TW200927494A - Support sheet for process release sheet, process release sheet and method for producing synthetic leather - Google Patents

Abstract

The present invention provides a support sheet which improves the stripping quality of synthetic leather from a process release sheet when the support sheet is used for the process release sheet. The present invention also provides a process release sheet which improves the stripping quality of synthetic leather. The support sheet for a process release sheet of the present invention includes: a support medium; and a cast-coated paper including a cast-coated layer, wherein the cast-coated layer includes a binder and a pigment for a coating layer; and the binder includes a styrene-butadiene copolymer which contains more than 40% by mass of butadiene unit. The process release sheet of the present invention includes; the support sheet for process release sheet; and a release layer being disposed on an overside of the support medium of the cast-coated layer, wherein the release layer includes stripping agent components and a pigment for the release layer containing a silica.

Description

200927494 IX. OBJECTS OF THE INVENTION: TECHNICAL FIELD The present invention relates to an engineered release sheet for use in the manufacture of synthetic leather, a substrate sheet for engineered release sheets for engineered release sheets, and a use engineering A method of producing a synthetic leather from a release sheet. The present application is based on Japanese Patent Application No. Hei. [Prior Art] ❹

Synthetic leather such as polyurethane leather or vinyl leather can be manufactured in a large amount compared with natural leather, and has a small number of restrictions, and is widely used in the fields of clothes, shoes, purses, and sofas. As a method of producing the synthetic leather, for example, a method of producing a synthetic leather including a urethane resin, a gas-ethylene resin, a guanamine resin, or an amine base is applied to the engineered release sheet. The coating material is dried and hardened, and then the woven fabric or the like is bonded to the applied synthetic leather production coating material via an adhesive, and then passed between cooling rolls, and then the engineered release sheet is peeled off. In the method for producing a synthetic leather using such an engineered release sheet, the surface state of various synthetic engineering release sheets having different hand feelings can be transferred to the synthetic leather, so that the surface state of the engineered release sheet is changed. leather. The engineered release sheet used in the method for producing a synthetic leather described above is generally used for forming a release layer for a synthetic leather production coating or a coated release layer on a substrate sheet. a substrate sheet, for example, (4) cast-coated 134277.doc 200927494 cast-coated paper, which is provided with a cast coating layer containing a binder and a pigment as a main component (cast_eoated layer) (Patent Document 1) 专利 [Patent Document 1] JP-A-2001-98495 [Disclosure] [Problems to be Solved by the Invention] However, when the engineered release sheet described in the patent document is used, When manufacturing synthetic leather, it is sometimes difficult to peel the synthetic leather from the engineered release sheet. The present invention has been made in view of the above circumstances, and it is an object of the invention to provide a substrate sheet which, when used for an engineered release sheet, can improve the peelability of the synthetic leather peeled off from the engineered release sheet. Further, it is an object of the present invention to provide an engineered release sheet which is detachable from the synthetic leather. [Technical means for solving the problem] [1] A substrate sheet for an engineered release sheet, comprising: a cast coated paper having a support and a cast coating layer, wherein the cast coating layer contains A binder for a binder and a coating layer, and the binder contains a styrene-butadiene copolymer having a butadiene unit content of more than 40% by weight. [2] The substrate sheet for an engineered release sheet according to [1], wherein the content of the styrene-butadiene copolymer in the binder is 50% by weight or more when the total amount of the binder is 100% by weight. [3] The substrate sheet for an engineered release sheet of [1] or [2], wherein the binder contains a protein. [4] An engineered release sheet comprising the substrate sheet for an engineered release sheet according to any one of [3], and a cast sheet formed on the substrate 134277.doc 200927494 The release layer on the surface of the coating layer opposite to the support, the release layer contains a release agent component and a pigment for the release layer containing the dicep. (7) The engineered release sheet of [4] wherein the release agent is an alkyd resin to which a fumarin adsorbent is added. [6] The engineered release sheet according to [4], wherein the cerium oxide contained in the pigment for the release layer has an average particle diameter of 丨 to μm and a maximum particle diameter of 1 Å or less. m such as the engineered release sheet # of (4) or [5], wherein the surface of the release layer on the opposite side to the substrate sheet for the sheet is measured according to JIS z 8741 > 75 degree gloss is 30 ~90%. [8] A method for producing a synthetic leather, comprising the steps of: coating a synthetic leather with a sapphire coating to form a leather on the engineered release sheet of any one of [4] to [7] Layer: and the above-mentioned engineered release sheet was peeled off from the leather layer of synthetic leather. [Effect of the Invention] When the substrate sheet of the present invention is used for an engineered release sheet, the peeling property of the self-processed release sheet peeled synthetic leather can be improved. According to the engineered release sheet of the present invention, the peelability of the synthetic leather can be improved. [Embodiment] <Substrate Sheet for Industrial Release Sheets> An embodiment of the substrate sheet for engineered release sheets of the present invention (hereinafter simply referred to as a substrate sheet) will be described. Fig. 1 shows a substrate sheet of this embodiment. The base material sheet 10 of the present embodiment is composed of cast-coated paper, and the cast-coated paper-based support u and the cast light 134277.doc 200927494 are formed by laminating the coating layer 12 via the barrier layer 13. (Support) As the support 11, paper, film, or the like is used. Examples of the paper include top paper, medium paper, low-quality paper, base paper for coated paper, base material for coated paper, base material for cast-coated paper, kraft paper, and cellophane. Examples of the plastic film include polyesters such as polypropylene, polyethylene, polyethylene terephthalate or polybutylene terephthalate, and various polymer films such as polyvinyl chloride. Further, vapor deposition paper, synthetic paper, cloth, non-woven fabric, metal foil, or the like can also be used. Further, the laminate or the like can be suitably used. Among these, a base material for a coated paper, a base material for a coated paper, and a base material for a gloss coated paper are preferred because the substrates can be easily formed into an engineering peeling of synthetic leather excellent in obtaining blackness. Sheet. Further, in view of the fact that the synthetic embossing processing of the synthetic leather is excellent, it is more preferable that the base material for the cast coating paper is used. The basis weight of the support 11 is preferably 50 to 400 g/m2. When the basis weight of the support 11 is 50 g/m2 or more, the engineering release sheet which can be repeatedly reused can be easily produced, and if it is 400 g/m2 or less, an engineered release sheet excellent in handleability can be produced. (Casting Coating Layer) The cast coating layer 12 is a coating layer which is subjected to mirror processing by a commonly used method such as a binder and a coating layer pigment. The binder contained in the cast coating layer 12 contains a styrene-butadiene copolymer containing styrene units and butyl diene 134,277.doc 200927494 as an essential component. [Binder] The styrene-butadiene copolymer contained in the binder has a butadiene unit content of more than 40% by weight, preferably 45 parts by weight. More preferably, the above is more than 5% by weight. It is difficult to self-engineer if the butadiene unit of the stupid ethylene-butadiene copolymer is 40 wt/° to produce synthetic leather by using the above-mentioned substrate sheet 1 工程 engineering release sheet. The release sheet is peeled off from the synthetic leather. Moreover, the appearance of the surface of the synthetic leather is liable to cause defects. In addition, the butadiene unit of the styrene-butadiene copolymer is more preferably 60% by weight or less, and more preferably 58% by weight or less, especially for the reason of excellent coating suitability. %the following. Further, the styrene-butadiene copolymer may contain other monomer units such as a (mercapto) acrylate unit and an acrylonitrile unit. The colloidal ratio of the styrene-butadiene copolymer is preferably from 9 〇 to 1 〇〇 by weight. When the colloid ratio of the styrene-butadiene copolymer is 9% by weight or more, when the synthetic leather is produced by using the engineered release sheet of the above-mentioned base material sheet 10, the peeling property of the synthetic leather is higher. Also, the appearance of the synthetic leather surface is less likely to occur. Here, the term "successful body rate" is a value obtained by the following method. That is, 'the latex coated with styrene-butadiene dilute copolymer on the sheet of polytetrafluoroethylene' was dried at 50 ° C for 24 hours to form a film thickness of 〇3~〇5 mm (after drying). Membrane. Then, the above film was cut into 3 em squares, and the weight was measured, and then immersed in a stupid for 24 hours. Thereafter, the mixture was dried for 1 hour and 5 minutes to completely evaporate toluene, and the weight of the obtained solid matter 134277.doc -10- 200927494 was measured. Then, the colloidal ratio was determined by the formula (1). Weight) 式 Formula (1) Colloidal rate = (weight after toluene impregnation / before toluene impregnation! 00 (%) The colloidal rate of styrene-butadiene copolymer, for example, by changing styrene-butadiene The polymerization conditions of the butadiene unit and the styrene-butadiene copolymer of the olefin copolymer (polymerization temperature, polymerization pressure, addition amount of the crosslinking agent, etc.) are adjusted.

Specifically, the more butadiene units of the styrene-butadiene copolymer, the higher the colloidal rate. The higher the polymerization temperature, the higher the colloidal rate. When a crosslinking agent is added, the more the amount of the crosslinking agent is added, the higher the colloidal rate. Further, other adhesives other than the styrene-butadiene copolymer may be contained in the cast light coating layer 12. Examples of other binders include road proteins, polyvinyl alcohol, enzyme-modified starch or oxidized modified starch, and cationized temple powder; and cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose. Wait. The better of these is casein' because the casein enhances the reusability of the engineered release sheet. The content of the present ethylene-butadiene-diluted copolymer in the binder is preferably 50% by weight or more, more preferably 6% by weight or more, and particularly preferably 70%, when the total amount of the binder is 100% by weight. More than weight%. When the content of the styrene butadiene copolymer is 50% by weight or more, when the synthetic leather is produced by using the engineered release sheet of the base material sheet 10, the surface of the synthetic leather is excellent in appearance. Further, the content of the present ethylene-butadiene copolymer is preferably 95% by weight to 134277.doc -11 - 200927494, more preferably 90% by weight or less, particularly preferably (10) by weight or less, for the reason. Therefore, the cast light can be well adapted. Cast light coating! The amount of the binder (4) in 2 is preferably 5 to 50 parts by weight, more preferably 1 to 3 parts by weight, per part by weight of the pigment for the coating layer. When the binder content is 5 parts by weight or more, the strength of the cast coating can be increased, and if it is 50 parts by weight or less, the peeling layer suitable for the engineered release sheet can be easily formed on the scale coating layer 12. . [Pigmented Coating Pigment] Examples of the coating layer pigments include clay 'kaolin, light carbonic acid, about heavy carbonic acid, titanium dioxide, forging white, barium sulfate, aluminum oxychloride, zinc oxide, and plastic pigment. In the case of ι or the like, from the viewpoint of smooth coating surface, kaolin and light carbon are preferred. Further, it is better to use kaolin and light carbon. The pigment for the coating layer may be any of the under-particles and the secondary particles. However, if the ruthenium is a secondary particle, the release layer suitable for the engineered release sheet can be easily formed on the cast coating layer. The average particle diameter of the pigment for the coating layer is preferably 0.01 to 10. If the average color of the pigment for the coating layer is 0. If the particle size is 0,01 μm or more, the drying property of the coating film is excellent. The lower layer is excellent in surface smoothness. The average particle diameter of a coating layer is the average particle diameter of i 1 when the pigment is a io-order particle, and the average particle diameter of the quaternary particle when the pigment is a secondary particle. 5 to & The average particle diameter of the pigment for the coating layer was 5% by volume measured using a laser diffraction degree distribution meter. [Thickness] 134277.doc 200927494 The thickness of the cast coating layer 12 is preferably 5 to 50 μm. When the thickness of the cast coating layer 12 is 5 pm or more, a peeling layer suitable for the engineered release sheet can be easily formed on the synthetic coating layer 12, and if it is 50 μm or less, the cast light can be easily formed. Coating layer 12. The 75 degree gloss of the surface 12a of the cast light coating layer 12 on the side opposite to the support 11 is preferably 80 to 99%. Here, the 75-degree gloss is a value measured in accordance with Jis Z 8741. If the gloss of the cast coating layer 12 is 8 〇 or more, the peeling layer suitable for the engineered release sheet can be easily formed on the cast coating layer 12, but more than 99% is not easy to manufacture. (Barrier Layer) Examples of the material for forming the barrier layer 13 include carboxymethyl cellulose, casein, dextrin, starch, modified starch, polyvinyl alcohol, modified polyvinyl alcohol, polyethylene oxide, and poly Ethylene: pyrrolidone, polyvinyl decyl ether, polyacrylic acid, polypropylene decylamine, acrylic resin, polyester, polyurethane, and the like. Among these, starch, modified starch, and polyvinyl alcohol are preferred because they are excellent in barrier properties against solvents and have good affinity with the cast coating layer 12. When the base material sheet 1 is formed by forming the barrier layer 13', the adhesive for forming the cast coating layer 12 and the pigment for the coating layer can be prevented from being impregnated into the support. The thickness of the barrier layer 13 is better! ~! 〇 μιη. If the thickness of the barrier layer 13 is! If it is more than μηι, it can prevent dip dyeing. If it is 1〇 μηη or less, it can be used for two costs. (Basic weight) 134277.doc -13- 200927494 The overall basis weight of the substrate sheet Η) is preferably 5()-. Since the production of synthetic leather sometimes needs to be carried out at a high temperature of 15 generations or more (4), it is required that the base sheet 1 has heat resistance, & since the engineered release sheet has to be reused, the substrate sheet (four) is required to have a certain degree. Strength. If the substrate sheet 10 has an overall basis weight of 5. ~50Gg/m2 ensures the heat and strength. (Manufacturing Method of Substrate Sheet) The following three typical methods can be used as a method for producing the cast coated paper to be the base sheet.

(1) In the wet casting method, the cast light in a wet state is applied and laminated on the surface of the heated mirror-finished drum (casting drum), dried, and then demolded and then subjected to gloss processing. (2) Re-wet-casting method "After temporarily drying the coating layer in a wet state, after being wetted again by re-wet solution, it is plasticized, and then crimped to the heated casting drum. After the surface is dried, the mold is released and then subjected to gloss processing. (3) Gluing and casting method, after the coating layer in a wet state is gelatinized, it is pressure-bonded to the surface of the heated casting drum, dried, and then demolded and then subjected to gloss processing. The common point of the casting process is that the coating in a wet and plasticized state is laminated on the surface of the heated casting drum, and after drying, the mold is released and then transferred to the drum. Mirror surface. The production method of (2) is preferable to (1) to (3), because the method (2) can obtain a substrate sheet for an engineered release sheet excellent in quality. Hereinafter, an example of the manufacturing method of (2) will be described. I34277.doc 200927494 First, a coating liquid comprising a barrier layer 13 forming a barrier layer 13 is applied on one side of the support 1 to form a barrier layer 13», and then the surface of the barrier layer 13 is coated with a bond. The coating liquid for coating the light-coating layer for the agent and the coating layer is dried and dried to form a coating layer. Thereafter, a rewetting liquid is applied onto the coating layer and pressed against the mirror-like metal surface of the heated casting drum, thereby drying it to form a cast coating layer 12 to obtain a substrate sheet. 1 〇. When applying a coating liquid containing a component forming a barrier layer, a roll coater, a blade coater, a bar coater, an air knife coater, a gravure coater, a curtain coater can be applied. A well-known applicator such as a belt coater or a die coater. The coating amount of the barrier layer 13 is preferably 丨~(10) g/m in terms of dry coating amount. When the dry coating amount of the barrier layer 13 is 1 g/m 2 or more, it is possible to prevent the coating liquid containing the binder and the coating layer pigment from being impregnated into the support u, and if it is 20 g/m 2 or less, The substrate sheet 1 is made thinner. The coating amount of the cast coating layer 12 is preferably 5 to 5 in terms of dry coating amount, and if the dry coating amount of the cast coating layer 12 is 5 g/m 2 or more, it can be peeled off by engineering. A suitable cast light-coated paper is obtained from the sheet, and if it is 5 Å or less, the base material sheet 10 can be made thin. After the surface of the cast coating layer 12 is rewet by the rewetting liquid, it is pressure-bonded to the casting drum at the following temperature to be dried, and then peeled off from the casting drum, whereby the casting process is performed. The rewet liquid is not particularly limited, and examples thereof include a polyvinyl acetate emulsion containing 0. 01 to 3.0% by weight, a fatty acid soap, a stearic acid dance, an ammonium stearate, a microcrystalline wax, a surfactant, and Turkey. Red oil and other release agent water 134277.doc 200927494 solution containing 0.01~3.0% by weight of zinc sulfate, calcium phosphate 'sodium polyphosphate, sodium hexametaphosphate, sodium formate, ammonium formate, potassium tartrate, sodium citrate, stick An aqueous solution of an inorganic salt or an organic salt such as potassium acid or sodium dioctylsulfosuccinate or the like. The temperature at which the rewet coating is laminated to the casting drum is preferably 50 to 150C. When the temperature at the time of pressure bonding is 5 〇〇 c or more, the rewet coating layer can be sufficiently and rapidly dried, and if it is 15 Å or less, the surface state of the cast coating layer 12 can be further improved. Furthermore, the calender can also be processed using a super calender. The substrate sheet described above! The tantalum is composed of cast-coated paper, so it has a thickness and a high paper strength. Therefore, it is suitable for the engineering release sheet for synthetic leather manufacture. Further, since the binder of the cast coating layer 12 contains the content of the butadiene unit, it is 40% by weight. The styrene-butadiene copolymer of ruthenium is excellent in solvent resistance of the cast coating layer. Therefore, the dissolution of the cast coating layer 12 can be prevented when the cast coating layer 12 is applied to the cast coating layer 12 in order to obtain an engineered release sheet. As a result, it is difficult for the components of the cast coating layer 12 to be mixed into the release layer, and the surface state of the cast coating layer 12 is good. Therefore, when the substrate sheet 1 is used for an engineered release sheet, it can be easily The synthetic leather is peeled off from the engineered release sheet. Further, it is presumed that the content of the butadiene unit is 5 〇 by weight. Further, the above styrene-butadiene copolymer tends to have a good hand feeling after peeling. Further, the I material sheet # of the present invention is not limited to the above embodiment. For example, in the substrate sheet of the present invention, the barrier layer 13 may not be formed between the support body and the cast coating layer 12. 134277.doc • 16- 200927494 <Engineering Release Sheet> An embodiment of the engineered release sheet of the present invention will be described. Fig. 2 shows an engineered release sheet of this embodiment. The engineered release sheet 1 of the present embodiment has the above-mentioned base material sheet 1 and a release layer 20 formed on the surface of the cast light coating layer 12 of the base material sheet 10 opposite to the support body 〇 ( Peeling layer) 剥离 剥离 The release layer 20 contains a release agent component and a pigment for a release layer containing cerium oxide. As the release agent component, for example, polyfluorene oxide, alkyd resin, acid alcohol-polyoxyl copolymer, polyoxygen modified amino acid resin, polyoxygen modified amino acid acrylic resin, and the like can be used. Wait. In view of the fact that the uniformity of the heat-resistant coating surface of the engineered release sheet for synthetic leather production is excellent, it is preferable that the alkyd tree is further used, and when the resin is polymerized, it is preferable to add A substance that causes a chemical reaction with Formalin to act as a formalin adsorbent. The adsorbent is, for example, a compound containing an amine group, an amine group, a quinone group, an imine group, a fluorenyl group, a bromo group, and a fluorenyl group. Thereby, the formalin produced as the by-product can be removed, and the glossiness of the surface 20a of the release layer 20 can be lowered, so that the content of the pigment for the release layer can be reduced, and the coating suitability can be improved, so that the aspect is better. . The dioxide contained in the pigment for the release layer is preferably an average particle (tetra) μιη and a maximum particle diameter of 1 () (four) or less. If the average particle size of the oxidized # is 1 μηι or more, the desired gloss value can be easily adjusted. If the average particle diameter of 100 -17 to 200927494 is 3 Å or less, stable and Also, if the maximum particle size is 1〇_, the synthetic scoop = 敫面. Good. The appearance of the double leather - the average particle size of the oxidized slave is better 〖5~2 〜2·2 μηι. Fork, two乂μ α : (4) Especially good is the best granules in the dream of oxidation, better: the average particle size of human dioxotomy is in the case of oxidized hard to primary particle = 2 = average particle size of the sub-particle In the case of dioxin...secondary particles, it is a diffraction diffraction of two thousand average particle diameters. Moreover, the average particle size of the dioxotomy is a particle of 5Q% volume cumulative value determined by using a thunder and a particle size distribution meter. The oxidized stone may be any of the primary particles and the secondary particles. However, if it is 2 scorpions, the surface of the delaminated layer 2 can be easily adjusted during the processing of the roof. The content of the peeling and the use of the pigment in the middle of the peeling agent is preferably in the range of 3 parts by weight to 15 parts by weight, more preferably 3 parts by weight to 15 parts by weight of the pigment layer. When the amount is more than or equal to the above, the gloss can be easily caused to be as follows: a uniform coated surface can be easily obtained. In the pigment for the release layer, it is also possible to contain the cerium other than the cerium oxide as needed. For the pigments other than Shi Xi, for example, high-grade soil, talc, gypsum, barite powder, white, non-oxidation, money, etc. The content of the pigment other than the dioxide is better. The whole is set to 5 〇 5 〇 when 1% % %. If the content of the pigment other than the cerium oxide is 5% by weight or more ′, the release layer 20 can be easily adjusted by a pigment other than dioxotomy. When the properties are 5 重量% or less, it is possible to prevent 134277.doc.18·200927494 from being oxidized and the pigments other than 5% are hindered from the effects of the present invention. In the release layer 20, the range of effects of the present invention is not impaired. In addition, various additives such as S dye, ultraviolet absorber, antifoaming agent, leveling agent, antistatic agent, etc. may be included. In the separation layer 20, the surface 20a opposite to the substrate sheet 10 has a 75 degree gloss. The degree is preferably 30 to 90%. Here, the 75 degree gloss The degree is measured according to JIS z 8 7 4 1. If the gloss of the surface 2〇a of the release layer 20 is 30 to 90%, a synthetic leather having a high-quality gloss which is moderately suppressed can be obtained. Method) The method for producing a synthetic leather of the present invention comprises the following steps: applying a resin coating for synthetic leather to form a leather layer on the above-mentioned engineering release sheet; and applying the above-mentioned engineered release sheet to a leather layer of synthetic leather In the case of the resin contained in the resin coating for synthetic leather, for example, a urethane resin, a vinyl chloride resin, a guanamine resin, an amino acid resin, etc. are used. When a resin coating material for synthetic leather is applied, The same apparatus as that used for the coating of the above-mentioned release agent coating can be applied. For example, a known coating such as a roll coater, a blade coater, a bar coater, an air knife coater, a gravure coater, a curtain coater, a belt coater, a die coater, or the like can be used. Application machine. Further, a printing machine can also be used, and is not limited to these. (Manufacturing method of synthetic leather) In the method for producing synthetic leather of the present invention, after the leather layer 134277.doc -19-200927494 is formed, a bottom layer such as a woven fabric or a non-woven fabric may be bonded to the leather layer. At this time, various well-known adhesives may be interposed between the leather layer and the base fabric. A synthetic leather obtained by such a manufacturing method is obtained by transferring the surface of the above-mentioned engineered release sheet having an intermediate gloss tone, so that it has a uniform feel. Further, the above-mentioned engineered release sheet has high peelability, and it is possible to easily peel the synthetic leather from the engineered release sheet, so that the leather can be easily produced. (Manufacturing Method of Engineering Release Sheet) ® An example of a method of manufacturing the engineered release sheet 1 will be described. The method for producing the engineered release sheet 1 of the present embodiment is a method in which a release agent coating liquid is applied onto the surface i2a of the cast coating layer 12 of the substrate sheet 10 to be dried. The release layer 20 is peeled and the delamination layer 20 is embossed as needed. The release agent coating liquid is one in which the above-mentioned release agent component is dissolved or dispersed in a solvent. Examples of the solvent include benzene, toluene, xylene, methanol, ethyl hexanol isobutanol, n-butanol, methyl ethyl ketone, acetone, and tetrahydrofuran. The solvent may be used singly or in combination of two or more. The concentration of the solid content of the release agent coating liquid is preferably from 10 to 60% by weight in view of both productivity and coating properties. As the apparatus for applying the release agent coating liquid, the same apparatus as that used for the application of the synthetic resin coating for leather production can be applied. The coating amount of the coating agent coating liquid is preferably 1 to 10 g/m in terms of dry coating amount. When the coating amount of the release agent coating liquid is not less than g/m2, the peeling property of the obtained engineering release sheet 1 is sufficient, and on the other hand, if it is 134277.doc -20-200927494 l〇g/m or less, Therefore, the peeling property is not saturated, and the economy is excellent. As a dry method after application, for example, hot air (four), red drying, or the like can be applied. The drying temperature is appropriately selected depending on the solvent to be used, but it is preferably 80 to fu. When the drying temperature is _ or more, it can be quickly dried, and if it is 250 C or less, thermal deterioration of the peeling layer 2 can be suppressed. • According to the engineered release sheet 1 described above, the synthetic leather can be easily peeled off. The reason for this is that since the solvent-coated coating layer 12 of the base material sheet has excellent solvent resistance, even if the release agent coating liquid is applied, the light-bonding coating layer 12 does not dissolve, and thus the cast coating is applied. The composition of the cladding layer 12 is difficult to be mixed into the peeling layer 20, and the surface state becomes good. [Examples] Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited to the Examples and Comparative Examples. In addition, the "77" and "°/〇" in the 'examples are "parts by weight" and "% by weight" except for the "%" of the gloss unit. ^ (Example 1) ❿ [Production of base paper] - Preparation of broad-leaf bleached kraft pulp (CSF 430 mL) containing multi-stage bleaching according to oxygen-ozone-sodium hydroxide-hydrogen peroxide-dioxide gas % by weight and multi-stage bleached conifer bleached kraft pulp (CSF 45 jaws "% by weight of pulp slurry) in the order of oxygen-ozone-sodium hydroxide-hydrogen peroxide-dioxide gas. Adding a light carbonic acid mother (trade name TAMAPEARL TP-121 manufactured by Odomo Industries Co., Ltd.) as a filler to separate the raw paper ash into 10 weight °/〇, and then adding sulfuric acid to the solid content of the pulp. 134277.doc -21 ^ 200927494 〇, 5% by weight, cationic powder (manufactured by 公司 〇〇〇 31 ^ 31^11 company, trade name eight (^ K-l00) 0.5% by weight, alkyl ketene dimer sizing agent (Arakawa Chemical Industry Co., Ltd. Product name: SIZEPINE Κ-287) 0.1% by weight, polyacrylamide (manufactured by Arakawa Chemical Industries, Ltd., trade name: 〇17^丁11(^851)〇, 〇2% by weight 'prepared paper stock. -Top Twin-Wire paper machine performs papermaking on the obtained paper stock, and then uses the door roller In a press (Gate r〇11 Size Press) apparatus, oxidized starch (trade name: Ace A, manufactured by 〇ji Cornstarch Co., Ltd.) was applied to both surfaces at a coating amount of 1.5 g/m 2 (converted into a solid content), and dried. After the smoothing treatment with a mechanical calender, a base paper having a net weight of 119 g/m2, a bulk density of 0.75 g/cm3, and a paper surface of ρΗ7·6 was obtained. [Formation of a barrier layer] The above-mentioned base paper was coated by a doctor blade. The coating liquid containing polyvinyl alcohol (manufactured by Kuraray Co., Ltd., trade name PVA110) was applied to have a dry coating amount of 10 g/m2' at 200. (: hot air drying was performed to form a barrier layer. [Preparation of a coating liquid for forming a coating layer] 85 parts by weight of kaolin (trade name: uW-90, manufactured by Engelhard Co., Ltd.) and a light carbonaceous dance (trade name, manufactured by Shiraishi Kogyo Co., Ltd.) using a Cowles Disperser 15 parts by weight and 5 parts by weight of sodium polyacrylate strontium were dispersed in water to prepare a pigment slurry having a solid concentration of 65 wt. / 〇. The pigment slurry was added in an amount of 1 part by weight based on the weight of the pigment. Ammonium stearate of the release agent 1. 〇 by weight, as a binder 15 parts by weight of ammonia dissolved in /5.5% by weight of casein solution (converted into solid knives), and 18.75 parts by weight of styrene-butadiene copolymer having a butadiene content of 41% by weight (conversion) Solid component 134277.doc • 22· 200927494 A coating liquid for forming a cast light coating layer having a concentration of 54% by weight. At this time, the weight ratio of styrene-butadiene copolymer to casein (styrene-butadiene copolymer/casein) was 75/25. The coating liquid for forming a cast coating layer is applied onto the barrier layer by a roll coater so that the dry coating amount is 10 g/m 2 and dried, and then the rewetting liquid is applied. The surface temperature was 8 (the RC cast drum was peeled off for the casting process. Thereby, a cast coating layer (75 degree gloss of 93%) was formed, and a cast light having a basis weight of 157 g/m2 was obtained. Coated paper ^ In addition, a granular cerium oxide having an average particle diameter of 2 〇μηι and a maximum particle diameter of 10 μm is added to 100 parts of an amine-based polyoxo-modified alkyd resin (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KS883). 5 parts of benzene sulfonate as an acid catalyst, and 3 parts of phthalic acid as a solvent, and a solid content concentration of 3〇% was prepared to prepare a release agent. Then, on the cast coating layer of the cast coated paper, the release agent coating liquid is applied by a gravure coater so that the dry coating amount is 6 g/m 2 , to 1 Drying was carried out at 50 ° C to form a release layer. Then, the release layer was embossed by an embossing roll to obtain an engineered release sheet. The surface of the release agent of the engineered release sheet is coated with a coating material for synthetic leather containing an amino formic acid brewing resin by a blade coater, and dried to provide a leather layer. Thereafter, a blade coater is used on the leather layer. The polyurethane adhesive is applied and dried to form an adhesive layer, and then 134277.doc -23-200927494 is attached to the adhesive layer and dried, thereby forming on the engineered release sheet. The synthetic layer of the leather layer and the base fabric is followed by the synthetic leather, and the synthetic leather with the engineered release sheet is obtained. Then, the synthetic leather is peeled off from the engineering release sheet. (Example 2) Casting of the cast coated paper Engineering release sheets and synthetic leathers were obtained in the same manner as in Example 1 except that the styrene-butadiene copolymer contained in the light-coated layer was changed to a butadiene content of 45%. (Example 3) The styrene-butadiene copolymer contained in the cast coating layer of the cast coated paper was changed to a butadiene content of 5% by weight, and the examples were 1 obtain the engineering peeling sheet in the same way (Example 4) The styrene-butadiene copolymer contained in the cast coating layer of the calender coated paper was changed to a butadiene content of 55%, and The engineered release sheet and the synthetic leather were obtained in the same manner as in Example 1. (Example 5) The pelletized cerium oxide was changed to an average particle diameter 丨μΙη, and the maximum particle diameter was 8, and the examples were (3) The engineered release sheet and the synthetic leather β were obtained in the same manner (Example 6) The same procedure as in Example 3 was carried out except that the particulate cerium oxide was changed to an average particle diameter of 18 μm and a maximum particle diameter of 8 μm. Obtained engineered release sheet and synthetic leather. 134277.doc •24- 200927494 (Example 7) The styrene-butadiene copolymer contained in the cast coating layer of the cast coated paper was changed to Ding Er An engineered release sheet and synthetic leather were obtained in the same manner as in Example 1 except that the lean content was 61%. (Example 8) The weight ratio of the styrene-butadiene copolymer and casein contained in the cast coating layer of the cast coated paper was changed to 40/60, and the same as Example 4 Engineering peeled sheets and synthetic leather were obtained in the same manner.

(Example 9) An engineered release sheet and a synthetic leather were obtained in the same manner as in Example 3 except that the granular silica dioxide was changed to an average particle diameter of 3·6 μηη and a maximum particle diameter of 15 μπι. (Example 10) The weight ratio of the styrene-butadiene copolymer and the cool protein contained in the cast coating layer of the cast coated paper was changed to 40/60, and the same as Example 1 Engineering peeled sheets and synthetic leather were obtained in the same manner. (Example 11) An engineered release sheet and a synthetic leather were obtained in the same manner as in Example 3 except that the particulate cerium oxide was changed to an average particle diameter of μ 6 μm and a maximum particle diameter of 6 pm. (Example 12) Large particle size 1 5 Exfoliation of the sheet and the synthetic leather were obtained in the same manner as in Example 3 except that the granular cerium oxide was changed to an average particle diameter of 18 μm and the most μπι. 134277.doc •25· 200927494 (Example 13) In the polymerization of an amine-based polyoxo-alcoholic alkyd resin, 1 part of bis-diyldiamine (a special grade reagent manufactured by Kanto Chemical Co., Ltd.) was added as a fumarin adsorption. Except for this, an engineered release sheet and synthetic leather were obtained in the same manner as in Example 3. (Example 14) An engineered release sheet and a synthetic leather were obtained in the same manner as in Example 13 except that the number of parts of the particulate cerium oxide was changed to 4 parts. © (Comparative Example 1) The styrene-butadiene copolymer contained in the cast coating layer of the cast coated paper was changed to a butadiene content of 38%, and In the same manner as in Example 1, an engineered release sheet and a synthetic leather were obtained. (Comparative Example 2) As the substrate sheet, a styrene-butadiene copolymer having a butadiene content of 38% was used as a binder in the pigment coating layer, and kaolin was used as a coating layer pigment. A coating layer was applied, and the coating layer was subjected to mirror processing by a super stone tooth machine to obtain a delamination machine coated paper having a basis weight of 157 g/m 2 'other than that', and engineering peeling was obtained in the same manner as in Example 1. Sheets and synthetic leather. The butadiene unit content of the styrene-butadiene copolymer (SBR) in the engineered release sheets of Examples 1 to 14 and Comparative Examples 1 to 2, the colloid ratio of the SBR, the type of the substrate sheet, and The type of other adhesives, the weight ratio of the stupid-butylene-diene copolymer to other binders, the average particle size a and the maximum particle size of the cerium oxide, and the surface of the peeling layer are determined according to JIS Z 8741. Light pen 134277.doc -26- 200927494 degree is shown in Table 1 β. Further, the colloidal rate is determined by the following method, that is, on the sheet of polytetrafluoroethylene, the latex of the polymer is dried at 5 〇t. 24 hours mm (after drying) of the film. Then, the film was cut into 3 coats of styrene-butadiene to form a film thickness of 0.3 to 0.05 cm square, and the weight was measured, followed by dipping in toluene for 24 hours. Thereafter, it was dried at 1 〇 5 〇 c for 3 hours or more to completely volatilize the benzene, and the weight of the obtained solid matter was measured. Then, the colloidal ratio was determined by the formula (1).

Formula (1) Colloidal rate = (weight after toluene impregnation / weight before amber impregnation) χ 100 (%) [Table 1] 134 134277.doc •27· 200927494 ο e (%3⁄4

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Lr>mL 0[<Ν ΝΜ W ΗΜ § ll/nlmL § 卜 SS 09/0 inch SSZ, 09/0 inch $ substrate sheet type 1 —————— _ cast coated paper Cast light coated paper cast light coated paper cast coated paper cast light coated paper cast coated paper cast light coated paper cast coated paper cast light coated paper cast coated paper coated light coated paper Cast light coated paper cast coated paper cast coated paper coated light coated paper super calender machine coated paper W § § □ Butadiene unit content rate % v v〇TH 00 m 〇〇CO implementation Example 1 | Example 2I | Example 3 I 1 Example 41 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 1 Comparative Example 2 134277.doc -28- 200927494 The engineered release sheets of Examples 1 to 14 and Comparative Example 2 were used [synthetic leather was produced by the following method. On the surface of the release layer of the engineered release sheet, a solution of a synthetic leather skin for the purpose of coating the surface of the peeling layer of the engineered release sheet was used to coat the synthetic leather skin with a polyurethane solution (NE31G manufactured by Daisei Seiki Co., Ltd.). The illusion is dried by hot air to produce a skin. Then, a polygas vinegar adhesive (UD603 manufactured by Dainipsu Seika Co., Ltd.) was applied to the obtained skin by a blade coater, and the base fabric was bonded via the adhesive (AcmLLES Co., Ltd.) BASE) 'Dry at 150 C. Then, the synthetic leather is obtained by peeling off the engineered release sheet. The following evaluations were carried out on the engineered release sheets obtained in the above Examples, Comparative Examples and Reference Examples, and synthetic leathers produced using the engineered release sheets. The results are shown in Table 2. [Coating adaptability of the release agent coating liquid] The surface state of the release layer formed by applying the release agent coating liquid was visually observed. The coating suitability of the release agent coating liquid was evaluated.髎 〇: The coating surface is uniform and there is no coating grain. △. Although a part of the coating texture can be seen, it is still a practical grade. X: The coated surface is uneven and has a coating texture. [Removability of Synthetic Leather] The peelability of the synthetic leather from the engineering release sheet was visually evaluated. 〇: There is no peeling of practical problems. △: The peeling is heavy, and there is a possibility that the peeling property of the practical problem is caused.

[Surface appearance of synthetic leather J 134277.doc -29-

200927494 The surface appearance of the obtained synthetic leather was visually observed and evaluated. ◎: It is uniform and excellent in blackness. 〇: There are almost no spots and the blackness is good. △: You can see some spots or lines. X: Can see uneven spots or lines. Further, as long as it is Δ or more, it has practicality. [Reuseability] In the dark room, the surface of the synthetic leather obtained after the first peeling and the second peeling was irradiated with the light of Cadnica Light, and the appearance was visually evaluated and judged. 〇: I can't see whitening, blurring, and peeling spots. X: See whitening, blurring, peeling spots. [Table 2]

Application of peeling agent coating liquid to the surface of the peelable synthetic leather surface of the synthetic synthetic leather. Reuse Example 1 〇〇Δ 〇 Example 2 〇〇〇〇 Example 3 〇〇 ◎ 〇 Example 4 〇 〇 ◎ 〇 Example 5 〇〇 ◎ 〇 Example 6 〇〇 ◎ 〇 Example 7 〇〇 ◎ 〇 Example 8 〇〇 △ (plaque) 〇 Example 9 △ 〇 △ (texture) 〇 Example 10 〇〇χ (non-uniform spot) 〇 Example 11 〇〇〇 (high gloss) 〇 Example 12 x (texture) 〇 X (texture) 〇 Example 13 〇〇 ◎ 〇 Example 14 ◎ 〇 ◎ 〇 Comparative Example 1 〇 Δ X (non-uniform spot) 〇Comparative Example 2 〇Δ 〇X According to the binder of the substrate sheet, the binder of the light-coated layer contains 50% by weight or more of 134277.doc -30·200927494 more than the content of butadiene units. The engineered release sheet of Examples 1 to 14 of the 40 〇/〇 styrene-diene copolymer can be easily peeled off and the synthetic leather is also excellent in reusability. Further, in particular, when the styrene-butadiene copolymer is used, the olefinic unit is 45% or more of the engineering release sheets of Examples 2 to 7, 13, and 14 Synthetic leather has a superior surface appearance. Moreover, the maximum particle size of the cerium oxide in the release layer is less than 1 〇μιη. The engineering stripping of the examples 1 to 8, 10, 11, 13, 14 is not detached from the moon, on the substrate. When the material is applied to the release agent coating liquid, the coating property is excellent. The line 'that is, the coating of the comparative examples i and 2 which are adapted to be different from the butadiene unit of the styrene butadiene copolymer contained in the binder of the cast coating layer by 4% or less. = The peeling properties of synthetic leather are lower from the sheet. In Comparative Example 2 in which a coated paper is used as a substrate sheet in a super-caffeine machine, the flexibility is not repeated. [Industrial Applicability] The substrate sheet of the present invention can be used for an engineered release sheet. The peeling property can be improved when the synthetic peeling sheet is peeled off from the synthetic leather. By using the engineered release sheet of the present invention, the peeling property of the synthetic leather can be improved. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an embodiment of a substrate sheet of the present invention. Figure 2 is a cross-sectional view showing an embodiment of the engineered release sheet of the present invention. 0 134277.doc -31 · 200927494 [Explanation of main component symbols] 1 Engineering release sheet 10 Substrate sheet (substrate for engineering release sheet) Sheet) 11 Support 12 Casting coating layer 13 Barrier layer * 20 Peeling layer ❹ 134277.doc -32-

Claims (1)

200927494 X. Patent Application Range: 1. A substrate sheet for engineering release sheet, characterized in that it comprises a light-binding coated paper having a support coating layer and a cast light coating layer, the cast light coating layer containing a binder and The coating layer is a pigment, and the binder contains a stupid ethylene-butadiene copolymer having a butadiene unit content of more than 40% by weight. For example, the substrate sheet for the engineered release sheet of the item 1 is prepared, wherein: the total amount of the adhesive is 1 〇〇 0/. When the content of the styrene-butadiene copolymer in the binder is 50% by weight. the above. 3. The substrate sheet for an engineered release sheet according to claim 1 or 2, wherein the binder contains casein. A 4'-type engineered release sheet, comprising the substrate sheet for an engineered release sheet according to any one of claims 3 to 3, and a cast coating layer formed on the substrate sheet The release layer on the surface opposite to the support, the release layer contains a release agent component and a release layer pigment containing cerium oxide. 5. The engineered release sheet of claim 4, wherein the release agent is an alkyd resin to which a fumarin adsorbent is added. 6. The engineered release sheet according to claim 4, wherein the diced layer contained in the pigment for the release layer has an average particle diameter of 3 _ and a maximum particle diameter of 1 〇 μηι or less. 7. The engineered release sheet of claim 4 or 5, wherein the surface of the release layer opposite to the substrate sheet for the engineered release sheet has a 75 degree gloss of 30 to 9 measured according to JIS Z 8741. %. A method for producing a synthetic leather, characterized by comprising the following steps: 134277.doc 200927494 * On a work release sheet according to any one of claims 4 to 7, a synthetic leather resin coating is applied to form a leather layer And peeling off the above-mentioned engineered release sheet from the leather layer of synthetic leather. 134277.doc