Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
  • B29B17/02—Separating plastics from other materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J11/00—Recovery or working-up of waste materials
  • C08J11/04—Recovery or working-up of waste materials of polymers
  • C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
  • B29B17/02—Separating plastics from other materials
  • B29B2017/0213—Specific separating techniques
  • B29B2017/0286—Cleaning means used for separation
  • B29B2017/0289—Washing the materials in liquids
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/20—Waste processing or separation
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

• the present invention relates to a laminate having at least a substrate and an intermediate layer, and a method for separating the substrate from the laminate.
• functional sheets such as release sheets have a laminated structure in which a functional layer for performing the function of the functional sheet is provided on a base material.
• Various plastic substrates are used.
• various methods are being studied for separating base materials with a high resin content from used functional sheets and recovering and reusing the resin. .
• Patent Document 1 discloses a release film in which a release layer is formed on at least one side of a base film via an easily soluble resin layer, and the release film after use is formed of an easily soluble resin is immersed in a solvent in which the easily soluble resin is dissolved in the solvent, thereby separating and removing the release layer on the surface of the film, and recovering only the base film. is disclosed. Further, in Patent Document 2, after using a laminated film formed by laminating a readily soluble resin layer and a surface functional layer in this order on at least one side of a base film, the resin constituting the readily soluble resin layer is soluble.
• the base film or its pulverized material is separated and recovered from the laminated film, and the separated and recovered material is remelted to form the base film.
• a method for recycling a laminated film is disclosed, which is characterized by regenerating the resin composition that has been used.
• a method of dissolving a readily soluble resin in a solvent is used to separate the base material.
• the solvent used to separate the base material contains a readily soluble resin dissolved therein, and there is a risk that the dissolved resin may re-deposit on the separated base material.
• COD Chemical Oxygen Demand
• Various types of waste liquid treatment are required. Also, in the waste liquid treatment process, it leads to an increase in the amount of CO 2 emissions, etc., depending on the degree of the load of the waste liquid treatment. Therefore, there is a demand for a method that is more effective in reducing the environmental load.
• the present invention has been made in view of the above circumstances, and in a method for separating a substrate from a laminate, the substrate can be easily separated by using water, and contamination of the water used for separating the substrate can be suppressed. , to provide a method for separating substrates.
• the present inventors have found that in a laminate having a substrate and a hydrophilic and water-insoluble intermediate layer on at least one surface side of the substrate, by bringing the intermediate layer into contact with water, the above The inventors have found that the problem can be solved and completed the present invention. That is, the present invention provides the following [1] to [10].
• [1] A laminate having a substrate and a hydrophilic and water-insoluble intermediate layer on at least one surface side of the substrate, wherein the intermediate layer is brought into contact with water to A method for separating a substrate, characterized in that the substrate is separated from.
• [3] The method for separating a substrate according to [1] or [2], wherein the substrate and the intermediate layer are directly laminated.
• [4] The method for separating a substrate according to any one of [1] to [3], wherein the intermediate layer is a layer having a siloxane bond.
• the layer having a siloxane bond is a layer formed from a silane-based compound exhibiting polycondensation properties by hydrolysis.
• the silane-based compound contains at least one selected from tetrafunctional silane-based compounds represented by the following general formula (a) and oligomers thereof as a main component.
• Si(OR) p (X) 4-p (a) [In general formula (a), R represents an alkyl group, and X represents a halogen atom. When a plurality of R and X are present, the plurality of R and X may be the same or different. p represents an integer of 0 to 4; ] [7] The method for separating a substrate according to [6] above, wherein the tetrafunctional silane compound is a tetraalkoxysilane represented by the following general formula (a1).
• Si(OR) 4 (a1) [In general formula (a1), R represents an alkyl group. When there are multiple R's, the multiple R's may be the same or different.
• [8] The method for separating a substrate according to any one of [1] to [7], wherein the substrate is a resin film. [9] The method for separating a substrate according to any one of [1] to [8], further comprising a functional layer on the side of the intermediate layer opposite to the substrate. [10] The method for separating a substrate according to [9] above, wherein the functional layer is a release agent layer, a printed layer, a hard coat layer, an easily adhesive layer, or an adhesive layer.
• the substrate in the method for separating the substrate from the laminate, the substrate can be easily separated by using water, and the contamination of the water used for separating the substrate can be suppressed.
• solid content refers to components contained in the target composition, excluding diluent solvents such as water and organic solvents.
• diluent solvents such as water and organic solvents.
• preferably 10 to 90, more preferably 30 to 60 combining “preferred lower limit (10)” and “more preferred upper limit (60)” to “10 to 60” can also Similarly, from the description of "preferably 10 or more, more preferably 30 or more” and “preferably 90 or less, more preferably 60 or less” for the same matter, “preferable lower limit (10)” and “more preferred upper limit Value (60)” can also be combined with “10 or more and 60 or less”.
• energy ray is a term that means known energy rays such as ⁇ -rays, electron beams, ultraviolet rays, and visible light.
• the method for separating a substrate of the present invention comprises a laminate having a substrate and a hydrophilic and water-insoluble intermediate layer on at least one surface side of the substrate, wherein the intermediate layer is brought into contact with water.
• the substrate is separated from the layered product by causing the substrate to be separated.
• the use of a hydrophilic and water-insoluble intermediate layer produces the above-mentioned excellent effects, and the reason for this is considered as follows. That is, before the substrate is separated from the laminate, the intermediate layer is in close contact with the substrate or other layers on the substrate side mainly through hydrogen bonding and anchoring effects.
• the intermediate layer is hydrophilic
• the intermediate layer when the intermediate layer is brought into contact with water, the interface between the substrate and the intermediate layer or the interface between the intermediate layer and another layer present on the substrate side water can easily enter. It is believed that the water entering the interface inhibits the hydrogen bonding, causing peeling at the interface, and as a result, the substrate can be easily separated from the laminate.
• the intermediate layer since the intermediate layer is both hydrophilic and water-insoluble, the above-mentioned water (hereinafter also referred to as "washing water”) used when separating the substrate from the laminate is used. It does not leach into the wash water when it comes into contact with Therefore, contamination of washing water can be prevented.
• the contact angle is preferably 50 degrees or less, more preferably 45 degrees or less.
• the lower limit of the contact angle of water on the substrate-side surface of the intermediate layer is not particularly limited, but is, for example, 0 degree.
• the contact angle of water on the substrate-side surface of the intermediate layer is preferably 0 to 55 degrees, more preferably 0 to 50 degrees, and even more preferably 0 to 45 degrees. degree.
• the contact angle is a value measured using the method described in Examples below.
• the intermediate layer is determined by the contact angle of water on the surface of the release agent layer, which is measured using the method described in Examples below, and the If the difference from the contact angle of water on the substrate-side surface is 30 degrees or more, the intermediate layer is determined to be water-insoluble.
• the contact angle difference is preferably 40 degrees or more, more preferably 50 degrees or more. When the value of this difference is small, it means that the component constituting the intermediate layer is eluted into water and the partly exposed release agent layer is measured.
• the upper limit of the contact angle difference is not particularly limited, but is preferably 150 degrees, more preferably 140 degrees, and still more preferably 130 degrees. As described above, these stepwise lower and upper limits can be independently combined.
• the contact angle difference is preferably 30 to 150 degrees, more preferably 40 to 140 degrees, and even more preferably 50 to 130 degrees.
• the contact angle of water on the release agent layer surface is not particularly limited, but is usually 80 degrees or more, preferably 85 degrees or more, and more preferably 90 degrees or more.
• the upper limit of the contact angle of water on the release agent layer surface is usually 150 degrees, preferably 140 degrees, and more preferably 130 degrees. As described above, these stepwise lower and upper limits can be independently combined.
• the contact angle of water on the release agent layer surface is preferably 80 to 150 degrees, more preferably 85 to 140 degrees, and even more preferably 90 to 130 degrees.
• the contact angle of water on the surface of the release agent layer is also a value measured using the method described in Examples below.
• the method for bringing the intermediate layer into contact with water is not particularly limited, but it is preferable to immerse the laminate in water.
• the laminated body may be immersed in the water tank as it is in the roll form.
• the laminate roll may be left still in a water tank, or the water tank may be agitated.
• the sheet fed out from the roll-shaped laminate in the middle of the process of continuously performing processing (roll-to-roll processing) until the sheet of the laminate is fed out from the feeding roll and wound up with the take-up roll. may be passed through a water tank, or the sheet may be rubbed with water with a brush or the like.
• the cut laminate may be immersed in a water tank.
• the cut laminate may be left still in a water tank, or the water tank may be agitated.
• a treatment such as rubbing water with a brush or the like may be performed on the cut laminate.
• the water to be brought into contact with the intermediate layer may be room temperature, but is preferably warm water.
• 40° C. or higher is preferable, and 60° C. or higher is more preferable.
• it is preferably less than 100°C, and more preferably 98°C or less.
• these stepwise lower and upper limits can be independently combined.
• the temperature of water to be brought into contact with the intermediate layer is preferably 40° C. or higher and lower than 100° C., more preferably 60° C. or higher and 98° C. or lower.
• the water being at "room temperature” means the same temperature as the temperature of the room environment, and refers to the temperature of the water in the state of not being heated by a heat source or the like under the room temperature environment.
• An example of the room temperature is not particularly limited, but may be, for example, 23°C.
• the laminate is not particularly limited as long as it has a base material and a hydrophilic and water-insoluble intermediate layer on at least one surface side of the base material. From the viewpoint of facilitating the recovery and reuse of resins and the like that constitute the substrate, it is preferable that the substrate and the intermediate layer are directly laminated.
• directly lamination refers to, for example, a configuration in which each layer is in direct contact with each other without another layer between the substrate and the intermediate layer.
• the laminate further includes a functional layer on the side of the intermediate layer opposite to the substrate.
• the substrate for example, a paper substrate, a resin film, or the like can be used, and a resin film is preferable from the viewpoint of easier separation. Moreover, when the resin film is separated, the recovered component is the resin. On the other hand, when the paper substrate is separated, the recovered component becomes pulp fibers.
• the resin film examples include polyester films such as polyethylene terephthalate film, polybutylene terephthalate film and polyethylene naphthalate film; polyolefin films such as polyethylene film and polypropylene film; polyimide film; polyamide film; polycarbonate film; vinyl copolymer (EVA) film; ethylene-(meth)acrylic acid copolymer film; ethylene-(meth)acrylic acid ester copolymer film; cycloolefin polymer film; polyurethane film; can be used.
• a polyester film is preferable from the viewpoint of heat resistance and strength.
• polyester film a polyester film containing polyethylene terephthalate, polybutylene terephthalate, or polyethylene naphthalate as a main component is preferable from the viewpoint of easy recovery and recycling of the resin.
• the "main component" refers to the component with the highest content among the components constituting the film.
• a polyethylene terephthalate film, a polybutylene terephthalate film, and a polyethylene naphthalate film are more preferable, and a polyethylene terephthalate film is even more preferable.
• the base material may be a resin film containing only one type of the above-mentioned resins, or may contain two or more types thereof.
• the substrate may be a single-layer film made of one resin film, or a multi-layer film in which a plurality of resin films are laminated. From the viewpoint of facilitating recovery of the resin, the substrate is preferably a single-layer film made of one resin film or a multi-layer film made by laminating one resin film.
• the resin film may contain known fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, and the like.
• the resin film may be transparent or colored as desired.
• the substrate may be previously subjected to surface treatment such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, etching treatment such as oxidation, etc., if necessary.
• surface treatment such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, etching treatment such as oxidation, etc.
• the substrate is also preferably water-insoluble, and more preferably both hydrophobic (non-hydrophilic) and water-insoluble.
• the thickness of the substrate is not particularly limited, but is preferably 10 to 500 ⁇ m, more preferably 15 to 300 ⁇ m, still more preferably 20 to 200 ⁇ m from the viewpoint of strength, rigidity and the like.
• the "thickness of the base material” means the thickness of the entire base material. means the total thickness of all layers
• the intermediate layer is preferably a layer having a siloxane bond (--Si--O--Si--) from the viewpoint of facilitating the effects of the present invention.
• the layer having a siloxane bond is preferably, for example, a layer formed from a silane-based compound that exhibits polycondensation properties due to hydrolysis.
• the silane-based compound exhibiting polycondensability by hydrolysis is a compound in which a hydrolyzed compound can undergo polycondensation.
• the silane-based compound exhibiting polycondensability by hydrolysis may be an alkoxysilane exhibiting polycondensation by hydrolysis.
• the silane-based compound exhibiting polycondensability by hydrolysis preferably contains, as a main component, at least one selected from tetrafunctional silane-based compounds represented by the following general formula (a) and oligomers thereof.
• Si(OR) p (X) 4-p (a) [In general formula (a), R represents an alkyl group, and X represents a halogen atom. When a plurality of R and X are present, the plurality of R and X may be the same or different.
• p represents an integer of 0 to 4; ]
• alkyl groups that can be selected as R include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n -hexyl group, neopentyl group, methylpentyl group and the like.
• a methyl group, an ethyl group, an n-propyl group, or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable, from the viewpoint of further improving the reactivity of the silane compound.
• the alkyl group that can be selected as R may be either straight-chain or branched-chain, preferably straight-chain.
• a halogen atom that can be selected as X is preferably a chlorine atom, a bromine atom, or an iodine atom, and more preferably a chlorine atom.
• the silane compound represented by the general formula (a) may be used alone or in combination of two or more.
• the silane-based compound represented by the general formula (a) includes a silane-based compound in which p is 4 in the general formula (a). That is, the tetrafunctional silane compound is preferably a tetraalkoxysilane represented by the following general formula (a1).
• Si(OR) 4 (a1) [In general formula (a1), R represents an alkyl group. When there are multiple R's, the multiple R's may be the same or different. ]
• Examples of the alkyl group that can be selected as R in general formula (a1) are the same as those for R in general formula (a) described above, and preferred embodiments thereof are also the same.
• More preferred specific examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and the like. Among these, at least one of tetramethoxysilane and tetraethoxysilane, or a mixture of tetramethoxysilane and tetraethoxysilane is preferable from the viewpoint of availability and reactivity of the hydrolysis reaction.
• the "main component" in the silane compound exhibiting polycondensation property by hydrolysis is the silane compound that is the most contained in the total amount of 100% by mass of the silane compound exhibiting polycondensation property by hydrolysis. refers to In the silane compound exhibiting polycondensation property by hydrolysis, the content of the silane compound represented by the general formula (a) and its oligomer contained as a main component is higher than the content of other silane compounds. Although there is no particular limitation as long as it is large, for example, it is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass in 100% by mass of the total amount of the silane-based compound that exhibits polycondensation properties due to hydrolysis.
• the content of the silane-based compound represented by the general formula (a) and its oligomer contained as a main component in the silane-based compound exhibiting polycondensability by hydrolysis is , preferably 50 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass, still more preferably 90% by mass of the total amount of 100% by mass of the silane compound that exhibits polycondensation by hydrolysis. ⁇ 100% by mass.
• the average degree of polymerization of the oligomer of the tetrafunctional silane compound represented by the general formula (a) or the oligomer of the tetraalkoxysilane represented by the general formula (a1) is not particularly limited, but Each independently may be, for example, 2 to 20 or 2 to 15. That is, it may be an average 2- to 20-mer of each silane-based compound, or an average 2- to 15-mer of each of the silane-based compounds.
• both the "oligomer of the tetrafunctional silane compound represented by the general formula (a)” and the “oligomer of the tetraalkoxysilane represented by the general formula (a1)” are simply the respective silane-based It is not limited to those obtained using the monomer of the compound as a starting material, and as a result of synthesis using another compound as a starting material, the structure of the compound obtained is a tetrafunctional silane represented by the general formula (a).
• silane-based compound exhibiting polycondensation properties by hydrolysis can also be used as the silane-based compound exhibiting polycondensation properties by hydrolysis, and preferred examples of such commercial products include “Colcoat (registered trademark) N-103X” and “Colcoat (registered trademark) PX”. , "methyl silicate 51” which is an average tetrameric oligomer of tetramethoxysilane, "methyl silicate 53A” which is an average heptamer oligomer of tetramethoxysilane, "ethyl silicate 40” which is an average pentamer oligomer of tetraethoxysilane.
• Ethylsilicate 48 which is an average decamer oligomer of tetraethoxysilane
• EMS-485" which is a mixture of an average decamer oligomer of tetramethoxysilane and an average decamer oligomer of tetraethoxysilane ( All of them are manufactured by Colcoat Co., Ltd.) and the like.
• silane-based compounds that the silane-based compound may contain include mono- to tri-functional silane-based compounds.
• a tetrafunctional silane-based compound as a main component.
• a catalyst such as an acid catalyst or a metal catalyst may be used.
• the thickness of the intermediate layer is preferably 0.01 to 1 ⁇ m, more preferably 0.03 to 0.5 ⁇ m, still more preferably 0, from the viewpoint of facilitating water infiltration when the intermediate layer comes into contact with water. 0.05 to 0.3 ⁇ m.
• the laminate preferably further has a functional layer on the side of the intermediate layer opposite to the substrate. That is, it is preferable that the laminate has a substrate, and the intermediate layer and the functional layer in this order on at least one surface side of the substrate. Further, as one aspect of the laminate, the base material, the intermediate layer, and the functional layer may be directly laminated in this order, and at least the base material and the intermediate layer may be laminated in this order. Direct lamination is more preferred.
• direct lamination refers to, for example, a structure in which each layer is in direct contact with each other without any other layer between the substrate, the intermediate layer, and the functional layer.
• the functional layer can be appropriately selected depending on the use of the laminate, and examples thereof include a release agent layer, a print layer, a hard coat layer, an easy adhesion layer, an adhesive layer, and the like.
• the functional layer is a release agent layer
• the contact angle of water on the surface of the release agent layer increases, and the contact angle of water on the surface of the release agent layer and the contact angle of water on the substrate-side surface of the intermediate layer The larger the difference from the corners, the easier the separation of the substrates.
• the laminate having a functional layer is preferably a laminate having a release agent layer, more preferably a release sheet, from the viewpoint of its use and usage amount.
• a release sheet is generally used for the purpose of protecting the surfaces of other functional sheets and various parts used for specific purposes during the production, transport, storage, etc. of these sheets and parts. After actually fulfilling the role of protecting these parts, etc., they are often peeled off from the surface and discarded. Therefore, the use of the method for separating the substrate from the release sheet as a method for separating the substrate from the release sheet is a highly contributory application from the viewpoint of resource conservation and environmental protection.
• the functional layer of the laminate is preferably a release agent layer
• a preferred aspect of the laminate is a release sheet. That is, as a preferred embodiment of the method for separating the substrate, a substrate, a water-insoluble and hydrophilic intermediate layer on at least one surface side of the substrate, and the substrate of the intermediate layer In a release sheet having a release agent layer on the opposite side, the intermediate layer is brought into contact with water to separate the intermediate layer from the substrate surface, thereby separating the substrate from the release sheet
• a method for separating a substrate characterized by:
• the release agent layer is preferably a layer formed from a release agent composition.
• the release agent composition used to form the release agent layer is not particularly limited as long as it has release properties. Examples include silicone compounds; fluorine compounds; long-chain alkyl group-containing compounds; A release agent composition containing a thermoplastic resin material such as a base resin as a main component can be used. Moreover, it is preferable to use a release agent composition containing an energy ray-curable or thermosetting resin as a main component. These release agent compositions may be used singly or in combination of two or more.
• the "main component" in the release agent composition refers to the component contained most in the total solid content of 100% by mass of the release agent composition.
• the release agent layer may contain other additives in addition to the main components described above.
• Other additives include, for example, antioxidants, light stabilizers, flame retardants, conductive agents, antistatic agents, plasticizers, and the like.
• the functional layer is preferably water-insoluble, and more preferably both hydrophobic (non-hydrophilic) and water-insoluble.
• the thickness of the functional layer can be appropriately selected depending on the application of the laminate, and is not particularly limited, but is preferably 0.02 to 200 ⁇ m, for example.
• the functional layer for example, when the functional layer is a release agent layer, it is preferably 0.02 to 5 ⁇ m, more preferably 0.03 to 2 ⁇ m, and still more preferably 0.05 to 1.5 ⁇ m. be.
• the method for producing the laminate that can be used in the present invention is not particularly limited as long as a laminate having a substrate and an intermediate layer on at least one surface side of the substrate can be produced. , can be produced by a known method.
• an intermediate layer may be formed by applying an intermediate layer-forming composition or a solution thereof to one surface of a substrate, followed by heating and drying, or curing by energy ray irradiation. can be done.
• the method for forming the functional layer can be appropriately selected depending on the type of the functional layer.
• the functional layer-forming composition or its solution is applied, and then heated and dried or cured by energy ray irradiation. It can be produced by forming a functional layer.
• the composition for forming a functional layer or a solution thereof is applied to the release-treated surface of another release material, and then heated and dried or cured by irradiation with an energy beam.
• a functional layer may be formed by forming a functional layer and bonding this functional layer to the surface of the intermediate layer opposite to the substrate.
• the release material may be peeled off before laminating the functional layer on the intermediate layer, or after lamination and before use of the laminate having the functional layer formed thereon. Moreover, when forming a functional layer by the former method, you may bond a peeling material further on the surface of the formed functional layer.
• the method for applying the composition for forming the intermediate layer, the composition for forming the functional layer, or the solution thereof is not particularly limited, and known methods can be used. Examples thereof include spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.
• the drying method and drying temperature for drying the intermediate layer or functional layer are not particularly limited, and can be appropriately selected according to the characteristics of the material forming the intermediate layer or functional layer.
• irradiation conditions such as the type of energy ray, illuminance, and light amount should be appropriately selected according to the characteristics of the material forming the intermediate layer or functional layer. can be done.
• the substrate can be easily separated from the laminate by using the method for separating the substrate.
• the intermediate layer in the laminate that contributes to the separation of the base material can reduce the contamination of the washing water used when separating the base material, and furthermore, the contamination of the washing water is suppressed.
• the resin recovered from the separated substrate is less likely to be contaminated.
• suppression of contamination of the wash water leads to reuse of the wash water and simplification of waste treatment. Therefore, it can be suitably used when the resin recovered from the base material is reused as it is, or when even the monomer, which is the raw material constituting the resin, is decomposed and recycled.
• the washing water can be easily separated from the separated base material by simply filtering the washing water, and the resin can be recovered and recycled. It also simplifies the whole process. Therefore, as one aspect of the present invention, for example, at least, using the method for separating the substrate, from the laminate having the substrate and the intermediate layer on at least one surface side of the substrate, the separating the substrate from the laminate by bringing the intermediate layer into contact with water to separate the intermediate layer from the surface of the substrate or the surface of the layer on the substrate side; and a step of recovering the resin; and a method for recycling the resin.
• the step of recovering the resin from the base material is not particularly limited, and a known recovery method can be appropriately used depending on the type of each resin and the raw material of the resin.
• the thickness of the substrate in the release sheet used in each example and each comparative example was measured using a constant pressure thickness measuring instrument manufactured by Teclock Co., Ltd. (model number: "PG-02J", standard specifications: JIS K6783: 1994, JIS Z1702: 1994, JIS Z1709: 1995).
• the thicknesses of the intermediate layers of Examples 1 to 4 and Comparative Example 2 were measured using a spectroscopic ellipsometer (manufactured by JA Woollam, product name "M-2000").
• the thickness of the release agent layer of each example and each comparative example was measured using a reflective film thickness meter (manufactured by Filmetrics, product name: "F20").
• test piece was separated into a laminate in which the release agent layer and the intermediate layer were integrally supported on the adhesive tape and the base material, and the adhesive carrying the release agent layer and the intermediate layer was separated.
• the tape was taken out of the hot water and dried at room temperature (23° C.) for 24 hours. After that, the contact angle was measured for the surface of the intermediate layer carried on the adhesive tape (the surface of the intermediate layer that was in contact with the substrate surface). The contact angle was measured according to JIS R3257:1999 by the sessile drop method using a contact angle meter (Kyowa Interface Science Co., Ltd., product name: "DM-701"). For droplets, distilled water was used.
• Comparative Example 2 was affected by the partially exposed release agent layer eluted in warm water in the measurement of the contact angle of water on the material side surface. Therefore, in Table 1 below, the evaluation of the hydrophilicity of the intermediate layer is shown only when the intermediate layer is water-insoluble.
• Comparative Example 2 a laminate sample was prepared in which only an intermediate layer was formed on a base material without forming a release agent layer, and the surface of the intermediate layer was subjected to the above "(1) Release agent layer surface The contact angle measured according to "Measurement of contact angle of water” was 35.2 degrees. From this point as well, it was confirmed that the intermediate layer of Comparative Example 2 was eluted into the hot water by the treatment in "(2) Measurement of the water contact angle of the substrate-side surface of the intermediate layer".
• a release sheet was produced by the method shown below.
• Example 1 A biaxially oriented polyethylene terephthalate film (thickness: 31 ⁇ m) was prepared as a substrate.
• a composition for forming an intermediate layer a silane compound exhibiting polycondensation properties by hydrolysis (manufactured by Colcoat Co., Ltd., product name “Colcoat (registered trademark) N-103X”) was prepared and mixed with isopropyl alcohol. to adjust the solid content concentration to 1.5% by mass.
• the resulting composition for forming an intermediate layer was uniformly coated on one side of the substrate with a bar coater so that the thickness of the intermediate layer after drying was 0.1 ⁇ m to form a coating layer.
• the coating layer was cured by heating for 1 minute to form an intermediate layer.
• thermosetting addition-reactive silicone manufactured by Shin-Etsu Chemical Co., Ltd., "KS-847H
• a platinum catalyst manufactured by Shin-Etsu Chemical Co., Ltd., "CAT-PL- 50T”
• the prepared coating liquid is applied with a bar coater onto the intermediate layer formed on the base material to form a coating layer, and the coating layer is cured by heating at 120 ° C.
• methylated melamine resin manufactured by Nippon Carbide Industry Co., Ltd., product name "MW-30”
• polyorganosiloxane both terminal carbinol-modified polydimethylsiloxane Shin-E
• a release sheet having a configuration in which a release agent layer of 1 ⁇ m was formed and a substrate/intermediate layer/release agent layer were laminated in this order was produced. Using the obtained release sheet, the separability evaluation of the substrate, which will be described later, was performed.
• Example 3 An intermediate layer was provided on one side of the substrate in the same manner as in Example 1. Next, a mixture of polyfunctional acrylates dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd., product name "Aronix (registered trademark) M-400", solid content 100% by mass) 94 parts by mass And, acrylic-modified polydimethylsiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "X-22-164A”, solid content 100% by mass) 1 part by mass, and a photopolymerization initiator (IGM Resins B.V., Trade name “Omnirad (registered trademark) 907” (2-methyl-1[4-(methylthio)phenyl]-2-morifolinopropan-1-one, solid content 100% by mass)) 5 parts by mass, isopropyl alcohol and methyl
• a coating liquid of the agent composition was obtained.
• the prepared coating solution was applied onto the intermediate layer formed on the substrate using a bar coater and dried at 80° C. for 1 minute to obtain a coating layer.
• the coating layer is irradiated with ultraviolet light (accumulated light amount: 250 mJ/cm 2 ) to form a release agent layer (thickness: 1 ⁇ m), and a structure in which the base material/intermediate layer/release agent layer are laminated in this order.
• a release sheet was produced. Using the obtained release sheet, the separability evaluation of the substrate, which will be described later, was performed.
• Example 4 In Example 1, the substrate/intermediate layer/releasing agent layer were laminated in this order in the same manner as in Example 1, except that the composition for forming the intermediate layer was changed as follows to form the intermediate layer.
• a release sheet having the structure was prepared.
• As a composition for forming an intermediate layer 100 parts by mass of a silane-based compound (manufactured by Colcoat Co., Ltd., product name "Methyl Silicate 53A") exhibiting polycondensation properties by hydrolysis, 35 parts by mass of distilled water, and an acid catalyst.
• a silane-based compound manufactured by Colcoat Co., Ltd., product name "Methyl Silicate 53A"
• Example 1 A release sheet having a structure in which a base material and a release agent layer were laminated in this order was prepared in the same manner as in Example 1, except that no intermediate layer was provided. Using the obtained release sheet, the separability evaluation of the substrate, which will be described later, was performed.
• Example 2 A biaxially oriented polyethylene terephthalate film (thickness: 31 ⁇ m) was prepared as a substrate. Next, a 2% by mass aqueous solution of partially saponified polyvinyl alcohol resin (manufactured by Mitsubishi Chemical Corporation, "Gosenol (registered trademark) GL-05") is applied to the substrate so that the thickness after drying is 0.1 ⁇ m. An intermediate layer was formed by uniformly coating one side and heating at 120° C. for 1 minute. A release agent layer was formed in the same manner as in Example 1, and a release sheet having a configuration in which substrate/intermediate layer/release agent layer were laminated in this order was produced. Using the obtained release sheet, the separability evaluation of the substrate, which will be described later, was performed.
• partially saponified polyvinyl alcohol resin manufactured by Mitsubishi Chemical Corporation, "Gosenol (registered trademark) GL-05
• a test piece was obtained by cutting the release sheet obtained by the method described in Examples and Comparative Examples into a size of 50 mm ⁇ 50 mm. Next, a glass beaker with a capacity of 500 mL was filled with 300 mL of hot water at 90°C, and the test piece was entirely immersed in the warm water and allowed to stand at 90°C for 1 hour. After that, the test piece taken out from the warm water was immersed in distilled water at room temperature (23° C.) and washed to obtain a sample for evaluation of separability.
• N nitrogen (N), which is a specific element derived from the chemical composition of the release agent layer measured by X-ray photoelectron spectroscopy (XPS), was applied to the substrate surface on the side where the release agent layer was provided. , the separability of the substrate was evaluated based on the amount of silicon (Si) detected. The ratio of each element was calculated by the following formula, and it was determined that the release agent layer was separated and removed from the substrate surface when the specific element derived from the chemical composition of the release agent layer was less than 0.05 atom %. The results are shown in Table 2 below. In addition, in Table 2, the case of less than 0.05 Atom % was described as not detected (N.D.).
• N represents the amount of nitrogen element
• Si represents the amount of silicon element
• C represents the amount of carbon element
• O represents the amount of oxygen element.
• Nitrogen (N) element ratio (Atom%) [N / (C + O + N + Si)] ⁇ 100
• Silicon (Si) element ratio (Atom%) [Si / (C + O + N + Si)] ⁇ 100
• the base material separated from the test piece was taken out from the water, and the release agent layer with the intermediate layer floating on the surface of the water was filtered to obtain the eluted water.
• Heat drying and vacuum drying were repeated to obtain components eluted in water from the release sheet, and the weight thereof was measured.
• Table 2 below as elution amounts. Since the substrate and the release agent layer constituting the release sheets obtained in Example 1 and Comparative Example 2 are water-insoluble, the components eluted by this method are the components of the intermediate layer. Therefore, this method can also be used as an evaluation method for determining whether or not the intermediate layer in the release sheet is water-insoluble.
• the value of the eluted amount in Table 2 below indicates the value (unit: ⁇ g/m 2 ) of (dry weight of eluted portion)/(area of immersed release sheet).
• the substrate As shown in Table 2, from the evaluation results of the separability of the substrate using the release sheets of Examples 1 to 4, it was formed from a substrate and a silane-based compound exhibiting polycondensation by hydrolysis on the substrate.
• the substrate In a release sheet having a laminate provided with an intermediate layer, the substrate may be separated from the release sheet by bringing the intermediate layer into contact with water to separate the intermediate layer from the surface of the substrate. confirmed to be possible.
• the intermediate layer is water-insoluble, the COD in the washing water used for separating the substrate It was confirmed that the value is low and it is excellent as a separation method for substrates with little environmental load.
• the release sheet of Comparative Example 1 when the release sheet of Comparative Example 1 was used, the Si element was detected on the release agent layer side of the substrate even after the separability evaluation of the substrate, and the release agent layer was removed from the substrate. Therefore, it was confirmed that it is not suitable as a method for separating the base material.
• the release sheet of Comparative Example 2 when the release sheet of Comparative Example 2 was used, the base layer was separated by bringing the intermediate layer into contact with water. However, since the intermediate layer is water-soluble, it was confirmed that the COD value in the washing water used for separating the substrate was increased.
• the substrate separation method of the present invention since the intermediate layer is insoluble in the washing water used, contamination of the washing water can be suppressed as compared with conventional products. Therefore, for example, in the process of separating the substrate, it is possible to treat the used wash water by a simple method such as filtration, thereby reducing the burden of waste liquid treatment. In addition, there is also the advantage of facilitating reuse of the washing water. Therefore, from the viewpoint of simplifying or omitting the step of treating the waste liquid of washing water, and from the viewpoint of enabling reuse of washing water, etc., the substrate separation method of the present invention can reduce the environmental load more than before. It is an effective substrate separation method. Furthermore, it is an industrially very effective method from the viewpoint of cost reduction in the separation of the substrate due to the simplification of the waste liquid treatment process and the like.

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