WO2019189057A1 - 剥離シート - Google Patents

剥離シート Download PDF

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Publication number
WO2019189057A1
WO2019189057A1 PCT/JP2019/012659 JP2019012659W WO2019189057A1 WO 2019189057 A1 WO2019189057 A1 WO 2019189057A1 JP 2019012659 W JP2019012659 W JP 2019012659W WO 2019189057 A1 WO2019189057 A1 WO 2019189057A1
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WO
WIPO (PCT)
Prior art keywords
polybutadiene
release
release sheet
functional group
agent composition
Prior art date
Application number
PCT/JP2019/012659
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English (en)
French (fr)
Japanese (ja)
Inventor
敦史 黒川
優季 遠藤
Original Assignee
リンテック株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to CN201980022311.9A priority Critical patent/CN111918770A/zh
Priority to KR1020207027644A priority patent/KR20200135962A/ko
Publication of WO2019189057A1 publication Critical patent/WO2019189057A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D109/00—Coating compositions based on homopolymers or copolymers of conjugated diene hydrocarbons
    • 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
    • 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
    • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34922—Melamine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners

Definitions

  • the present invention relates to a release sheet.
  • a release sheet has a base material, such as paper, a plastic film, or polyethylene laminated paper, and a release layer provided on the base material.
  • the release layer is formed by applying and curing a release agent composition containing a reactive compound on a substrate.
  • Release sheets are widely used as, for example, a protective sheet for a pressure-sensitive adhesive layer possessed by a pressure-sensitive adhesive sheet, a process sheet for producing a resin sheet, a process film for forming a ceramic green sheet, a process film for producing synthetic leather, and the like.
  • a silicone release agent composition for forming a release layer a silicone release agent composition containing a silicone compound such as silicone resin, siloxane, or silicone oil is widely used.
  • the silicone compound may migrate to the contact surface with the release layer, for example, the adhesive layer surface of the adhesive sheet. It may also gradually evaporate after the transition. For this reason, when a release sheet having a release layer formed from a silicone-based release agent composition is used in an electronic material application, the silicone compound may migrate to the electronic component and cause corrosion or malfunction of the electronic component.
  • the release force with the object laminated on the release layer is usually compared to a release layer formed from a silicone release agent composition, Get higher.
  • a higher peeling force is preferable, and therefore a non-silicone release agent composition is often selected.
  • Patent Document 1 is formed from a release agent composition containing at least a polyolefin, an isocyanate having three or more isocyanate groups in a molecule, and a polyolefin polyol.
  • a release sheet having a release layer is described.
  • a release layer formed of a release agent composition other than the silicone release agent composition has a large change in release force with time, and the release force tends to increase greatly with time.
  • the peeling force of the release layer is set to be high, a change with time tends to be large, and a release layer having a stable release force is rare.
  • the present invention provides a release sheet having a release layer having a stable release force even at a high temperature storage even when the initial release force is set to be high even when the initial change is small. Objective.
  • the present inventors have found that a release sheet having a release layer formed from a release agent composition containing a specific polybutadiene and a melamine compound can solve the above problems.
  • the crosslinkable functional group is a functional group that reacts with the melamine compound (B), and the polybutadiene (A) having the crosslinkable functional group is a 1,2-vinyl compound based on the total constitutional unit of the polybutadiene (A).
  • the peel strength of the release sheet after being exposed to a high temperature environment of 70 ° C. for 7 days is defined as the peel strength after heating Y, and the peel strength of the release sheet in the state without exposure to the high temperature environment is initially set.
  • the peeling force X is defined, the change rate represented by ⁇ (peeling force after heating Y ⁇ initial peeling force X) / initial peeling force X ⁇ ⁇ 100 is within ⁇ 30%.
  • the present invention it is possible to provide a release sheet having a release layer having a stable release force even at a high temperature storage even when the initial release force is set to be high even when the initial change is small. It becomes possible.
  • the number average molecular weight (Mn) is a value in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method.
  • an "active ingredient” refers to the component remove
  • the release sheet of the present invention has a base material and a release layer provided on the base material.
  • FIG. 1 is a schematic cross-sectional view illustrating a release sheet of one embodiment of the present invention.
  • the release sheet 1 includes a base material 10 and a release layer 11 provided on the base material 10.
  • the release layer 11 is a cross-linked product formed from a release agent composition containing a specific polybutadiene (A) and a melamine compound (B). Note that other layers such as an easy adhesion layer and an antistatic layer (not shown) may be provided between the substrate 10 and the release layer 11.
  • A specific polybutadiene
  • B a melamine compound
  • the release layer of the release sheet of the present invention can be formed from a release agent composition containing a specific polybutadiene (A) and a melamine compound (B).
  • A a specific polybutadiene
  • B a melamine compound
  • the release agent composition which is a material for forming the release layer will be described.
  • “content of each component relative to the total amount of active ingredients in the release agent composition” is regarded as “content of each component in the release layer formed from the release agent composition”. You can also.
  • the release agent composition is a specific polybutadiene (A), that is, a polybutadiene (A) having a crosslinkable functional group and containing 50 mol% or more of a 1,2-vinyl body based on the total constituent units of the polybutadiene (A). And a melamine compound (B).
  • A polybutadiene
  • polybutadiene (A) having a crosslinkable functional group and containing 50 mol% or more of a 1,2-vinyl compound based on all structural units of polybutadiene (A)” is referred to as “polybutadiene (A)”.
  • A polybutadiene
  • the present inventors can reduce the change over time of the peeling force of the release layer formed from the release agent composition with respect to the release agent composition other than the silicone-based release agent composition, and sufficiently ensure the film strength.
  • Various studies were conducted on prescriptions for the purpose. As a result, a combination of a polybutadiene (A) having a crosslinkable functional group and containing 50 mol% or more of a 1,2-vinyl compound on the basis of all structural units of the polybutadiene (A) and a melamine compound (B) is effective. I found out that it was a prescription.
  • the polybutadiene has a cross-linkable functional group and contains 50 mol% or more of a 1,2-vinyl body based on all the structural units of the polybutadiene (A). It was also found that the film strength could not be secured even when (A) was used.
  • the present inventors have a polybutadiene (A) having a crosslinkable functional group and containing 50 mol% or more of a 1,2-vinyl compound on the basis of all structural units of the polybutadiene (A) and a melamine compound ( It has been found that a release sheet having a release agent layer formed from a release agent composition containing B) can solve the above problems, and has led to the present invention.
  • the release agent composition may contain additives other than the above components (A) and (B) as long as the effects of the present invention are not impaired.
  • polybutadiene (A) a polybutadiene having a crosslinkable functional group and containing 50 mol% or more of a 1,2-vinyl body on the basis of all structural units of the polybutadiene (A) is used.
  • the “crosslinkable functional group” means a functional group that reacts with the melamine compound (B) as a crosslinking agent.
  • the crosslinkable functional group possessed by the polybutadiene (A) is selected in relation to the melamine compound (B).
  • a crosslinkable functional group which polybutadiene (A) has a hydroxyl group, a carboxyl group, an epoxy group, an amino group, an isocyanate group, a thiol group, a vinyl group etc. are mentioned, for example.
  • the crosslinkable functional group is preferably a hydroxyl group.
  • the polybutadiene (A) may have at least one crosslinkable functional group, but preferably has two or more crosslinkable functional groups. When the polybutadiene (A) has two or more crosslinkable functional groups, these functional groups may be the same or different from each other, but are preferably the same as each other.
  • the position of the crosslinkable functional group that the polybutadiene (A) has is not particularly limited as long as the crosslinkable functional group can react with the melamine compound (B).
  • at least one end of the molecular chain constituting the polymer skeleton of polybutadiene (A) It preferably has a crosslinkable functional group, more preferably has a crosslinkable functional group at both ends of the molecular chain constituting the polymer backbone of polybutadiene (A), and the main chain constituting the polymer backbone of polybutadiene (A) It is more preferable to have a crosslinkable functional group only at both ends.
  • the polybutadiene (A) contains 50 mol% or more of a 1,2-vinyl body based on the total constitutional unit of the polybutadiene (A).
  • Polybutadiene is a polymer having units of 1,4-cis, 1,4-trans, and 1,2-vinyl.
  • Various polybutadienes having different content ratios of the respective units are commercially available.
  • polybutadienes having different content ratios of the respective units can be synthesized by a conventional method.
  • the use of polybutadiene (A) containing 50 mol% or more of a 1,2-vinyl body on the basis of all structural units of polybutadiene (A) in the release agent composition exhibits a high initial peel strength.
  • the peeled layer has a low initial peel force and a large change in peel force with time.
  • the content ratio of the 1,2-vinyl body in the polybutadiene (A) is preferably 60 mol% or more, more preferably 70 to 90 mol%, further preferably from the viewpoint of facilitating the synthesis of the polybutadiene (A). Is 80 to 90 mol%.
  • the number average molecular weight (M n ) of the polybutadiene (A) is preferably 1,000 to 30,000, more preferably 1,000 to 20,000, still more preferably 1,000 to 10,000, and still more preferably. 1,000 to 5,000.
  • the polybutadiene (A) may be a hydrogenated product.
  • the degree of hydrogenation of the polybutadiene (A) may be partially hydrogenated or fully hydrogenated. From the viewpoint of improving the chemical stability of the peeling force of the release layer, a vinyl group is used. A partially hydrogenated product having a low residual ratio is more preferable, and a completely hydrogenated product is more preferable. From this viewpoint, it is preferable that the polybutadiene (A) has a low bromine number. The lower the bromine value, the lower the residual ratio of vinyl groups in the polybutadiene (A), and the less the chemical change such as oxidation, the better the aging stability of the peel strength of the release layer.
  • the bromine number of the hydrogenated product of polybutadiene (A) is preferably 100 g / 100 g or less, more preferably 20 g / 100 g or less, still more preferably 10 g / 100 g or less, and even more preferably 8 g / 100 g or less. is there.
  • the bromine number is a value measured according to JIS K 2605.
  • polybutadiene (A) may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the polybutadiene (A) may be a mixture of a hydrogenated product and a non-hydrogenated product.
  • the melamine compound (B) is not particularly limited as long as it is a compound that can be used as a crosslinking agent for the polybutadiene (A) and can undergo a crosslinking reaction with the crosslinking functional group of the polybutadiene (A).
  • the release agent composition contains the melamine compound (B)
  • the film strength of the release layer formed by the release agent composition can be improved. Such an effect cannot be obtained when an isocyanate compound or the like is used instead of the melamine compound.
  • the melamine compound (B) is preferably a methylolated melamine resin, iminomethylolated melamine resin, methylated melamine resin, ethylated melamine resin, propylated melamine resin, butylated melamine resin, hexylated melamine resin, and octylated melamine
  • One or more selected from the group consisting of resins are more preferable, and a methylated melamine resin is more preferable.
  • the total content of the polybutadiene (A) and the melamine compound (B) in the release agent composition is preferably 70% by mass or more based on the total amount (100% by mass) of the release agent composition. More preferably, it is 80 mass% or more, More preferably, it is 90 mass% or more, More preferably, it is 95 mass% or more.
  • the total content of the polybutadiene (A) and the melamine compound (B) is an amount excluding the solvent (active ingredient amount).
  • the content ratio (A / B) of the polybutadiene (A) to the melamine compound (B) is preferably a mass ratio, preferably 5/95. It is ⁇ 95 / 5, and more preferably 10/90 to 90/10.
  • the more preferable range of the content ratio (A / B) of the polybutadiene (A) and the melamine compound (B) varies depending on the value required as the peel force from the object to be laminated.
  • a more preferable content ratio (A / B) is 5/95 to 30/70, more preferably 10/90 to 20/80 in terms of mass ratio.
  • a more preferable content ratio (A / B) is 70/30 to 95/5 in mass ratio, and still more preferably 80/20 to 90/10.
  • the release agent composition may further contain an acid catalyst.
  • an acid catalyst By using an acid catalyst, the cross-linking reactivity between the polybutadiene (A) and the melamine compound (B) can be improved, and the aging stability of the peeling force of the release layer can be more easily improved.
  • the acid catalyst is not particularly limited, but organic acid catalysts such as p-toluenesulfonic acid, methanesulfonic acid, and alkyl phosphate are suitable. The above acid catalysts may be used alone or in combination of two or more.
  • the amount of the acid catalyst used is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, and still more preferably 100 parts by mass of the total amount of polybutadiene (A) and melamine compound (B). 1 to 5 parts by mass.
  • the release agent composition may contain additives other than the above-described components (A) and (B) and an acid catalyst, if necessary.
  • additives include various additives such as antioxidants, ultraviolet absorbers, inorganic or organic fillers, antistatic agents, surfactants, photoinitiators, and light stabilizers.
  • the release agent composition preferably contains substantially no silicone compound. If a release sheet having a release layer formed from a release agent composition containing a silicone compound is used in an electronic material, the silicone compound may migrate to the electronic component and cause corrosion or malfunction of the electronic component. It is.
  • the content of the silicone compound in the release agent composition is preferably less than 5.0% by mass, more preferably 2.0%, based on the total amount (100% by mass) of the release agent composition. It is less than mass%, more preferably less than 1.0 mass%, still more preferably less than 0.1 mass%, and still more preferably less than 0.01 mass%.
  • the release agent composition contains the melamine compound (B)
  • other crosslinking agents may or may not be used together. It is preferable that the agent composition does not substantially contain an isocyanate compound. Isocyanate compounds are expected to react with the melamine compound (B) to form a crosslinked product when the functional group of the polybutadiene (A) is a hydroxyl group. Can not form.
  • an unreacted isocyanate compound remains in the release agent layer, there is a correlation with an object to be laminated, and the peel force may increase with time.
  • the isocyanate compound content in the release agent composition is preferably less than 1.0% by mass, more preferably 0.1%, based on the total amount (100% by mass) of the release agent composition. It is less than mass%, more preferably less than 0.01 mass%, still more preferably less than 0.001 mass%.
  • the release agent composition contains substantially no non-reactive polyolefin.
  • the “non-reactive polyolefin” means a non-hydrogenated polyolefin having no crosslinkable functional group or a hydrogenated polyolefin having no crosslinkable functional group.
  • the content of the non-reactive polyolefin in the release agent composition is preferably less than 5.0% by mass, more preferably 2 based on the total amount (100% by mass) of the release agent composition. Less than 0.0% by mass, more preferably less than 1.0% by mass, still more preferably less than 0.1% by mass, and still more preferably less than 0.01% by mass.
  • the release agent composition contains substantially no poly (meth) acrylic acid ester.
  • “(meth) acrylic acid” means both “acrylic acid” and “methacrylic acid”.
  • the content of the poly (meth) acrylic acid ester having a crosslinkable functional group in the release agent composition is preferably 5. based on the total amount (100% by mass) of the release agent composition. It is less than 0% by mass, more preferably less than 2.0% by mass, still more preferably less than 1.0% by mass, still more preferably less than 0.1% by mass, and still more preferably less than 0.01% by mass.
  • the release agent composition may be in the form of a solution by adding a diluent solvent to the various active ingredients described above.
  • the dilution solvent is selected from organic solvents in which the above-described components (A) and (B) have good solubility.
  • organic solvent examples include toluene, xylene, heptane, octane, methanol, ethanol, isopropyl alcohol, isobutanol, n-butanol, ethyl acetate, acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran and the like. These may be used alone or in combination of two or more.
  • the organic solvent used as a diluting solvent may use the organic solvent used at the time of the synthesis
  • the concentration of the active ingredient (solid content) contained in the solution of the release agent composition is preferably 0.1 to 15% by mass, more preferably 0.2 to 10% by mass, and still more preferably 0.5. It is prepared to be in the range of ⁇ 5% by mass.
  • the thickness of the release layer is not particularly limited, but is usually 25 to 1000 nm, preferably 50 to 500 nm. If the thickness of the release layer is 25 nm or more, it is possible to suppress variations in the peel force due to variations in the coating amount. Moreover, if the thickness of a peeling layer is 1000 nm or less, sclerosis
  • the base material used for the release sheet of the present invention include, for example, high-quality paper, clay-coated paper, cast-coated paper, kraft paper, and other paper, laminated paper obtained by laminating a thermoplastic resin such as polyethylene resin to these papers, Paper sheets such as synthetic paper, polyolefin resins such as polyethylene resin and polypropylene resin; polyester resins such as polybutylene terephthalate resin, polyethylene terephthalate resin and polyethylene naphthalate resin; polyetherimide resin; acetate resin; polystyrene resin; And a synthetic resin sheet.
  • the substrate may be a single layer or a multilayer of two or more layers of the same or different types.
  • the thickness of the substrate is not particularly limited, but is usually 10 to 300 ⁇ m, preferably 20 to 200 ⁇ m. If the thickness of the base material is 10 to 300 ⁇ m, for example, a stiffness and strength suitable for applying processing such as printing, cutting, and sticking to an adhesive sheet using a release sheet can be provided.
  • the surface on which the release layer of the base material is provided is formed by a method such as an oxidation method or a concavo-convex method as desired in order to improve the adhesion between the base material and the release layer.
  • Processing can be performed.
  • the oxidation method include corona discharge surface treatment, chromic acid surface treatment (wet), flame surface treatment, hot air surface treatment, ozone / ultraviolet irradiation surface treatment, and the like.
  • the unevenness method include a sand blast method and a solvent treatment method. These surface treatment methods are appropriately selected depending on the type of substrate, but generally, the corona discharge surface treatment method is preferably used from the viewpoints of effects and operability.
  • primer treatment can also be performed.
  • the surface on the release layer side may be embossed to form irregularities on the surface of the release sheet.
  • other layers such as an easy adhesion layer and an antistatic layer may be provided between the substrate and the release layer.
  • the release sheet includes the easy-adhesion layer, it is possible to effectively prevent the release layer from falling off the release sheet.
  • the easy-adhesion layer is usually formed by applying an easy-adhesion coating agent on the surface of the base material on the release layer side.
  • the easily adhesive coating agent include polyester resins, urethane resins, acrylic resins, melamine resins, oxazoline group-containing resins, carbodiimide group-containing resins, epoxy group-containing resins, isocyanate-containing resins, and copolymers thereof.
  • examples thereof include a coating agent mainly composed of natural rubber or synthetic rubber. These resins may be used alone or in combination of two different types.
  • the surface of the substrate to which the easy-adhesion coating agent is applied is subjected to chemical treatment and discharge treatment.
  • a surface treatment such as the above may be performed.
  • the thickness of the easy adhesion layer is preferably 50 nm or more, and more preferably 100 nm or more.
  • the thickness is preferably 5 ⁇ m or less, and more preferably 1 ⁇ m or less.
  • the effect of an easily bonding layer can be acquired favorably because the said thickness is 50 nm or more.
  • the thickness is 5 ⁇ m or less, the slipping property of the surface of the easy-adhesive layer on the side opposite to the substrate becomes good, and the workability of applying the release agent composition on the easy-adhesive layer is good. become.
  • the rate of change in peel force before and after heating is preferably within ⁇ 30%, more preferably within ⁇ 25%, and even more preferably within ⁇ 20%.
  • the rate of change in peel force before and after heating can be measured by the following method.
  • the peel strength of the release sheet after being exposed to a high temperature environment of 70 ° C. for 7 days is defined as the peel strength Y after heating.
  • the rate of change of the peel force before and after heating can be calculated using the following equation.
  • Change rate of peeling force before and after heating ⁇ (peeling force after heating Y ⁇ initial peeling force X) / initial peeling force X ⁇ ⁇ 100
  • the initial peeling force X is not only exposed to a high temperature environment of 70 ° C. but also exposed to other high temperature environments, and used a release sheet stored at room temperature after production. Measured.
  • the initial peeling force X and the post-heating peeling force Y can be measured by the method as described in the Example mentioned later, for example.
  • the rate of change in peel force within ⁇ Z% means that the rate of change is ( ⁇ Z)% or more and (+ Z)% or less.
  • the preferable value of the release force of the release sheet varies depending on the application to be applied and the type of objects to be laminated. In some cases, a low release force is preferable so that the release operation at the time of release is smooth, or the release operation is performed. In some cases, a high peeling force is preferable in order to improve the retention of the object.
  • the release sheet of the present invention is preferably used when the setting of the initial release force is high. In one embodiment of the present invention, the peeling force of the release layer exhibited by the release sheet is preferably 2500 mN / 20 mm or more, more preferably 3000 mN / 20 mm or more, and further preferably 3500 mN / 20 mm or more.
  • the upper limit of the peeling force of the release sheet is usually preferably 6000 mN / 20 mm.
  • the peeling force of a peeling sheet changes with the target objects laminated
  • the release sheet of the present invention can be used as a protective sheet for various pressure-sensitive adhesive bodies such as pressure-sensitive adhesive sheets.
  • the pressure-sensitive adhesive layer side of a pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer provided on one surface of the base material. Used on the surface. It can also be used as a process film when producing various resin sheets, ceramic green sheets, synthetic leather, various composite materials and the like. When used as a process film, it is used in a process of peeling from the release sheet various sheet materials formed by casting, applying, or the like, a resin, a ceramic slurry or the like on the release layer side surface of the release sheet.
  • the release sheet of the present invention is particularly preferably used for electronic equipment because the release layer is formed of a non-silicone release agent composition.
  • the release layer is formed of a non-silicone release agent composition.
  • it can be suitably used as a release sheet for pressure-sensitive adhesive sheets for temporary fixing during assembly of electronic components and component content display.
  • a release agent composition is applied on at least one surface of a substrate, heat-treated, and the polybutadiene (A) and the melamine compound (B) are crosslinked to form a crosslinked layer as a release layer. It can be manufactured by forming a body.
  • the release agent composition may be in the form of a solution diluted with a diluent solvent.
  • the heat treatment temperature is preferably 100 to 170 ° C, more preferably 130 to 160 ° C.
  • the heat treatment time is not particularly limited, but is preferably 30 seconds to 5 minutes.
  • Examples of the method for applying the release agent composition include gravure coating, bar coating, spray coating, spin coating, air knife coating, roll coating, blade coating, gate roll coating, and die coating. Can be mentioned.
  • the coating thickness of the release agent composition is adjusted so that the thickness of the obtained release layer is in the above range.
  • the physical property values in the following examples and comparative examples are values measured by the following methods.
  • the thickness of the release layer was measured using a spectroscopic ellipsometer (manufactured by JA Woollam Japan, trade name: spectroscopic ellipsometry 2000U).
  • polybutadiene (A) As the polybutadiene (A), polybutadiene (A1) (manufactured by Nippon Soda Co., Ltd., trade name: GI-2000, bromine number: 8 g / 100 g, solid content concentration: 100 mass%, number average molecular weight: 2,000) was used. .
  • Polybutadiene (A1) is a hydrogenated product of polybutadiene having hydroxyl groups only at both ends of the main chain.
  • the composition ratio of 1,4-cis form, 1,4-trans form, and 1,2-vinyl form (Cis / trans / 1,2-vinyl) is 0/15/85 in molar ratio.
  • hexamethoxymethylmelamine manufactured by Nippon Cytec Industries, product name: Cymel 303 (trade name), solid content concentration: 100% by mass
  • the acid catalyst p-toluenesulfonic acid was used.
  • a release agent composition was obtained by adding 10 parts by weight of a crosslinking agent and 2.0 parts by weight of p-toluenesulfonic acid to 90 parts by weight of polybutadiene (A1).
  • “mass part” here means the mass part in conversion of an active ingredient (solid content), and is the same meaning hereafter unless there is particular notice.
  • p-Toluenesulfonic acid was added as a solution diluted to a solid content concentration of 50 mass% using a mixed solvent of methanol and isopropyl alcohol (mass ratio 41.2: 9.4).
  • the obtained release agent composition was prepared by diluting the solid content concentration to 2.5% by mass using a mixed solvent of toluene and methyl ethyl ketone (mass ratio 6: 4). It was.
  • the coating solution of the obtained release agent composition was applied to one side of a 50 ⁇ m thick polyethylene terephthalate film (product name: Diafoil T-100, manufactured by Mitsubishi Chemical Corporation) using a Meyer bar to form a coating film did. Subsequently, the said coating film was hardened by drying at 150 degreeC for 1 minute, the 150-nm-thick peeling layer was formed, and the peeling sheet was obtained.
  • a 50 ⁇ m thick polyethylene terephthalate film product name: Diafoil T-100, manufactured by Mitsubishi Chemical Corporation
  • Example 2 A release sheet was obtained in the same manner as in Example 1 except that the blending ratio of the polybutadiene (A1) and the crosslinking agent was changed and 50 parts by mass of the crosslinking agent was added to 50 parts by mass of the polybutadiene (A1). It was.
  • Example 3 A release sheet was obtained in the same manner as in Example 1 except that the blending ratio of the polybutadiene (A1) and the crosslinking agent was changed and 90 parts by mass of the crosslinking agent was added to 10 parts by mass of the polybutadiene (A1). .
  • polybutadiene (A2) (manufactured by Nippon Soda Co., Ltd., trade name: GI-1000, bromine number: 7 g / 100 g, solid content concentration: 100 mass%, number average molecular weight: 1,500)
  • a release sheet was obtained in the same manner as in Example 1 except that it was used.
  • the polybutadiene (A2) is a hydrogenated product of polybutadiene having hydroxyl groups only at both ends of the main chain, like the polybutadiene (A1).
  • the component ratio (cis / trans / 1,2-vinyl) to the vinyl body is 0/15/85 in molar ratio.
  • the number average molecular weight and bromine number differ from polybutadiene (A1).
  • Example 5 Instead of polybutadiene (A1), polybutadiene (A3) (manufactured by Nippon Soda Co., Ltd., trade name: GI-3000, bromine number: 13 g / 100 g, solid content concentration: 100 mass%, number average molecular weight: 3,100) A release sheet was obtained in the same manner as in Example 1 except that it was used.
  • polybutadiene (A1) polybutadiene (A3) (manufactured by Nippon Soda Co., Ltd., trade name: GI-3000, bromine number: 13 g / 100 g, solid content concentration: 100 mass%, number average molecular weight: 3,100)
  • a release sheet was obtained in the same manner as in Example 1 except that it was used.
  • the polybutadiene (A3) like the polybutadienes (A1) and (A2), is a hydrogenated product of polybutadiene having hydroxyl groups only at both ends of the main chain, and includes 1,4-cis isomer, 1,4-trans isomer,
  • the composition ratio (cis / trans / 1,2-vinyl) to the 1,2-vinyl body is 0/15/85 in molar ratio.
  • the number average molecular weight and bromine number are different from those of polybutadienes (A1) and (A2).
  • Example 6> instead of polybutadiene (A1), polybutadiene (A4) (manufactured by Nippon Soda Co., Ltd., trade name: G-1000, bromine number: 400 g / 100 g, solid content concentration: 100 mass%, number average molecular weight: 1,400) A release sheet was obtained in the same manner as in Example 1 except that it was used.
  • the polybutadiene (A4) like the polybutadienes (A1) to (A3), is a polybutadiene having hydroxyl groups only at both ends of the main chain, and the 1,4-cis isomer, the 1,4-trans isomer,
  • the component ratio (cis / trans / 1,2-vinyl) to the vinyl body is 0/15/85 in molar ratio.
  • it differs from the polybutadienes (A1) to (A3) in that they are not hydrogenated. Further, the number average molecular weight and the bromine number are different.
  • Example 7 In addition to polybutadiene (A), a release sheet was obtained in the same manner as in Example 1 except that polybutadiene (A ′) different from polybutadiene (A) was blended and the blending ratio of each component was changed.
  • Polybutadiene (A) was polybutadiene (A1).
  • Polybutadiene (A ′) was polybutadiene (A4).
  • the blending ratio of each component was as follows. With respect to 45 parts by mass of polybutadiene (A1), 45 parts by mass of polybutadiene (A4), 10 parts by mass of melamine compound, and 2.0 parts by mass of p-toluenesulfonic acid were used.
  • a release sheet was obtained in the same manner as in Example 7.
  • polybutadiene (A5) (manufactured by Idemitsu Kosan Co., Ltd., trade name: Poly bd R-45HT, bromine number: 398 g / 100 g, solid content concentration: 100 mass%, number average molecular weight: 2,800 ) was used in the same manner as in Example 7 except that a release sheet was obtained.
  • polybutadiene (A4) polybutadiene (A5) is a polybutadiene having hydroxyl groups only at both ends of the main chain and is not hydrogenated.
  • composition ratio (cis / trans / 1,2-vinyl), number average molecular weight, and bromine number of 1,4-cis, 1,4-trans, and 1,2-vinyl are different.
  • the composition ratio (cis / trans / 1,2-vinyl) of the 1,4-cis isomer, 1,4-trans isomer, and 1,2-vinyl isomer of polybutadiene (A5) is 20 / 60/20.
  • polybutadiene (A6) (manufactured by Evonik, trade name: Polyvest 110, bromine number: 400 g / 100 g, solid content concentration: 100 mass%, number average molecular weight: 1,000) was used. Except for the above, a release sheet was obtained in the same manner as in Example 1.
  • Polybutadiene (A6) is a polybutadiene which has no hydroxyl group and is not hydrogenated.
  • the composition ratio (cis / trans / 1,2-vinyl) of the 1,4-cis body, 1,4-trans body, and 1,2-vinyl body of polybutadiene (A6) is a molar ratio, 75/24/1.
  • polybutadiene (A7) (manufactured by Evonik, trade name: Polybest HT, bromine number: 400 g / 100 g, solid content concentration: 100 mass%, number average molecular weight: 2,900) was used. Except for the above, a release sheet was obtained in the same manner as in Example 1.
  • the polybutadiene (A7) is a polybutadiene having hydroxyl groups only at both ends of the main chain, as in the case of the polybutadienes (A4) and (A5), and is not hydrogenated.
  • composition ratio (cis / trans / 1,2-vinyl), number average molecular weight, and bromine number of 1,4-cis, 1,4-trans, and 1,2-vinyl are different.
  • the composition ratio (cis / trans / 1,2-vinyl) of the 1,4-cis isomer, 1,4-trans isomer, and 1,2-vinyl isomer of polybutadiene (A7) is 20 / 58/22.
  • ⁇ Comparative example 4> As in Example 1, except that an isocyanate compound (manufactured by Nippon Polyurethane Co., Ltd., trade name: Coronate L, solid content concentration: 75% by mass, diluting solvent: ethyl acetate) was used as the crosslinking agent instead of the melamine compound. A release sheet was prepared by this method.
  • an isocyanate compound manufactured by Nippon Polyurethane Co., Ltd., trade name: Coronate L, solid content concentration: 75% by mass, diluting solvent: ethyl acetate
  • a 20 mm wide adhesive tape (manufactured by Nitto Denko Corporation, product number: No. 31B) was applied to the release layers of the release sheets of Examples 1 to 9 and Comparative Examples 1 to 4 using a 5 kg roller, and the release force A sample for measurement was prepared. 30 minutes after application, the obtained sample was fixed to a universal tensile tester (manufactured by Shimadzu Corporation, trade name: Autograph AGS-20NX), and in accordance with JIS K6854: 1999, the tensile speed was 0 in the 180 ° direction. The peel strength (mN / 20 mm) of the release sheet was measured by peeling the adhesive tape from the release layer at a rate of 3 m / min.
  • the measurement of the peel force on the release sheets of Examples 1 to 9 and Comparative Examples 1 to 4 was performed before and after exposure to a high temperature environment of 70 ° C. for 7 days. Then, the peel strength of the release sheet after being exposed to the high temperature environment for 7 days is defined as the peel strength after heating Y, and the peel strength of the release sheet in the state without exposure to the high temperature environment is defined as the initial peel force X.
  • a non-woven fabric impregnated with methyl ethyl ketone (trade name: Bem Cotton) impregnated with methyl ethyl ketone is placed on the release layers of the release sheets of Examples 1 to 9 and Comparative Examples 1 to 4, and 5 times with a load of 100 g from above. Wiped out.
  • the surface of the release layer was visually observed, and the case where there was no change on the surface of the release layer was evaluated as ⁇ , and the case where the surface of the release layer was whitened by scratches was evaluated as x.
  • Example having a release layer formed from a release agent composition having a crosslinkable functional group and containing a polybutadiene (A) containing 50 mol% or more of a 1,2-vinyl body on the basis of all the structural units of polybutadiene and a melamine compound It can be seen that the release sheets 1 to 9 have very little change in peel force before and after heating, and the rate of change in peel force before and after heating is within ⁇ 30%. It can also be seen that the release layers of the release sheets of Examples 1 to 9 are excellent in solvent resistance.
  • the release sheets of Examples 1 to 9 have a peel strength of 2500 mN / 20 mm or more before and after heating, and have excellent temporal stability at high temperatures even when the initial peel force is high. I understand.
  • the release sheets of Comparative Examples 1 to 3 using polybutadiene having a 1,2-vinyl content ratio of less than 50 mol% based on the total constitutional unit of polybutadiene have a very large change in peel strength before and after heating. Thus, it can be seen that the peel strength increases significantly after heating.
  • the release layer of this example has insufficient solvent resistance as compared with the release layers of the release sheets of Examples 1 to 9, and the film strength is inferior so that the evaluation of the release force becomes impossible.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Laminated Bodies (AREA)
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Citations (7)

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JPS5411943A (en) * 1977-06-30 1979-01-29 Hitachi Chem Co Ltd Back surface treatment for acrylic adhesive tapes
JP2009131977A (ja) * 2007-11-29 2009-06-18 Lintec Corp 剥離シート及び剥離シート積層体
JP2011052207A (ja) * 2009-08-07 2011-03-17 Nitto Denko Corp 剥離剤、離型材および粘着テープ
JP2011110878A (ja) * 2009-11-30 2011-06-09 Lintec Corp 剥離シート、ラベル用粘着シートおよびラベル用粘着シート積層体の製造方法
WO2012153776A1 (ja) * 2011-05-11 2012-11-15 日本曹達株式会社 離型剤組成物及びそれを用いた転写箔
JP2014054811A (ja) * 2012-09-14 2014-03-27 Unitika Ltd 離型シートおよびその製造方法
JP2018027642A (ja) * 2016-08-18 2018-02-22 東洋紡株式会社 凹凸転写フィルム

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JP2013020047A (ja) * 2011-07-11 2013-01-31 Fujifilm Corp 感光性組成物
JP2013184462A (ja) * 2012-03-12 2013-09-19 Unitika Ltd 離型シートおよびその製造方法
JPWO2013146939A1 (ja) * 2012-03-29 2015-12-14 リンテック株式会社 再剥離型エマルション系粘着剤組成物、再剥離型粘着シート、及び再剥離型粘着シートの製造方法
JP6714387B2 (ja) * 2016-02-25 2020-06-24 リンテック株式会社 剥離シート

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5411943A (en) * 1977-06-30 1979-01-29 Hitachi Chem Co Ltd Back surface treatment for acrylic adhesive tapes
JP2009131977A (ja) * 2007-11-29 2009-06-18 Lintec Corp 剥離シート及び剥離シート積層体
JP2011052207A (ja) * 2009-08-07 2011-03-17 Nitto Denko Corp 剥離剤、離型材および粘着テープ
JP2011110878A (ja) * 2009-11-30 2011-06-09 Lintec Corp 剥離シート、ラベル用粘着シートおよびラベル用粘着シート積層体の製造方法
WO2012153776A1 (ja) * 2011-05-11 2012-11-15 日本曹達株式会社 離型剤組成物及びそれを用いた転写箔
JP2014054811A (ja) * 2012-09-14 2014-03-27 Unitika Ltd 離型シートおよびその製造方法
JP2018027642A (ja) * 2016-08-18 2018-02-22 東洋紡株式会社 凹凸転写フィルム

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