JP5254698B2 - Release sheet - Google Patents

Description

  The present invention relates to a release sheet.

  Release sheets are widely used industrially. For example, adhesive sheet, adhesive material such as adhesive tape, adhesive surface protection material or process material, printed wiring board, flexible printed wiring board, multilayer printed wiring board, etc. Process materials for the production of the above, protective materials for polarizing plates and retardation plates, which are parts for liquid crystal displays, and further, molding applications of sheet-like structures.

  As a configuration of the release sheet, a release resin film is generally formed, or a release layer containing a release agent is laminated on a substrate such as a film or paper. Since the resin having releasability is generally expensive, there is a problem that what is formed into a single film as in the former becomes expensive.

  Therefore, many methods for laminating a release layer on an inexpensive substrate by extrusion lamination or coating have been proposed. However, in extrusion lamination, it is difficult to form a thin film on a substrate, and the cost reduction effect is low. There was also a problem in adhesion to the substrate.

  Lamination by coating is an effective formulation in terms of thinning the release layer, and various methods have been proposed. As a method using a solvent-based coating agent, for example, a method of laminating a vinyl group-containing polydimethylsiloxane (Patent Document 1) and a method of laminating a fluorine compound (Patent Document 2) are disclosed.

  Examples of the method using a water-based release coating agent include a method of laminating a wax (Patent Document 3), a low molecular weight silicone compound, and a fluorosurfactant as a release layer. There is a problem that the mold release agent is transferred to reduce the function of the adherend, for example, the adhesiveness.

  Therefore, through a coating process, a method of laminating a silicone resin (Patent Documents 4 and 5), a method of laminating a fluorine-containing resin (Patent Document 6), a method of laminating a polyolefin resin having a special composition (Patent Documents 7, 8) is disclosed.

JP 2002-182037 A JP 2007-002066 A Japanese Patent Publication No. 5-62897 Japanese Patent Application Laid-Open No. 07-196984 JP 2005-125656 A JP 2004-114620 A JP 2007-031639 A JP 2002-265719 A

  However, the resin layer described in Patent Document 1 has a problem of requiring treatment at a high temperature for lamination and curing. In addition, the resin described in Patent Document 2 is expensive and has a problem that it is difficult to burn in the waste incineration treatment after use and generates toxic gas. In both cases, there is a problem that a large amount of an organic solvent is used in order to uniformly coat the release agent.

  The olefin-based aqueous liquid described in Patent Document 3 that uses a water-based coating agent is a laminate of substantially low-molecular-weight olefin-based waxes and contains a surfactant, so that the adherend is contaminated. There is a risk. The resin layers described in Patent Documents 4 and 5 have a problem that the adhesiveness to the base material is poor and the releasability and the like are insufficient. Further, the method of Patent Document 6 has the same problem as that of Patent Document 2.

  In order to solve these problems, methods using the coating agents of Patent Documents 7 and 8 have been proposed. However, Patent Document 7 does not actually evaluate as a release sheet. Moreover, since the surfactant is contained in the coating agent, the adherend may be contaminated. On the other hand, since the resin used in Patent Document 8 is expensive and has a high melting point, a high-temperature treatment is required to obtain a release sheet.

  In view of these problems, the present invention is intended to provide a release sheet that is easy to manufacture, has no migration of the release layer to the adherend, and has a low environmental impact during disposal.

  As a result of intensive studies to solve the above problems, the present inventors have found that a polyolefin resin having a specific composition is excellent in releasability and is effective as a release sheet by being laminated on a substrate. The invention has been reached.

That is, the gist of the present invention is a release sheet in which a resin layer is provided on a substrate, and the resin layer has 85 to 99 mass% of an olefin component having 2 to 4 carbon atoms and 1 to 15 mass of an acid component. % Of the acid-modified polyolefin resin and a crosslinking agent, and the crosslinking agent includes a carbodiimide compound, an oxazoline group-containing compound, an isocyanate compound, a melamine compound, a urea compound, an epoxy compound, an aziridine compound, a zirconium salt compound, and a silane cup. A release sheet comprising any one or more of ring agents .

  The release sheet of the present invention has good release properties while having wettability. In addition, in order to develop releasability, release agents such as waxes, low molecular weight silicone compounds, and surfactants are not required. For this reason, the adherend is not contaminated during peeling. In addition, since it is not necessary to use a release agent containing a halogen element such as fluorine, the burden on the environment at the time of disposal is small. Furthermore, when using antistatic treated substrates, it is possible to reduce the generation of static electricity when the adherend and the release sheet are peeled off, so the quality of the product deteriorates due to the adsorption of dust and dirt in the atmosphere. And a decrease in adhesive strength can be suppressed.

  The release sheet of the present invention is used for protective materials such as adhesive materials and liquid crystal display parts, process materials for manufacturing printed wiring boards, and sheet-like structure forming applications such as ion exchange membranes and ceramic green sheets. Is preferred.

  According to the method for producing a release sheet of the present invention, the release sheet of the present invention can be easily obtained industrially.

  The present invention will be described in detail below.

  The release sheet of the present invention is formed by providing a resin layer on a substrate.

  The polyolefin resin having a specific composition used as the resin layer needs to be an acid-modified polyolefin resin composed of 85 to 99% by mass of an olefin component having 2 to 4 carbon atoms and 1 to 15% by mass of an acid component. When other components are copolymerized, the releasability may decrease.

  Examples of the acid component contained in the acid-modified polyolefin resin include an unsaturated carboxylic acid component. Examples of unsaturated carboxylic acid components include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, and the like, as well as unsaturated dicarboxylic acid half esters and half amides. It is done. Among these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable from the viewpoint of stabilizing the dispersion of the resin, and acrylic acid, methacrylic acid, and maleic anhydride are particularly preferable. Two or more of these acid components may be contained in the polyolefin resin. The unsaturated carboxylic acid component only needs to be copolymerized in the acid-modified polyolefin resin, and the form thereof is not limited. Examples of the copolymerization state include random copolymerization, block copolymerization, and graft copolymerization. (Graft modification) and the like.

  The acid component needs to be 1 to 15% by mass of the acid-modified polyolefin resin, preferably 1 to 12% by mass, more preferably 2 to 10% by mass, and particularly preferably 2 to 9% by mass. When the amount of the acid component is less than 1% by mass, sufficient adhesion to the substrate may not be obtained, and it becomes difficult to obtain a solution or an aqueous dispersion. On the other hand, when it exceeds 15 mass%, mold release property may fall.

  It is essential that the olefin component is composed of an ethylene hydrocarbon having 2 to 4 carbon atoms. In the present invention, the ethylene-based hydrocarbon having 2 to 4 carbon atoms means ethylene, propylene or butene, and specifically is an alkene having 2 to 4 carbon atoms such as ethylene, propylene, isobutylene and 1-butene. Ethylene or propylene is preferable, and ethylene is most preferable from the viewpoint of productivity. When the carbon number exceeds 4, the productivity is poor and the cost becomes high. In addition, the adhesion with the resin substrate may be reduced.

  The olefin component needs to be 85 to 99% by mass of the acid-modified polyolefin resin, preferably 88 to 99% by mass, more preferably 90 to 98% by mass, and particularly preferably 91 to 98% by mass. When the olefin component exceeds 99% by mass, sufficient adhesion to the substrate may not be obtained, and it becomes difficult to obtain an aqueous dispersion. On the other hand, if it is less than 85% by mass, the releasability may decrease.

  The melting point of the acid-modified polyolefin resin is preferably 90 to 150 ° C, more preferably 95 to 130 ° C. When the temperature exceeds 150 ° C., a treatment at a high temperature may be required for forming the resin layer. When the temperature is lower than 90 ° C., the releasability is lowered.

  The Vicat softening point of the acid-modified polyolefin resin is preferably 50 to 130 ° C, more preferably 53 to 110 ° C, and more preferably 55 to 90 ° C. When the Vicat softening point is less than 50 ° C., the releasability is lowered, and when it exceeds 130 ° C., a treatment at a high temperature is required for forming the resin layer.

  The melt flow rate of the acid-modified polyolefin resin is preferably 1 to 1000 g / 10 minutes at 190 ° C. and 2160 g load, more preferably 1 to 500 g / 10 minutes, and 1 to 100 g / 10 minutes. Is more preferable. In particular, when the acid component is 10% by mass or more, it is preferably less than 1 to 30 g / 10 minutes. If it is less than 1 g / 10 min, it is difficult to produce a resin, and it becomes difficult to make an aqueous dispersion, which will be described later. Transition to the body is likely to occur.

  Examples of commercially available acid-modified polyolefin resins that can be used in the present invention include Lexpearl EAA “A210K” and “ET530H” manufactured by Nippon Polyethylene Co., Ltd., Nucleel “AN42115C”, “N1108C”, and “N0903H” manufactured by Mitsui DuPont Polychemical Co., Ltd. , “N1050H”, “N1110H”, and the like.

  The resin layer of the release sheet of the present invention preferably contains a cross-linking agent or polyvinyl alcohol in order to improve releasability from the adherend. Examples of the crosslinking agent include carbodiimide compounds, oxazoline group-containing compounds, isocyanate compounds, melamine compounds, urea compounds, epoxy compounds, aziridine compounds, zirconium salt compounds, silane coupling agents, and the like. It is effective and preferable, and an oxazoline group-containing compound is particularly preferable. The content is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, and still more preferably 5 to 10 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin. If it is less than 1 part by mass, the effect of addition is poor, and if it exceeds 30 parts by mass, the releasability may decrease.

  As a commercially available crosslinking agent, Nippon Shokubai Epochros series is mentioned as an oxazoline compound. Product names include water-soluble types “WS-500”, “WS-700”; emulsion types “K-1010E”, “K-1020E”, “K-1030E”, {K-2010E}, “K -2020E "," K-2030E "and the like. Examples of carbodiimide compounds include Nisshinbo Carbodilite series. The trade names include water-soluble type “SV-02”, “V-02”, “V-02-L2”, “V-04”; emulsion type “E-01”, “E-02”; Organic solution type “V-01”, “V-03”, “V-07”, “V-09”; solventless type “V-05” may be mentioned. Examples of the isocyanate compound include Elastron series manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and examples of the trade name include “E-37”, “H-3”, and “H-38”.

  The polyvinyl alcohol is not particularly limited, and examples thereof include a completely or partially saponified polymer of vinyl ester. As the saponification method, a known alkali saponification method or acid saponification method can be used, and among them, a method of alcoholysis using an alkali hydroxide in methanol is preferable. As will be described later, it is preferable to have water solubility for use as a liquid material. Examples of the vinyl ester include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate, etc. Among them, vinyl acetate is industrially most preferable. It is also possible to copolymerize other vinyl compounds with the vinyl ester as long as the effects of the present invention are not impaired. Other vinyl monomers include unsaturated monocarboxylic acids such as crotonic acid, acrylic acid, and methacrylic acid and their esters, salts, anhydrides, amides, nitriles, and unsaturated acids such as maleic acid, itaconic acid, and fumaric acid. Examples thereof include dicarboxylic acids and salts thereof, α-olefins having 2 to 30 carbon atoms, alkyl vinyl ethers, vinyl pyrrolidones and the like.

  The average degree of polymerization of polyvinyl alcohol is not particularly limited, but is preferably 300 to 2,000.

  5-50 mass parts is preferable with respect to 100 mass parts of acid-modified polyolefin resin, and, as for content of polyvinyl alcohol, 10-45 mass parts is more preferable. If the amount is less than 5 parts by mass, the effect of addition is poor, and if the amount exceeds 50 parts by mass, the improvement of the effect of addition is poor.

  As a commercially available polyvinyl alcohol, specific product names of J-Poval manufactured by Nippon Vinegar Poval Co., Ltd. “JC-05”, “VC-10”, “ASC-05X”, “UMR-10HH”; manufactured by Kuraray Co., Ltd. Specific product names “PVA-103” and “PVA-105” of Kuraray Poval, specific product names “AQ4104” and “HR3010” of Exebar; specific product name “PC-1000” of Denka Poval manufactured by Denki Kagaku Kogyo Co., Ltd. And “PC-2000”.

  You may mix and use a crosslinking agent and polyvinyl alcohol, In that case, the addition amount of the crosslinking agent with respect to acid-modified polyolefin resin and polyvinyl alcohol is a range with which each satisfy | fills the relationship with the acid-modified polyolefin resin mentioned above. I just need it.

  In the resin layer of the release sheet, the total content of the silicon compound, the fluorine compound, the waxes, and the surfactant is preferably 1 part by mass or less with respect to 100 parts by mass of the acid-modified polyolefin resin. The smaller the amount, the better the adhesion between the resin layer and the substrate, and the contamination of the adherend is suppressed. Therefore, the amount is preferably 0.5 parts by mass or less, and 0.1 parts by mass or less. Is more preferable, and it is particularly preferable that it does not contain.

  The wax means a plant wax, animal wax, mineral wax, petrochemical wax or the like having a number average molecular weight of 10,000 or less. Specifically, candelilla wax, carnauba wax, rice wax, wood wax, berry wax, jojoba wax, shea butter, beeswax, shellac wax, lanolin wax, whale wax, montan wax, ceresin, paraffin wax, microcrystalline wax, synthetic Examples thereof include polyethylene wax, synthetic polypropylene wax, and synthetic ethylene-vinyl acetate copolymer wax.

  Surfactants include cationic surfactants, anionic surfactants, nonionic (nonionic) surfactants, amphoteric surfactants, fluorosurfactants, and reactive surfactants. In addition to those used for emulsion polymerization, emulsifiers are also included. For example, anionic surfactants include sulfates of higher alcohols, higher alkyl sulfonic acids and salts thereof, alkyl benzene sulfonic acids and salts thereof, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyl sulfone salts. Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, ethylene oxide propylene oxide block copolymer, polyoxyethylene fatty acid amide, ethylene oxide. -Compounds having a polyoxyethylene structure such as propylene oxide copolymer and sorbitans such as polyoxyethylene sorbitan fatty acid ester It includes conductors, and examples of the amphoteric surfactant, lauryl betaine, lauryl dimethyl amine oxide, and the like. Examples of reactive surfactants include alkylpropenylphenol polyethylene oxide adducts and their sulfate esters, allyl alkylphenol polyethylene oxide adducts and their sulfate esters, allyl dialkylphenol polyethylene oxide adducts and their sulfate esters, etc. Examples thereof include compounds having a reactive double bond.

  Examples of the base material for the release sheet include resin materials, paper, synthetic paper, cloth, metal materials, and glass materials. Although the thickness of a base material is not specifically limited, Usually, what is necessary is just 1-1000 micrometers, 1-500 micrometers is preferable, 1-100 micrometers is more preferable, and 1-50 micrometers is especially preferable.

  Examples of paper that can be used for the substrate include Japanese paper, craft paper, liner paper, art paper, coated paper, carton paper, glassine paper, semi-glassine paper, and the like.

  The structure of the synthetic paper that can be used for the substrate is not particularly limited, and may be a single layer structure or a multilayer structure. As a multilayer structure, for example, a two-layer structure of a base material layer and a surface layer, a three-layer structure in which a surface layer exists on the front and back surfaces of the base material layer, and another resin film layer exists between the base material layer and the surface layer. A multilayer structure can be exemplified. Moreover, each layer may contain the inorganic or organic filler, and does not need to contain it. A microporous synthetic paper having a large number of fine voids can also be used.

  Examples of resin materials that can be used for the base material include thermoplastic resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyester resins such as polylactic acid (PLA), polyolefin resins such as polypropylene, polystyrene resins, Polyamide resins such as 6-nylon and poly-m-xylylene adipamide (MXD6 nylon), polycarbonate resin, polyacrylonitrile resin, polyimide resin, and multilayers of these resins (for example, nylon 6 / MXD6 / nylon 6) , Nylon 6 / ethylene-vinyl alcohol copolymer / nylon 6) and mixtures. The resin material may be stretched. In addition, the resin material may contain known additives and stabilizers such as antistatic agents, plasticizers, lubricants, antioxidants, etc., in order to improve the adhesion when laminating with other materials, The surface may be subjected to corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment, etc. as pretreatment. Moreover, silica, alumina, etc. may be vapor-deposited, and other layers, such as a barrier layer, an easily bonding layer, an antistatic layer, an ultraviolet absorption layer, and an adhesive layer, may be laminated.

  Examples of the cloth that can be used for the substrate include fibers made of the above-described synthetic resins, nonwoven fabrics made of natural fibers such as cotton, silk, and hemp, woven cloth, and knitted cloth.

  Examples of the metal material that can be used for the base material include metal foil such as aluminum foil and copper foil, and metal plate such as aluminum plate and copper plate. Examples of the glass material include cloth made of glass plate and glass fiber. Is mentioned.

  In the base material using the resin material, paper, synthetic paper, cloth, other resin material, metal material, or the like may be further laminated on the side opposite to the resin layer of the base material.

  The base material can be subjected to an antistatic treatment. It can be applied to any material such as paper, synthetic paper, cloth, and glass material. However, when using a resin material for the base material, it is likely to be damaged by charging, so it must be antistatic treated. Is preferred. When used as a process film, by using a base material that has been antistatic treated, generation of static electricity due to frictional charging or peeling charging is suppressed in the peeling process, and the product absorbs dust, dust, dust, etc. in the atmosphere. It is possible to prevent the quality from being deteriorated. Moreover, even when used as a protective material for an adhesive, it is possible to suppress the adhesion of dust and dirt to the adhesive surface due to static electricity generated by peeling electrification, and to prevent a decrease in adhesive force.

When an antistatic treatment is applied to the substrate, the surface specific resistance value is desirably 10 ¹⁰ Ω / □ or less. If the surface resistivity is greater than 10 ¹⁰ Ω / □, the antistatic property is not sufficient, and it is easy to be charged with static electricity. There is a possibility that the adhesive strength of will be reduced.

  Methods for obtaining an antistatic treated substrate include a method of kneading an antistatic material into a resin constituting the substrate, a method of laminating a layer containing an antistatic material on the substrate, and an antistatic material. The method of laminating the layers is preferable because the antistatic treatment can be performed at a lower cost. When the antistatic layer is laminated, it may be laminated between the substrate and the resin layer, either on the opposite side of the substrate from the resin layer, or may be laminated on both surfaces of the substrate. When an antistatic layer is laminated between the substrate and the resin layer, it is effective to prevent adhesion of dust and dirt in the atmosphere when the release sheet is peeled off from the adherend. When an antistatic layer is laminated on the opposite side of the layer, it is effective for preventing adhesion of dust and dirt in the atmosphere when used as a transport / process film with a release sheet laminated on the adherend. is there. From the viewpoint of preventing contamination of the adherend after peeling, it is more preferable that an antistatic layer is laminated between the substrate and the resin layer.

  In the case of laminating a layer containing an antistatic material, a thickness of 0.01 to 100 μm is preferable, since a uniform film that is sufficiently antistatic, strong, and hardly scratched is obtained. The range of 20 μm is more preferable, and the range of 0.1 to 5 μm is particularly preferable.

  Antistatic materials that can be used for antistatic treatment include conductive polymers such as polyaniline, polypyrrole, and thiophene, conductive carbon such as carbon black and ketjen black, tin oxide, antimony-doped tin oxide, and tin oxide doped Examples include tin oxide ultrafine particles such as indium. By kneading these antistatic materials into a resin material or the like as a composition mixed with a single substance or a binder resin, or by coating the surface of a substrate as a liquid material of a composition mixed with a single substance or a binder resin. , Antistatic treatment can be performed. Among these, the use of tin oxide-based ultrafine particles is preferable in that it is excellent in transparency, and therefore it becomes easy to grasp foreign matters in the inspection process.

  As the antistatic material, commercially available materials can be used. For example, as the polypyrrole dispersion, PPY-12 manufactured by Maruhishi Oil Chemical Co., Ltd. is used, and as the conductive carbon dispersion, W manufactured by Lion Corporation is used. -310A and the like. EPS-6 manufactured by Yamanaka Chemical Co., Ltd., AS11T, AS20I manufactured by Unitika Co., Ltd., and SN100D manufactured by Ishihara Sangyo Co., Ltd. as an antimony-doped tin oxide ultrafine particle aqueous dispersion are used as tin oxide ultrafine particle aqueous dispersion. There is ITO manufactured by CI Kasei.

  The binder resin to be mixed with the antistatic material includes polyester resin, polyolefin resin, polyamide resin, polyvinyl alcohol resin, polyvinyl acetate, urethane resin, polyvinyl chloride resin, polyvinylidene chloride resin, ethylene- (meth) acrylic acid copolymer Examples include coalescence, styrene-maleic acid resin, styrene-butadiene resin, butenedien resin, poly (meth) acrylonitrile resin, (meth) acrylamide resin, chlorinated polyethylene resin, chlorinated polypropylene resin, etc., depending on the substrate used It can select suitably and may mix and use 2 or more types.

  The thickness of the resin layer in the release sheet is preferably in the range of 0.01 to 5 μm, more preferably 0.1 to 2 μm, still more preferably 0.2 to 1 μm, and A thickness of 3 to 0.7 μm is particularly preferable. If the thickness is less than 0.01 μm, sufficient releasability cannot be obtained, and if it exceeds 5 μm, the releasability may not only be lowered but also the cost may be increased. In particular, when a resin layer is laminated on a base material that has been subjected to antistatic treatment, if the thickness of the resin layer exceeds 5 μm, sufficient antistatic properties cannot be obtained, and the surface is charged with dust in the atmosphere during the peeling process. If dust or dirt adheres to the product, it may cause a product defect and a decrease in adhesive strength.

  The wetting tension on the surface of the resin layer is preferably 30 mN / m or more, and more preferably 32 mN / m or more. If the wetting tension is less than 30 mN / m, it may be difficult to laminate another coating agent or liquid on the resin layer. The wetting tension means a critical surface tension by Zisman and can be measured by the method described in JIS K6768.

  By using the release sheet of the present invention, the peel strength between the resin layer and the adhesive material after thermocompression bonding is 10 N / 50 mm or less, preferably 8 N / 50 mm or less, more preferably 7 N / 50 mm or less. be able to. If the peel strength exceeds 10 N / 50 mm, it is difficult to use as a release sheet.

  The release sheet of the present invention can be easily obtained industrially by a production method in which a liquid containing an acid-modified polyolefin resin is coated on a substrate and then dried.

  In the production method of the present invention, the solvent in the liquid material containing the acid-modified polyolefin resin is not particularly limited as long as it can be applied on the substrate, and water, an organic solvent, or water and an amphiphilic organic solvent. In view of the environment, it is preferable to use water or an aqueous medium.

  Examples of organic solvents include diethyl ketone (3-pentanone), methyl propyl ketone (2-pentanone), methyl isobutyl ketone (4-methyl-2-pentanone), 2-hexanone, 5-methyl-2-hexanone, and 2-to. Ketones such as butanone, 3-heptanone, 4-heptanone, cyclopentanone, cyclohexanone, aromatic hydrocarbons such as toluene, xylene, benzene, Solvesso 100, Solvesso 150, butane, pentane, hexane, cyclohexane, heptane Aliphatic hydrocarbons such as octane and nonane, methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, Halogen-containing compounds such as p-dichlorobenzene, acetic acid Esters such as chill, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, methyl propionate, ethyl propionate, diethyl carbonate, γ-butyrolactone, isophorone, etc. Examples include hydrophilic organic solvents described below.

  The aqueous medium in the present invention means a solvent composed of water and an amphiphilic organic solvent and having a water content of 2% by mass or more. The amphiphilic organic solvent is an organic solvent having a water solubility of 5% by mass or more at 20 ° C. [For the solubility of water in an organic solvent at 20 ° C., for example, “Solvent Handbook” (Kodansha) Scientific, 1990, 10th edition)]. Specifically, alcohols such as methanol, ethanol (hereinafter abbreviated as “EA”), n-propanol (hereinafter abbreviated as “NPA”), isopropanol (hereinafter abbreviated as “IPA”), tetrahydrofuran, Diethylamine containing ethers such as 4-dioxane, ketones such as acetone and methyl ethyl ketone, esters such as methyl acetate, n-propyl acetate, isopropyl acetate, methyl propionate, ethyl propionate, dimethyl carbonate, and others Organic amines such as triethylamine (hereinafter abbreviated as “TEA”), diethanolamine, triethanolamine, N, N-dimethylethanolamine (hereinafter abbreviated as “DMEA”), N, N-diethylethanolamine, N-diethanolamine, etc. Compound, 2-pyro Don, and the like lactams such as N- methyl-2-pyrrolidone.

  The method for dispersing the acid-modified polyolefin resin in the aqueous medium as described above is not particularly limited, and examples thereof include those described in International Publication No. 02/055598, International Publication No. 2004/104090, and the like.

  The dispersed particle size of the acid-modified polyolefin resin in the aqueous medium preferably has a number average particle size of 1 μm or less from the viewpoint of stability when mixed with other components and storage stability after mixing. More preferably, it is 8 μm or less. Such a particle size can be achieved by the production method described in the pamphlet.

  Various additives can be added at any stage of liquefaction.

  The solid content of the liquid material used in the present invention can be appropriately selected depending on the lamination conditions, the target thickness and performance, and is not particularly limited. In order to form a resin layer, 1-60 mass% is preferable and 5-30 mass% is more preferable.

  As a method of coating a liquid material on a substrate, known methods such as gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, brush coating method After coating uniformly on the surface of the substrate, etc., setting it near room temperature as necessary, and then subjecting it to drying treatment or heat treatment for drying, a uniform resin layer is formed in close contact with the substrate be able to.

  Since the release sheet of the present invention has a good releasability for various adherends, a laminate can be obtained by laminating the adherend via a resin layer. . Specifically, it can be suitably used as a protective material such as an adhesive material or a liquid crystal display component, a press process material for a printed wiring board, or a molding process material for a sheet-like structure.

  Examples of the adhesive material include an adhesive sheet, an adhesive sheet, an adhesive tape, and an adhesive tape. More specifically, an adhesive is laminated on a base material. The components and base material of the pressure-sensitive adhesive are not particularly limited, but examples of the pressure-sensitive adhesive include acrylic pressure-sensitive adhesives, natural rubber-based pressure-sensitive adhesives, and synthetic rubber-based pressure-sensitive adhesives. Here, rosin-based, coumarone-indene-based, A terpene, petroleum, styrene, phenol or xylene tackifier may be included. Examples of the substrate include the above-described paper, cloth, and resin material.

  Examples of the printed wiring board include a single-sided printed wiring board, a double-sided printed wiring board, a flexible printed wiring board, and a multilayer printed wiring board.

  Examples of the liquid crystal display component include a polarizing plate, a retardation polarizing plate, and a retardation plate.

  Examples of the sheet-like structure include an ion exchange membrane made of a polymer electrolyte such as perfluorosulfonic acid resin, and a ceramic green sheet made of dielectric ceramics or glass. These are formed by casting a raw material in a paste or slurry form with a solvent onto a release sheet.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

(1) Configuration of acid-modified polyolefin resin
^It calculated | required from <1> H-NMR analysis (GEMINI2000 / 300, 300MHz by a Varian company). Orthodichlorobenzene (d ₄ ) was used as a solvent, and measurement was performed at 120 ° C.
(2) Melting point of acid-modified polyolefin resin 10 mg of resin was used as a sample, and measurement was performed using a DSC (Differential Scanning Calorimetry) apparatus (DSC7, manufactured by PerkinElmer Co., Ltd.) under a temperature rising rate of 10 ° C./min. The melting point was determined from the temperature rise curve.
(3) Vicat softening point of acid-modified polyolefin resin Measured by the method described in JIS K7206.
(4) Melt flow rate (MFR) of acid-modified polyolefin resin
It was measured by the method described in JIS K7210 (190 ° C., 2160 g load).

(5) Organic solvent content of aqueous dispersion Shimadzu Corporation gas chromatograph GC-8A [FID detector used, carrier gas: nitrogen, column packing material (manufactured by GL Sciences): PEG-HT (5%) − Uniport HP (60/80 mesh), column size: diameter 3 mm × 3 m, sample charging temperature (injection temperature): 150 ° C., column temperature: 60 ° C., internal standard substance: n-butanol] A dispersion diluted with water was directly charged into the apparatus, and the content of the organic solvent was determined. The detection limit was 0.01% by mass.
(6) Solid Concentration of Liquid Material An appropriate amount of the liquid material was weighed and heated at 150 ° C. until the mass of the residue (solid content) reached a constant weight to determine the solid content concentration.
(7) Number average particle diameter of acid-modified polyolefin resin particles The number average particle diameter was determined using a Microtrac particle size distribution analyzer UPA150 (MODEL No. 9340, dynamic light scattering method) manufactured by Nikkiso Co., Ltd. The refractive index of the resin used for particle diameter calculation was 1.50.

(8) Thickness of resin layer From a total thickness of a film (hereinafter referred to as a release film) in which a liquid material is coated on a base film by a contact-type film thickness meter and dried to laminate a resin layer, the base film Obtained by reducing the thickness.
(9) Wetting tension of resin layer surface According to the measurement method described in JIS K6768, a standard solution (ethylene glycol monoethyl ether / formamide) adjusted so that the surface tension is changed sequentially is applied to the treated surface, and the resin layer surface is coated. The surface tension of the standard solution judged to be wet was shown.

(10) Peel strength A 50 mm wide and 150 mm long polyester pressure-sensitive adhesive tape (Nitto Denko No. 31B / acrylic pressure-sensitive adhesive) is pressure-bonded to a resin layer side of the obtained release film with a rubber roll to obtain a sample. A sample is sandwiched in the form of a metal plate / rubber plate / sample / rubber plate / metal plate, left in a 2 kPa load, 70 ° C. atmosphere for 20 hours, then cooled to room temperature for 30 minutes or longer, and a sample for peel strength measurement Got. The peel strength between the adhesive tape and the release film of the peel strength measurement sample was measured with a tensile tester (precision universal material tester 2020 manufactured by Intesco) in a constant temperature room at 25 ° C. The peeling angle is 180 degrees and the peeling speed is 300 mm / min. (11) Retackiness Polyester pressure-sensitive adhesive tape (Nitto Denko No. 31B / acrylic pressure-sensitive adhesive) having a width of 50 mm peeled from the surface of the release film by the above-described peel strength test was applied to a biaxially stretched polyester resin film (Unitika Ltd.). It was affixed to a corona-treated surface of “Embret PET-12” (thickness: 12 μm) and left at room temperature for 20 hours under a load of 2 kPa. Thereafter, the peel strength between the polyester adhesive tape and the film was measured with a tensile tester (precision universal material tester type 2020 manufactured by Intesco) in a thermostatic chamber at 25 ° C. The peeling angle is 180 degrees and the peeling speed is 300 mm / min. When the pressure-sensitive adhesive surface of the pressure-sensitive adhesive tape is contaminated by the release film, the re-adhesiveness of the pressure-sensitive adhesive tape is lowered and the performance as the pressure-sensitive adhesive tape is impaired. That is, it is preferable that the re-adhesion strength is higher.

(12) Antistatic property of resin layer Based on JIS-K6911, the surface resistance value of the resin layer was measured at 23 ° C. and 65% humidity using a digital ultra-high resistance / microammeter, R8340 manufactured by Advantest Corporation. Measured below.

Reference example 1
[Production of acid-modified polyolefin resin aqueous dispersion E-1]
30.0 g of Lexpearl EAA “A210K” (manufactured by Nippon Polyethylene Co., Ltd., acrylic acid-modified polyethylene resin), 105.0 g of NPA (sum) Kogaku Pharmaceutical Co., Ltd.), 7.8 g of TEA (Wako Pure Chemical Industries, Ltd.), and 157.2 g of distilled water were charged into a glass container, and the rotation speed of the stirring blade was 300 rpm. The system temperature was kept at 170 ° C. and stirred for 30 minutes. After cooling to room temperature (about 25 ° C.) while stirring at a rotational speed of 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300-mesh stainless steel filter (wire diameter 0.035 mm, plain weave) is used to produce a slightly cloudy aqueous solution. Dispersion E-1 was obtained. At this time, almost no resin remained on the filter.

Reference example 2
[Production of acid-modified polyolefin resin aqueous dispersion E-2]
As an acid-modified polyolefin resin, Nuclel “AN42115C” (Mitsui / DuPont Polychemical Co., Ltd., methacrylic acid-modified polyethylene resin), NPA (Wako Pure Chemical Industries, Ltd.) 105.0 g, DEA (Wako Pure Chemical Industries, Ltd.) 9.0 g, distilled The same operation as in the production of the aqueous dispersion E-1 was performed using 156.0 g of water to obtain an acid-modified polyolefin resin aqueous dispersion E-2.

Reference example 3
[Production of acid-modified polyolefin resin aqueous dispersion E-3]
Nucleel “N1108C” (Mitsui / DuPont Polychemical Co., Ltd., methacrylic acid modified polyethylene resin), NPA (Wako Pure Chemical Industries) 105.0 g, TEA (Wako Pure Chemical Industries, Ltd.) 9.0 g, distilled The same operation as in the production of the aqueous dispersion E-1 was performed using 156.0 g of water to obtain an acid-modified polyolefin resin aqueous dispersion E-3.

Reference example 4
[Production of acid-modified polyolefin resin aqueous dispersion E-4]
Using a stirrer equipped with a hermetic pressure-resistant 1 liter glass container with a heater, 60.0 g bondine “HX-8290” (manufactured by Arkema, maleic anhydride-modified polyolefin resin), 90.0 g IAP (Japanese Kogyo Pharmaceutical Co., Ltd.), 3.0 g of TEA (Wako Pure Chemical Industries, Ltd.) and 147.0 g of distilled water were charged into a glass container, and the rotation speed of the stirring blade was 300 rpm. Then, the system temperature was kept at 140 to 145 ° C. and further stirred for 30 minutes. Then, after putting in a water bath and cooling to room temperature (about 25 ° C.) while stirring at a rotational speed of 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) As a result, a milky white uniform acid-modified polyolefin resin aqueous dispersion E-4 was obtained.

Reference Example 5
[Production of acid-modified polyolefin resin aqueous dispersion E-5]
Using a stirrer equipped with a hermetic pressure-resistant 1 liter glass container with a heater, 60.0 g Primacol 5980I (manufactured by Dow Chemical Co., acrylic acid-modified polyethylene resin), 16.8 g TEA, and 223.2 g Of distilled water was charged into a glass container and stirred at a rotation speed of 300 rpm. The system temperature was maintained at 140 to 145 ° C. and stirred for 30 minutes. Then, after putting in a water bath and cooling to room temperature (about 25 ° C.) while stirring at a rotational speed of 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) As a result, a slightly cloudy aqueous dispersion E-5 was obtained. At this time, almost no resin remained on the filter.

Reference Example 6
[Production of acid-modified polyolefin resin solution E-6]
Using a stirrer equipped with a hermetically sealed 1 liter glass container equipped with a heater, 10.0 g of Nucrel "AN42115C" (Mitsui / DuPont Polychemical Co., Ltd., methacrylic acid-modified polyethylene resin), toluene (Wako Pure Chemical Industries, Ltd.) 90.0 g was prepared in a glass container, and the rotation speed of the stirring blade was 300 rpm. The system temperature was kept at 150 ° C. and stirred for 60 minutes. While stirring at a rotation speed of 300 rpm, the mixture was cooled to about 50 ° C. to obtain a colorless and transparent solution E-6.

  The composition of the acid-modified polyolefin resin used for the production of the aqueous dispersions E-1 to E-6 is shown in Table 1, and the composition of the aqueous dispersion is shown in Table 2.

Reference Example 7
[Production of Aqueous Dispersion E-7]
A transparent aqueous dispersion is obtained by adding isopropyl alcohol to a tin oxide ultrafine particle dispersion (AS11T solid content concentration: 11.5% by mass, manufactured by Unitika Ltd.) to 20% by mass of the obtained aqueous dispersion and stirring. Got the body. To this, an aqueous polyester resin dispersion (manufactured by Unitika Co., Ltd., Elitel KZA-3556, solid content concentration: 30% by mass) so that tin oxide ultrafine particles are 800 parts by mass with respect to 100 parts by mass of the polyester resin solid content. By adding and stirring, an aqueous dispersion E-7 containing a polyester resin and tin oxide ultrafine particles was obtained. The solid content concentration was 10.0% by mass.

Reference Example 8
[Production of Aqueous Dispersion E-8]
In Reference Example 7, in place of the tin oxide ultrafine particle dispersion AS11T, an antimony-doped tin oxide ultrafine particle aqueous dispersion (manufactured by Ishihara Sangyo Co., Ltd., SN100D solid content concentration: 30.0% by mass) was used. Operation was performed to obtain an aqueous dispersion E-8.

Reference Example 9
[Aqueous dispersion E-9]
In Reference Example 7, the same operation was performed except that a polypyrrole dispersion (PPY-12 solid content concentration: 8.0% by mass manufactured by Maruhishi Oil Chemical Co., Ltd.) was used instead of the tin oxide ultrafine particle dispersion AS11T. Thus, an aqueous dispersion E-9 was obtained.

Reference Example 10
[Aqueous Dispersion E-10]
In Reference Example 7, aqueous dispersion was carried out in the same manner except that a conductive carbon dispersion liquid (WS310A solid content concentration: 17.5 mass%) manufactured by Lion Corporation was used instead of the tin oxide ultrafine particle dispersion AS11T. Body E-10 was obtained.

Reference Example 11
[Production of Polyester Resin Film F-1 Laminated with Antistatic Layer]
The aqueous dispersion E-7 was coated on a corona-treated surface of a biaxially stretched polyester resin film (“Embret PET-12” manufactured by Unitika Ltd., thickness 12 μm) using a Mayer bar, and then dried at 120 ° C. for 30 seconds. Thus, a polyester resin film F-1 on which an antistatic layer having a thickness of 0.3 μm was laminated was obtained.

Reference Example 12
[Production of Polyester Resin Film F-2 Laminated with Antistatic Layer]
In Reference Example 11, a polyester film F-2 in which an antistatic layer having a thickness of 0.3 μm was laminated by performing the same operation except that the aqueous dispersion E-8 was used instead of the aqueous dispersion E-7. Got.

Reference Example 13
[Production of Polyester Resin Film F-3 Laminated with Antistatic Layer]
In Reference Example 11, a polyester film F-3 obtained by laminating an antistatic layer having a thickness of 0.3 μm by performing the same operation except that the aqueous dispersion E-9 was used instead of the aqueous dispersion E-7. Got.

Reference Example 14
[Production of Polyester Resin Film F-4 Laminated with Antistatic Layer]
In Reference Example 11, a polyester film F-4 obtained by laminating an antistatic layer having a thickness of 0.3 μm by performing the same operation except that the aqueous dispersion E-10 was used instead of the aqueous dispersion E-7. Got.

  In Reference Examples 11 to 14, Table 3 shows polyester resin films obtained by laminating the obtained antistatic layers.

Production Example 1
After coating the acid-modified polyolefin resin aqueous dispersion E-1 on a corona-treated surface of a biaxially stretched polyester resin film (“Embret PET-12” manufactured by Unitika Ltd., thickness 12 μm) using a Mayer bar, at 150 ° C. A release film was obtained by drying for 90 seconds and laminating a 0.6 μm resin layer on the film.

Production Examples 2 to 4
In Production Example 1, a release film was obtained by performing the same operation as in Production Example 1 except that E-2, E-3, and E-6 were used instead of the acid-modified polyolefin resin aqueous dispersion E-1. It was. In addition, the solution of E-6 was applied while maintaining the liquid temperature at 50 ° C.

Example 1
With respect to the acid-modified polyolefin resin aqueous dispersion E-3, an aqueous solution of an oxazoline group-containing compound (manufactured by Nippon Shokubai Co., Ltd., Epocros “WS-500”, solid content concentration: 40% by mass) is added to 100 parts by mass of the acid-modified polyolefin resin. A release film was obtained by performing the same operation as in Production Example 3 except that a liquid substance added so that the oxazoline group-containing compound was 5 parts by mass was used.

Production Example 5
In Production Example 1, 30 parts by mass of polyvinyl alcohol (“VC-10”, manufactured by Nihon Acetate / Poval) with respect to 100 parts by mass of the resin solid content of the acid-modified polyolefin resin aqueous dispersion E-1 000) was added as a 10% by mass aqueous solution to obtain a release film in the same manner as in Production Example 1.

Production Examples 6-9
In Production Example 1, instead of the biaxially stretched polyester resin film “PET-12”, polyester resin films F-1, F-2, F-3, and F-4 on which an antistatic layer was laminated were used. A release film was obtained by performing the same operation as in Production Example 1 except that a resin layer was laminated on the substrate.

Production Examples 10-11
In Production Example 2, instead of the biaxially stretched polyester resin film “PET-12”, polyester resin films F-1 and F-2 having an antistatic layer laminated thereon were used, and a resin layer was laminated on the antistatic layer. Except for the above, the same operation as in Production Example 2 was performed to obtain a release film.

Examples 2-3
In Example 1 , instead of the biaxially stretched polyester resin film “PET-12”, polyester resin films F-1 and F-2 each having an antistatic layer laminated thereon were used, and a resin layer was laminated on the antistatic layer. Except for the above, the same operation as in Example 1 was performed to obtain a release film.

Comparative Example 1
The peel strength and re-tackiness were evaluated on the corona-treated surface of a biaxially stretched polyester resin film ("Embret PET-12" manufactured by Unitika Ltd., thickness 12 µm).

Comparative Example 2
Production Example 1, in place of the acid-modified polyolefin resin aqueous dispersion E-1, polyurethane resin aqueous dispersion (manufactured by Adeka Corporation, Adeka BONTIGHTER HUX380, solid concentration: 38 wt%) was used for the preparation Example 1 A release film was obtained in the same manner as described above.

Comparative Example 3
Production Example 1, in place of the acid-modified polyolefin resin aqueous dispersion E-1, a polyester resin aqueous dispersion (manufactured by Unitika Ltd., ELITEL KZA-3556, solid content concentration: 30 mass%), except for using the Production Example 1 A release film was obtained in the same manner as described above.

Comparative Example 4
In Production Example 1, a release film was obtained by performing the same operation as in Production Example 1 except that E-4 was used instead of the acid-modified polyolefin resin aqueous dispersion E-1.

Comparative Example 5
In Production Example 1, a release film was obtained by performing the same operation as in Production Example 1 except that E-5 was used instead of the acid-modified polyolefin resin aqueous dispersion E-1.

Comparative Example 6
In Comparative Example 5, an aqueous solution of 10 parts by mass of an oxazoline group-containing compound (manufactured by Nippon Shokubai Co., Ltd., Epocros “WS-500”, solid content concentration: 40% by mass) with respect to 100 parts by mass of the resin solid content of E-5. A release film was obtained in the same manner as in Comparative Example 5 except that the added coating agent was used.

For each of the release films obtained in Examples 1 to 3, Production Examples 1 to 11 and Comparative Examples 1 to 6, in addition to Unitika's fluorine-coated film "FT" (Comparative Example 7), the adhesion of the release layer, Wetting tension, releasability and re-tackiness were measured. The results are shown in Tables 3 and 4.

As in Example 1 and Production Examples 1 to 5 , a release film modified with only an acid component and containing an acid-modified polyolefin resin having a content of 1 to 15% by mass as a resin layer is a silicon compound or a fluorine compound. Even if it did not contain waxes, surfactants, etc., it showed good releasability. That is, after a peeling test after being left in an atmosphere of 2 kPa load and 70 ° C., a peeling strength of 10 N / 50 mm or less was shown. Moreover, as a result of re-adhesive evaluation, it was confirmed that there was no contamination of the adhesive surface by the resin layer. As the acid-modified polyolefin resin, the smaller the amount of acid modification, the better the releasability. Further, as in Examples 2 to 3 and Production Examples 6 to 11 , release films in which an antistatic layer was laminated on a substrate exhibited excellent antistatic properties in addition to good release properties.

  On the other hand, when the resin layer was not laminated, the releasability was not expressed (Comparative Example 1). When a resin outside the range of the present invention was used for the resin layer, the releasability was not expressed (Comparative Examples 2 to 6). Moreover, the performance was not fully improved even if the additive was added (Comparative Example 6). The material used in Comparative Example 7 was excellent in releasability and re-tackiness, but poor in wetting tension.

Claims (11)

A release sheet comprising a resin layer provided on a substrate, wherein the resin layer comprises 85 to 99% by mass of an olefin component having 2 to 4 carbon atoms and 1 to 15% by mass of an acid component. A carbodiimide compound, an oxazoline group-containing compound, an isocyanate compound, a melamine compound, a urea compound, an epoxy compound, an aziridine compound, a zirconium salt compound, and a silane coupling agent. A release sheet characterized by comprising: 2. The release according to claim 1, wherein the total content of the silicon compound, the fluorine compound, the wax, and the surfactant contained in the resin layer is 1 part by mass or less with respect to 100 parts by mass of the acid-modified polyolefin resin. Mold sheet. The release sheet according to claim 1 or 2, wherein a peel strength between the resin layer and a sheet or tape on which the acrylic pressure-sensitive adhesive is laminated is 10 N / 50 mm or less. The release sheet according to any one of claims 1 to 3, wherein the substrate is any one of a resin material, paper, synthetic paper, cloth, metal material, and glass material. The release sheet according to any one of claims 1 to 4, which is used for an adhesive material. The release sheet according to any one of claims 1 to 4, which is used for any of a printed wiring board, a polarizing plate and a retardation plate. The release sheet according to any one of claims 1 to 4, wherein the release sheet is used for forming a sheet-like structure. The release sheet according to any one of claims 1 to 7 , wherein an antistatic treatment is applied to the substrate. The sheet for mold release according to claim 8, wherein the surface resistance value is 10 ¹⁰ Ω / □ or less. A claim 1-9 or a method of manufacturing a release sheet according to the acid-modified polyolefin resin consisting of 1-15 wt% 85 to 99 wt% olefin component having 2 to 4 carbon atoms and an acid component A carbodiimide compound, an oxazoline group-containing compound, an isocyanate compound, a melamine compound, a urea compound, an epoxy compound, an aziridine compound, a zirconium salt compound, and a silane coupling agent. method of manufacturing a release sheet, wherein a liquid material comprising the step of drying After coating onto a substrate comprising a. The method for producing a release sheet according to claim 10 , wherein the liquid medium contained in the liquid material is an aqueous medium.