embodiment. The release paper with embossing shown in FIG. 13 is that the unevenness on the surface of the embossing layer 13 is formed by an extrusion method (Chill roll extrusion) using a cooling roll (chill roll). Different.

  As the embossing layer 13 in FIG. 13, for example, a resin containing an acrylic resin and a silicone resin is used. As the emboss layer 13, a material having a relatively high melting point such as polyester or nylon may be used.

  Conventionally, when the unevenness of the embossed layer 13 is formed by hot pressing or the like, there is a problem that it is difficult to mold a fine embossed pattern because the molding rate is only about 80%. On the other hand, according to the release paper with embossing according to the third example, the unevenness of the embossed layer 13 is formed by an extrusion method using a chill roll, so the embossing rate of the embossed layer 13 is almost 100%. It is possible to form a fine emboss pattern on the surface of the release paper with emboss.

  Further, similarly to the release paper according to the first and second examples, in the release paper with embossing according to the third example, the release layer 2 having a film thickness of about 1 to 100 nm is formed on the surface of the release substrate 1. Therefore, when urethane resin is used as the skin layer of the synthetic leather, the release paper can be easily peeled from the skin layer. Since the peeling layer 2 is deposited to such an extent that the shape of the embossed pattern of the embossed layer 13 is not impaired, the delicate pattern formed on the surface of the release substrate 1 is reproduced on the surface of the skin layer of the synthetic leather. Can be imparted with good quality.

  FIG. 14 shows an example of a manufacturing apparatus that can be used for manufacturing the release paper with embossing shown in FIG. The manufacturing apparatus shown in FIG. 14 shows an example of an apparatus that forms irregularities on the surface of the embossed layer 13 formed on the release substrate 1 by extrusion using a chill roll. Note that the example shown in FIG. 14 is merely an example, and various other modes are of course used.

  The manufacturing apparatus shown in FIG. 14 includes a first extruder 70A that extrudes molten resin, and a second extruder 70B that extrudes molten resin. The molten resin extruded from each of the first extruder 70 </ b> A and the second extruder 70 </ b> B reaches a flat die (T die) 75 via the adapter 73. The molten resin extruded from each of the first extruder 70A and the second extruder 70B by the flat die 75 is molded into a two-layer sheet. A backup roll 60 and a cooling roll 50 are arranged below the flat die 75. By the backup roll 60 and the cooling roll 50, for example, the resin for the emboss layer including the resin for the intermediate layer and the acrylic ionizing radiation curable resin can be laminated on the support sheet 11.

  When manufacturing the release paper with embossing of FIG. 13, as shown in the flowchart of FIG. 15, first, the support sheet 11 is prepared in step S31, and as shown in step S32, corona treatment or the like is performed on the support sheet 11. Pre-processing is performed. Thereafter, a molten resin for an intermediate layer containing a composition of polypropylene resin, polymethylpentene resin, or polyethylene resin and an embossed layer molten resin containing an acrylic ionizing radiation coin resin are prepared.

  In step S33, the molten resin for intermediate layer is filled into the first extruder 70A shown in FIG. 14, and the molten resin for embossed layer is filled into the second extruder 70B. According to the melting point of the resin contained in the molten resin for the intermediate layer and the molten resin for the embossed layer, the MFR, the matting agent, and the blending amount of the resin and the matting agent, the first extruder 70A and the second extruder 70B are Heat. Thereafter, the intermediate layer molten resin and the embossed layer molten resin are extruded to the flat die 75 through the adapter 73, and the intermediate layer molten resin and the embossed layer molten resin molded into a layer shape from the flat die 75 are coextruded. .

  In step S <b> 34, the support sheet 11, the intermediate layer molten resin and the embossed layer molten resin molded in layers are laminated by the backup roll 60 and the cooling roll 50 cooled to 20 to 30 ° C. The intermediate layer 12 and the embossed layer 13 having irregularities disposed on the intermediate layer 12 are formed. Thereafter, in step S34, the sheet on which the embossed layer 13 is formed is carried into a CVD apparatus. A mixed gas is introduced into the vacuum chamber of the CVD apparatus at a flow rate ratio of 0 to 500 with respect to the flow rate of the monomer material 100, so that the pressure is maintained at 50 mTorr and the flat plate installed in the vacuum chamber. A release layer 2 made of a silica film having a thickness of about 1 to 100 nm is generated by applying an RF alternating voltage of 13.56 MHz between an electrode and a ground electrode disposed in parallel with the flat plate electrode to generate glow discharge plasma. To obtain a release paper with embossing as shown in FIG.

(Example of release layer)
The mold release substrate 1 according to the embodiment of the present invention is placed in a parallel plate type plasma CVD apparatus PE401 (manufactured by Anelva Co., Ltd.), the ultimate vacuum before film formation is 0.02 mTorr, and Ar gas is used. As a carrier gas, oxygen and HMDSO (hexamethyldisiloxane) were bubbled at room temperature as source gases and supplied into the apparatus.

  The Ar gas flow rate was adjusted so that the flow rate of oxygen gas was 30 sccm and the flow rate of monomer was 6.0 sccm. The conductance valve was adjusted so that the film forming pressure was 50 mTorr.

  Plasma was generated by applying power of 100 W, 13.56 MHz between the upper plate electrode and the lower ground electrode. The release substrate 1 was placed on the lower ground electrode, and a silica film was formed. The film formation time was 10 minutes. A silicon wafer was simultaneously placed in the deposition chamber and the film thickness was measured by ellipsometry to confirm that a silica film of about 100 nm was formed. The presence of the methyl group was confirmed by IR spectroscopy. The evaluation method was based on the contact angle with diiodomethane.

  For comparison, an oxygen gas flow rate of 30 sccm, a monomer flow rate of 3.0 sccm, and a film having no methyl group remaining on the surface m were prepared and evaluated. As a result, the former contact angle was 65.1 degrees, while the latter contact angle was 53.0 degrees.

  The apparatus used for the CVD method was a vacuum winder. The ultimate pressure of the chamber was set to 0.05 Torr, and a source gas composed of oxygen gas and HMDSO was introduced into the chamber to a pressure of 45 mTorr. The flow rates of the introduced source gases were 0 slm for oxygen gas and 2 slm for HMDSO. HMDSO used a gas supply system heated to 80 ° C. and did not use a carrier gas. The film formation drum was cooled to −10 ° C. in order to eliminate the heat damage of the film substrate. An Rf AC voltage of 13.56 MHz was applied to a flat plate electrode (distance 3 cm from the film formation drum, electrode area 70 cm × 20 cm) at a position facing the film formation drum (1.5 kW) to be electrically grounded. Plasma was created between the film formation drums and film formation was performed on the substrate. The running speed of the film was 30 m / min.

  The embossed release paper with a release layer according to the embodiment created in this way is compared with the release paper with an emboss without a release layer, that is, the release paper manufactured under the same conditions when the CVD film is not formed. However, there was no difference between the two. That is, even when the release layer was formed on the embossed release paper film by the CVD method, the embossed shape was not impaired.

  Thus, although this invention was described by embodiment, it should not be understood that the description and drawings which form a part of this disclosure limit this invention. From this disclosure, various alternative embodiments, examples and operational techniques will be apparent to those skilled in the art. It should be understood that the present invention includes various embodiments and the like not described herein. Therefore, the present invention is limited only by the invention specifying matters in the scope of claims reasonable from this disclosure.

DESCRIPTION OF SYMBOLS 1 ... Mold release base material 2 ... Release layer 3 ... Skin layer 4 ... Endothelial sheet 5 ... Synthetic leather 11 ... Support sheet 12 ... Intermediate layer 13 ... Embossed layer 14 ... Coat layer 17 ... Sheet 28, 37 ... CVD apparatus

Claims (5)

In a method for producing an embossed release paper comprising a release substrate with embossment having irregularities on the surface and a release layer formed by a CVD method on the surface of the release substrate,
A step of forming an embossed release substrate having irregularities on the surface by bringing an embossing roll cooled to a predetermined temperature into contact with the hot-melting resin and cooling and solidifying the hot-melting resin with the embossing roll; The manufacturing method of the release paper with an emboss characterized by these.   2. The method for producing an embossed release paper according to claim 1, wherein the release layer is a silica film formed so that at least one of a methyl group and an ethyl group is left on the surface.   The method for producing a release paper with embossment according to claim 1 or 2, wherein the thickness of the release layer is 1 nm or more, and the contact angle of the surface of the release layer with respect to jodomethane is 60 ° or more. . Forming the release layer includes
Introducing an embossed release substrate with irregularities on the surface into the vacuum chamber,
In the vacuum chamber, a mixed gas containing a monomer material containing Si atoms and CH ₃ groups and / or C ₂ H ₅ and oxygen gas is used in an amount of 0 to 500 parts by weight or more of oxygen gas with respect to 100 parts by weight of the monomer material. The embossing according to any one of claims 1 to 3, further comprising a step of forming the release layer so that a contact angle of the surface of the release layer with respect to the jodomethane is 60 ° or more. A method for producing a release paper.   The monomer material is a material selected from xamethyldisiloxane, tetramethyldisiloxane, octamethylcyclotetrasiloxane, methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, and ethylsilane. The manufacturing method of the release paper with an embossing of any one of Claims 1-4.

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