JP6992827B2 - Release film for manufacturing ceramic green sheets - Google Patents

Description

The present invention relates to a release film for manufacturing a ceramic green sheet. More specifically, the present invention relates to a release film for manufacturing a ceramic green sheet, which can prevent pinholes and partial thickness variations and reduce unwinding charge even when the ceramic green sheet is thinned.

Conventionally, the surface roughness of the surface (rear surface) opposite to the surface on which the release agent layer of the base film is provided is made relatively rough, so that the release film for manufacturing a ceramic green sheet is stored in a rolled state. Disclosed is a technique for eliminating problems such as the front and back of a release film for manufacturing a ceramic green sheet sticking (blocking) when the film is used (see, for example, Patent Document 1). However, such a conventional technique has a problem that pinholes and partial thickness variations occur because the protrusions are large.

Therefore, a technique has been disclosed that attempts to prevent pinholes and partial thickness variations from occurring in the ceramic green sheet by filling the protrusions on the back surface with a coating layer in order to reduce the height of the protrusions (for example). , Patent Document 2). However, according to the conventional technique, although the protrusion height is low, the protrusion density is low, so that the pressure applied to the protrusions is large, and when the ceramic green sheet is further thinned, pinholes are generated. there were.

Japanese Patent Application Laid-Open No. 2003-203822 Japanese Unexamined Patent Publication No. 2014-144636

The present invention has been made in the background of the problems of the prior art. That is, an object of the present invention is to produce an excellent ceramic green sheet that can prevent pinholes and partial thickness variations and reduce unwinding charge even when the ceramic green sheet is thinned. The purpose is to provide a release film.

The present inventor has completed the present invention as a result of diligent studies to achieve such an object. That is, the present invention has the following configuration.
1. 1. A polyester film is used as a base material, a release coating layer is provided on one surface of the substrate, and an easy-slip coating layer containing particles is provided on the other surface, and the easy-slip coating layer is acrylic. A ceramic green sheet in which a composition containing a resin and at least one cross-linking agent selected from an oxazoline-based cross-linking agent or a carbodiimide-based cross-linking agent is cured, and the acrylic resin is neutralized with a basic neutralizing agent. Release film for manufacturing.
2. 2. The release film for producing a ceramic green sheet according to the first item above, wherein the acrylic resin is an acrylic resin having a long-chain alkyl group introduced therein.
3. 3. The first or second item above, wherein the basic neutralizing agent is an amine compound selected from ammonia, trimethylamine, triethylamine, and dimethylaminoethanol, or an inorganic basic substance selected from potassium hydroxide and sodium hydroxide. A release film for manufacturing ceramic green sheets.
4. The release film for producing a ceramic green sheet according to any one of the above 1 to 3, wherein the glass transition temperature of the acrylic resin is 50 ° C. or higher and 110 ° C. or lower.
5. The release film for producing a ceramic green sheet according to any one of the above 1 to 4, wherein the acid value of the acrylic resin is 40 mgKOH / g or more and 400 mgKOH / g or less.
6. The region surface average roughness (Sa) of the easy-slip coating layer is 1 nm or more and 25 nm or less, the maximum protrusion height (P) is 60 nm or more and 500 nm or less, and the average length (RSm) of the roughness curve element is 10 μm or less. The release film for manufacturing a ceramic green sheet according to any one of the first to fifth.
7. The release film for producing a ceramic green sheet according to any one of 1 to 6 above, wherein the thickness of the easy-slip coating layer is 0.001 μm or more and 2 μm or less.
8. The method for producing a ceramic green sheet using the release film for producing a ceramic green sheet according to any one of the above 1 to 7.
9. The method for producing a ceramic green sheet according to the eighth item above, wherein the thickness of the ceramic green sheet to be produced is 0.2 μm or more and 2.0 μm or less.
10. A method for manufacturing a ceramic capacitor, which employs the method for manufacturing a ceramic green sheet according to the eighth or ninth.

According to the present invention, even when the ceramic green sheet is thinned, it is possible to prevent pinholes and partial thickness variations, and to reduce unwinding charge. It becomes possible to provide a film.

Hereinafter, the present invention will be described in detail.
The release film for producing a ceramic green sheet of the present invention (hereinafter, may be simply referred to as a release film) has a release coating layer on one side and particles on the other side of a biaxially oriented polyester film which is a base film. A release film having an easy-to-slip coating layer.

In order to increase the protrusion density of the easy-slip surface, the present inventors can cope with the recent thinning of the green sheet by keeping the average length (RSm) of the roughness curve element of the easy-slip coated surface within a specific range. We are proposing a release film (International Application No. PCT / JP2017 / 017354). It is preferable to increase the protrusion density by such a technique because it is possible to provide good winding property and prevention of pinholes and partial thickness variation while keeping the protrusion height low.

In the present invention, the easy-slip coating layer is formed by curing a composition containing an acrylic resin and at least one cross-linking agent selected from an oxazoline-based cross-linking agent or a carbodiimide-based cross-linking agent. The hardness of the coating layer becomes moderately high, and the easy-slip coating layer is less likely to be deformed when it is wound up after coating the release coating layer. It is generally known that the larger the contact area of two objects in contact with each other, the greater the charge at the time of peeling when the two objects are peeled off. When the amount of deformation of the easy-slip coating layer is small, the contact area between the easy-slip coating layer and the release layer becomes small, and it is preferable because unwinding charge when the release film roll is unwound can be suppressed. It is preferable that the unwinding charge is small because it is possible to prevent quality abnormality of the ceramic capacitor due to adhesion of environmental foreign matter to the release surface. In the thinning of ceramic sheets, which is a trend in recent years, even the adhesion of minute environmental foreign matter to the release surface, which has not been a problem in the past, becomes a problem. A release film having a composition is effective, and it is further preferable to add that the average length (RSm) of the roughness curve element of the slippery coating layer is kept within a specific range.

(Base film)
The film preferably used as a base material in the present invention is a film made of a polyester resin, and a polyester film mainly containing at least one selected from polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate is used. preferable. Further, a film made of polyester in which a third component monomer is copolymerized as a part of the dicarboxylic acid component or the diol component of the polyester as described above may be used. Among these polyester films, polyethylene terephthalate film is most preferable from the viewpoint of the balance between physical properties and cost.

Further, the polyester film may be a single layer or a plurality of layers. Further, as long as the desired effect in the present invention is exhibited, each of these layers may contain various additives in the polyester resin, if necessary. Examples of the additive include antioxidants, lightfasteners, antigelling agents, organic wetting agents, antistatic agents, ultraviolet absorbers and the like.

(Easy-slip coating layer)
The release film of the present invention has an easy-slip coating layer on one surface of the polyester base film as described above. It is preferable that the slippery coating layer contains at least a binder resin and particles.

(Binder resin in the easy-slip coating layer)
Acrylic resin is preferably contained as the binder resin constituting the easy-slip coating layer in the present invention. The acrylic resin is preferably an acrylic resin having a hydroxyl group and a carboxyl group in the molecule. It is more preferable that the constituent unit having a hydroxyl group is contained in an amount of 20 to 90 mol% in 100 mol% of all the constituent units. When the content of the constituent unit having a hydroxyl group is 20 mol% or more, the water solubility of the acrylic resin can be appropriately maintained, which is preferable. On the other hand, when it is 90 mol% or less, the hydroxyl group of the acrylic resin and the particles contained in the easy-to-slip coating layer do not cause an extreme interaction, and the particles are uniformly dispersed, which is preferable.

To introduce a hydroxyl group into an acrylic resin, a monomer having a hydroxy group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, or 2-hydroxyethyl ( A ring-opening adduct of γ-butyrolactone or ε-caprolactone to meth) acrylate may be used as a copolymerization component. Of these, 2-hydroxyethyl (meth) acrylate is preferable because it does not inhibit water solubility. In addition, these may be used in combination of 2 or more types. Needless to say, the acrylic resin in the present invention contains a methacrylic resin.

The hydroxyl value of the acrylic resin is preferably 2 mgKOH / g or more, more preferably 5 mgKOH / g or more, still more preferably 10 mgKOH / g or more. When the hydroxyl value of the acrylic resin is 2 mgKOH / g or more, the water solubility of the acrylic resin is good, which is preferable.

The hydroxyl value of the acrylic resin is preferably 250 mgKOH / g or less, more preferably 230 mgKOH / g or less, still more preferably 200 mgKOH / g or less. When the hydroxyl group value of the acrylic resin is 250 mgKOH / g or less, it is preferable that the hydroxyl group of the acrylic resin and the particles contained in the easy-to-slip coating layer do not cause an extreme interaction and the particles are uniformly dispersed.

The acrylic resin used in the present invention is preferably a resin having a carboxyl group in addition to the hydroxyl group. Having a carboxyl group makes it possible to form a crosslinked structure with a crosslinking agent and easily impart water solubility. Examples thereof include monomers containing a carboxy group such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid, and monomers containing an acid anhydride group such as maleic anhydride and itaconic anhydride.

The monomer having a carboxyl group is preferably 4 mol% or more, more preferably 10 mol% or more, out of 100 mol% of all the constituent units of the acrylic resin. When it is 4 mol% or more, it is easy to form a crosslinked structure in the easy-to-slip coating layer and to impart water solubility, which is preferable. The monomer having a carboxyl group is preferably 65 mol% or less, more preferably 50 mol% or less. When it is 65 mol% or less, the Tg of the obtained coating film does not become too high with respect to the preferable range described later, and the film-forming property and the stretching suitability in the in-line coating are good, which is preferable.

In order to develop good water solubility, it is preferable to neutralize the carboxyl group introduced into the acrylic resin by copolymerizing acrylic acid or methacrylic acid. Examples of the basic neutralizing agent include amine compounds such as ammonia, trimethylamine, triethylamine and dimethylaminoethanol, and inorganic basic substances such as potassium hydroxide and sodium hydroxide. Among them, the neutralizing agent is volatile. It is preferable to use an amine compound as a neutralizing agent in order to facilitate the formation of a crosslinked structure. Of these, ammonia is most preferable because it does not cause agglutination of particles. The neutralization rate is preferably 30 mol% to 95 mol%, more preferably 40 mol% to 90 mol%. When the neutralization rate is 30 mol% or more, the water solubility of the acrylic resin is sufficient, the acrylic resin is easily dissolved at the time of preparing the coating liquid, and there is no risk of whitening of the coating film surface after drying. preferable. On the other hand, when the neutralization rate is 95 mol% or less, the water solubility is not too high, and alcohol and the like can be easily mixed in the preparation of the coating liquid, which is preferable.

The acid value of the acrylic resin is preferably 40 mgKOH / g or more, more preferably 50 mgKOH / g or more, still more preferably 60 mgKOH / g or more. When the acid value of the acrylic resin is 40 mgKOH / g or more, the number of cross-linking points with the oxazoline cross-linking agent or the carbodiimide cross-linking agent increases, and a strong coating film having a higher cross-linking density can be obtained, which is preferable.

The acid value of the acrylic resin is preferably 400 mgKOH / g or less, more preferably 350 mgKOH / g or less, still more preferably 300 mgKOH / g or less. When the acid value of the acrylic resin is 400 mgKOH / g or less, it is preferable that the carboxyl group of the acrylic resin and the particles contained in the easy-to-slip coating layer do not cause an extreme interaction and the particles are uniformly dispersed. Good particle dispersibility is preferable because coarse protrusions do not occur on the slippery coated surface and pinholes of the ceramic sheet do not occur.

The glass transition temperature (Tg) of the acrylic resin is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, still more preferably 60 ° C. or higher. When the glass transition temperature of the acrylic resin is 50 ° C. or higher, the hardness of the easy-to-slip coating layer becomes moderately high, which is preferable.

The glass transition temperature (Tg) of the acrylic resin is preferably 110 ° C. or lower, more preferably 105 ° C. or lower, still more preferably 100 ° C. or lower. When the glass transition temperature of the acrylic resin is 110 ° C. or lower, it is preferable because the coating film is uniformly stretched without cracks in the stretching step after the easy-slip coating layer is applied.

As the Tg adjusting monomer copolymerized to bring Tg within the above range, a (meth) acrylic monomer or a non-acrylic vinyl monomer can be used. Specific examples of the (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and n-amyl (meth). Acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, (Meta) acrylic acid alkyl esters such as stearyl (meth) acrylate; nitrogen-containing acrylic monomers such as (meth) acrylamide, diacetone acrylamide, n-methylol acrylamide, and (meth) acrylonitrile; vinyl methacrylate and the like. These can be used alone or in combination of two or more.

Examples of the non-acrylic vinyl monomer include styrene-based monomers such as styrene, α-methylstyrene, vinyltoluene (mixture of m-methylstyrene and p-methylstyrene), and chlorostyrene; vinyl acetate, vinyl propionate, and vinyl butyrate. , Vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, vinyl pivalate, vinyl octylate, vinyl monochromoacetate, divinyl adipate, Vinyl esters such as vinyl crotonate, vinyl sorbate, vinyl benzoate, vinyl silicate; vinyl halide monomers such as vinyl chloride and vinylidene chloride; may be used, and one or more of them can be used.

As the monomer for adjusting Tg, it is preferable to determine the appropriate amount of the hydroxyl group-containing monomer and the carboxyl group-containing monomer, and then use the balance thereof. The Tg of the copolymer is calculated by the following Fox formula.

Ｗ_n：各モノマーの質量分率（質量％）
Ｔｇ_n：各モノマーのホモポリマーのＴｇ（Ｋ）

W _n : Mass fraction (mass%) of each monomer
Tg _n : Tg (K) of homopolymer of each monomer

As the monomer copolymerized for Tg adjustment, it is preferable that a component that lowers the surface free energy, such as a long-chain alkyl group, is introduced. As the acrylic resin into which a long-chain alkyl group is introduced, a resin having an alkyl group having about 8 to 20 carbon atoms in the side chain of the acrylic resin is preferable. Further, a polymer having a (meth) acrylic acid ester as a main repeating unit and having a transesterified portion containing a long-chain alkyl group having 8 to 20 carbon atoms can also be preferably used.

The monomer having a long-chain alkyl group in the monomer copolymerized for Tg adjustment is preferably 50 mol% or less, more preferably 40 mol% or less, based on 100 mol% of all the constituent units of the acrylic resin. When it is 50 mol% or less, the Tg of the obtained coating film does not become too low with respect to the preferable range, and the hardness of the coating film can be maintained high, which is preferable. In the present invention, the monomer having a long-chain alkyl group may be 0 mol% as long as the Tg can be maintained in a suitable range, but if it is 5 mol% or more, the effect of adjusting the Tg of the acrylic resin is sufficient. Is clear and preferable.

The acrylic resin used in the present invention can be obtained by known radical polymerization. Emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization and the like can all be adopted. From the viewpoint of handleability, solution polymerization is preferable. Examples of the water-soluble organic solvent that can be used for solution polymerization include ethylene glycol n-butyl ether, isopropanol, ethanol, n-methylpyrrolidone, tetrahydrofuran, 1,4-dioxane, 1,3-oxolane, methylsolosolve, and ethylsolosolve. , Ethylcarbitol, butylcarbitol, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like. These may be mixed with water and used.

The polymerization initiator may be any known compound that generates radicals, but for example, a water-soluble azo-based polymerization initiator such as 2,2-azobis-2-methyl-N-2-hydroxyethylpropionamide is preferable. The temperature and time of polymerization are appropriately selected.

The mass average molecular weight (Mw) of the acrylic resin is preferably about 10,000 to 200,000. A more preferred range is 20,000 to 150,000. When Mw is 10,000 or more, there is no risk of thermal decomposition in the tenter, which is preferable. When Mw is 200,000 or less, the viscosity of the coating liquid does not increase significantly, and the coatability is good, which is preferable.

In addition to the acrylic resin, another binder resin may be used in combination as the binder for the slippery coating layer in the present invention. Examples of other binder resins include polyester resins, urethane resins, polyvinyl resins (polyvinyl alcohol and the like), polyalkylene glycols, polyalkylene imines, methyl celluloses, hydroxycelluloses, starches and the like.

The content of the acrylic resin in the easy-to-slip coating layer is preferably 20% by mass or more and 95% by mass or less in the total solid content. More preferably, it is 30% by mass or more and 90% by mass or less. When it is 20% by mass or more, it is preferable because the carboxyl group which is a cross-linking component does not become too small and the cross-linking density does not decrease. When it is 95% by mass or less, the amount of the cross-linking agent to be cross-linked does not become too small and the cross-linking density does not decrease, which is preferable.

(Crosslinking agent)
In the present invention, in order to form a crosslinked structure in the easy-slip coated layer, the easy-slip coated layer preferably contains at least one cross-linking agent selected from an oxazoline-based cross-linking agent or a carbodiimide-based cross-linking agent. By containing an oxazoline-based cross-linking agent or a carbodiimide-based cross-linking agent, the adhesion to the PET substrate is improved, and the cross-linking with the carboxyl group of the acrylic resin is promoted to improve the coating strength of the slippery layer. As a result, unwinding charge when the release film roll is unwound can be suppressed. Further, other cross-linking agents may be used in combination, and specific cross-linking agents that can be used in combination include urea-based, epoxy-based, melamine-based, isocyanate-based, silanol-based, and the like. Further, in order to promote the cross-linking reaction, a catalyst or the like can be appropriately used as needed.

As the cross-linking agent having an oxazoline group, for example, a conventionally known method (for example, solution polymerization, emulsion polymerization, etc.) of a polymerizable unsaturated monomer having an oxazoline group together with other polymerizable unsaturated monomers is used. Examples thereof include a polymer having an oxazoline group obtained by copolymerizing with the above.

Examples of the polymerizable unsaturated monomer having an oxazoline group include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, and 2-. Examples thereof include isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline and the like. These may be used alone or in combination of two or more.

Examples of other polymerizable unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth). Alkyl or cycloalkyl ester of (meth) acrylic acid having 1 to 24 carbon atoms such as acrylate, lauryl (meth) acrylate and isobornyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and the like. Hydroxyalkyl esters of (meth) acrylic acid with 2 to 8 carbon atoms; vinyl aromatic compounds such as styrene and vinyltoluene; (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, Additives of glycidyl (meth) acrylate and amines; polyethylene glycol (meth) acrylate; N-vinylpyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, vinyl acetate, (meth) acrylonitrile and the like. These may be used alone or in combination of two or more.

The other polymerizable unsaturated monomer uses the obtained cross-linking agent having an oxazoline group as a water-soluble cross-linking agent, and is a hydrophilic single amount from the viewpoint of improving compatibility with other resins, wettability, cross-linking reaction efficiency and the like. It is preferably a body. Examples of the hydrophilic monomer include 2-hydroxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, a monomer having a polyethylene glycol chain such as a monoester compound of (meth) acrylic acid and polyethylene glycol, and 2-. Examples thereof include aminoethyl (meth) acrylate and salts thereof, (meth) acrylamide, N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, (meth) acrylonitrile, sodium styrene sulfonate and the like. Among these, a monomer having a polyethylene glycol chain such as methoxypolyethylene glycol (meth) acrylate having high solubility in water and a monoester compound of (meth) acrylic acid and polyethylene glycol is preferable.

The cross-linking agent having an oxazoline group preferably has an oxazoline group content of 3.0 to 9.0 mmol / g. More preferably, it is in the range of 4.0 to 8.0 mmol / g. The range of 4.0 to 8.0 mmol / g is preferable because an appropriate crosslinked structure can be formed.

Examples of the carbodiimide-based cross-linking agent include monocarbodiimide compounds and polycarbodiimide compounds. Examples of the monocarbodiimide compound include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide, di-β-naphthylcarbodiimide and the like. .. As the polycarbodiimide compound, a compound produced by a conventionally known method can be used. For example, it can be produced by synthesizing an isocyanate-terminated polycarbodiimide by a condensation reaction involving decarbonization of diisocyanate.

Examples of the diisocyanate which is a synthetic raw material of the polycarbodiimide compound include isomers of toluylene diisocyanate, aromatic diisocyanates such as 4,4-diphenylmethane diisocyanate, aromatic aliphatic diisocyanates such as xylylene diisocyanate, isophorone diisocyanate and 4 , 4-Dicyclohexylmethane diisocyanate, alicyclic diisocyanates such as 1,3-bis (isocyanatemethyl) cyclohexane, hexamethylene diisocyanate, and aliphatic diisocyanates such as 2,2,4-trimethylhexamethylene diisocyanate. From the viewpoint of yellowing, aromatic aliphatic diisocyanates, alicyclic diisocyanates, and aliphatic diisocyanates are preferable.

Further, the diisocyanate may be used by controlling the molecule to an appropriate degree of polymerization by using a compound that reacts with a terminal isocyanate such as monoisocyanate. Examples of the monoisocyanate for sealing the end of polycarbodiimide and controlling the degree of polymerization thereof include phenyl isocyanate, toluylene isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, and naphthyl isocyanate. In addition, a compound having an OH group, -NH ₂ group, COOH group, and SO ₃ H group can be used as the terminal encapsulant.

The condensation reaction involving decarbonization of diisocyanate proceeds in the presence of a carbodiimidization catalyst. Examples of the catalyst include 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, and 3-methyl-1-phenyl-2. Examples thereof include -phospholene-1-oxide and phosphorene oxides such as these 3-phosphoren isomers, and 3-methyl-1-phenyl-2-phospholene-1-oxide is preferable from the viewpoint of reactivity. The amount of the catalyst used can be the amount of the catalyst.

It is desirable that the above-mentioned mono or polycarbodiimide compound be maintained in a uniformly dispersed state when blended into an aqueous paint, and for this purpose, it can be emulsified with an appropriate emulsifier and used as an emulsion, or polycarbodiimide. It is preferred to add a hydrophilic segment within the molecular structure of the compound and blend it into the paint in the form of a self-emulsifying product or in the form of a self-dissolving product.

Examples of the carbodiimide-based cross-linking agent used in the present invention include water dispersibility and water solubility. Water solubility is preferable because it has good compatibility with other water-soluble resins and improves the cross-linking reaction efficiency of the easy-to-slip coating layer. In order to make the carbodiimide compound water-soluble, an isocyanate-terminated polycarbodiimide is synthesized by a condensation reaction involving decarbonation of isocyanate, and then a hydrophilic moiety having a functional group reactive with the isocyanate group is added. Can be manufactured by

Examples of the hydrophilic moiety include (1) a quaternary ammonium salt of a dialkylaminoalcohol, a quaternary ammonium salt of a dialkylaminoalkylamine, (2) an alkylsulfonate having at least one reactive hydroxyl group, and (3). Examples thereof include poly (ethylene oxide) terminally sealed with an alkoxy group, and a mixture of poly (ethylene oxide) and poly (propylene oxide). When the above hydrophilic site is introduced, the carbodiimide compound becomes (1) cationic, (2) anionic, and (3) nonionic. Of these, nonionic properties that can be compatible with each other are preferable regardless of the ionicity of other water-soluble resins.

The content of the cross-linking agent in the easy-to-slip coating layer is preferably 5% by mass or more and 80% by mass or less in the total solid content. More preferably, it is 10% by mass or more and 70% by mass or less. When it is 5% by mass or more, it is preferable because the crosslink density of the resin of the coating layer does not decrease. When it is 80% by mass or less, the amount of the carboxyl group of the acrylic resin to be crosslinked does not become too small, and the crosslinking density does not decrease, which is preferable.

(Particles in the easy-to-slip coating layer)
The slippery coating layer preferably contains lubricant particles in order to impart slipperiness to the surface. The particles may be inorganic particles or organic particles, and are not particularly limited. (1) Silica, kaolinite, talc, light calcium carbonate, heavy calcium carbonate, zeolite, alumina, etc. Barium Sulfate, Carbon Black, Zinc Oxide, Zinc Sulfate, Zinc Carbonate, Zinc Oxide, Titanium Dioxide, Satin White, Aluminum Silate, Caesole Soil, Calcium Silica, Aluminum Hydroxide, Hydrochlorite, Calcium Carbonate, Magnesium Carbonate, Calcium Phosphate, Hydroxide Inorganic particles such as magnesium and barium sulfate, (2) acrylic or methacrylic, vinyl chloride, vinyl acetate, nylon, styrene / acrylic, styrene / butadiene, polystyrene / acrylic, polystyrene / isoprene, polystyrene / Examples thereof include organic particles such as isoprene-based, methyl methacrylate / butyl methacrylate-based, melamine-based, polycarbonate-based, urea-based, epoxy-based, urethane-based, phenol-based, diallyl phthalate-based, and polyester-based. Silica is particularly preferably used in order to impart appropriate slipperiness to the coating layer.

The average particle size of the particles is preferably 10 nm or more, more preferably 20 nm or more, still more preferably 30 nm or more. When the average particle size of the particles is 10 nm or more, it is difficult to aggregate and slipperiness can be ensured, which is preferable.

The average particle size of the particles is preferably 1000 nm or less, more preferably 800 nm or less, still more preferably 600 nm or less. When the average particle size of the particles is 1000 nm or less, transparency is maintained and the particles do not fall off, which is preferable.

Further, for example, it is also possible to mix small particles having an average particle size of about 10 to 270 nm and large particles having an average particle size of about 300 to 1000 nm, which will be described later in terms of region surface average roughness (Sa) and maximum protrusion height (Sa). It is preferable to reduce the average length (RSm) of the roughness curve element while keeping P) small to achieve both slipperiness and smoothness, and particularly preferably, small particles of 30 nm or more and 250 nm or less and average particles. Large particles with a diameter of 350 to 600 nm are used in combination. When small particles and large particles are mixed, it is preferable that the mass content of the small particles is larger than the mass content of the large particles with respect to the total solid content of the coating layer.

It is also particularly preferable to use organic particles in terms of preventing the particles from falling off from the I Ching coating layer. It is preferable to use organic particles because the interaction with the binder of the easy-to-slip coating layer and the cross-linking agent component becomes strong, and it becomes easy to prevent falling off. Among the organic particles, acrylic resin particles and / or methacrylic resin particles having a chemical structure similar to that of the acrylic resin present in the easy-slip coating layer are particularly preferable in terms of preventing the particles from falling off from the easy-slip coating layer. .. These organic particles are preferably contained as particles having a relatively large average particle size, which tends to cause a problem of particles falling off from the easy-to-slip coating layer, and are contained, for example, as particles having an average particle size of 300 to 1000 nm. Is preferable. More preferably, it is contained as particles having an average particle size of 350 to 600 nm. Of course, it is a particularly preferable embodiment that the organic particles having the average particle size are acrylic resin particles and / or methacrylic resin particles.

The method for measuring the average particle size of the particles is to observe the particles in the cross section of the processed film with a transmission electron microscope or a scanning electron microscope, observe 100 non-aggregated particles, and use the average value as the average grain. It was done by the method of making the diameter.

The shape of the particles is not particularly limited as long as it satisfies the object of the present invention, and spherical particles and amorphous non-spherical particles can be used. The particle size of the amorphous particles can be calculated as the equivalent circle diameter. The equivalent circle diameter is a value obtained by dividing the observed particle area by π, calculating the square root, and doubling it.

The ratio of the particles to the total solid content of the slippery coating layer is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less. When the ratio of the particles to the total solid content of the easy-slip coating layer is 50% by mass or less, the transparency is maintained and the particles do not significantly fall off from the easy-slip coating layer, which is preferable.

The ratio of the particles to the total solid content of the slippery coating layer is preferably 1% by mass or more, more preferably 1.5% by mass or more, and further preferably 2% by mass or more. When the ratio of the particles to the total solid content of the easy-slip coating layer is 1% by mass or more, slipperiness can be ensured, which is preferable.

As a method for measuring the content of particles contained in the easy-slip coating layer, for example, when the easy-slip coating layer contains an organic resin and inorganic particles, the following method can be used. First, the easy-slip coating layer provided on the processed film is extracted from the processed film using a solvent or the like and dried to dryness to take out the easy-slip coating layer. Next, heat is applied to the obtained easy-slip coating layer, and the organic component contained in the easy-slip coating layer is burned and distilled off by heat, whereby only the inorganic component can be obtained. By measuring the weights of the obtained inorganic component and the easy-slip coating layer before combustion distillation, the mass% of the particles contained in the easy-slip coating layer can be measured. At this time, accurate measurement can be performed by using a commercially available differential thermal / thermogravimetric simultaneous measuring device. The ratio of the above particles to the total solid content of the easy-to-slip coating layer means the ratio of the total amount of the plurality of types of particles when a plurality of types are present.

(Additives in the easy-to-slip coating layer)
In order to impart other functionality to the slippery coating layer, various additives may be contained within a range that does not impair the coating appearance. Examples of the additive include fluorescent dyes, fluorescent whitening agents, plasticizers, ultraviolet absorbers, pigment dispersants, defoaming agents, defoaming agents, preservatives and the like.

The easy-slip coating layer may contain a surfactant for the purpose of improving the leveling property at the time of coating and defoaming the coating liquid. The surfactant may be any of a cationic type, an anionic type, a nonionic type and the like, but a silicone type, an acetylene glycol type or a fluorine type surfactant is preferable. It is preferable that these surfactants are contained in the coating layer to the extent that an abnormality in the appearance of the coating does not occur due to excessive addition.

As the coating method, either a so-called in-line coating method in which the polyester base film is applied at the same time as the film is formed and a so-called offline coating method in which the polyester base film is separately applied with a coater after the film is formed can be applied, but the in-line coating method can be applied. Is more efficient and more preferable.

As a coating method, any known method can be used as the method for coating the coating liquid on the polyethylene terephthalate (hereinafter, may be abbreviated as PET) film. For example, reverse roll coat method, gravure coat method, kiss coat method, die coater method, roll brush method, spray coat method, air knife coat method, wire bar coat method, pipe doctor method, impregnation coat method, curtain coat method, etc. Can be mentioned. These methods are applied alone or in combination.

In the present invention, as a method of providing the easy-slip coating layer on the polyester film, a method of applying a coating liquid containing a solvent, particles and a resin to the polyester film and drying it can be mentioned. Examples of the solvent include an organic solvent such as toluene, water, or a mixed system of water and a water-soluble organic solvent. However, from the viewpoint of environmental problems, water alone or a so-called water system in which a water-soluble organic solvent is mixed with water is preferable. Solvent is preferred.

The solid content concentration of the easy-slip coating liquid depends on the type of binder resin, the type of solvent, and the like, but is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The solid content concentration of the coating liquid is preferably 35% by mass or less, more preferably 20% by mass or less.

The drying temperature after coating also depends on the type of binder resin, the type of solvent, the presence or absence of a cross-linking agent, the solid content concentration, and the like, but is preferably 70 ° C. or higher, and preferably 250 ° C. or lower.

(Manufacturing of polyester film)
In the present invention, the polyester film to be the base film can be produced according to a general method for producing a polyester film. For example, a non-oriented polyester obtained by melting a polyester resin and extruding it into a sheet is stretched in the vertical direction at a temperature equal to or higher than the glass transition temperature by utilizing the speed difference of the rolls, and then stretched in the horizontal direction by a tenter. A method of applying heat treatment can be mentioned. Further, a method of biaxially stretching in the tenter at the same time in both vertical and horizontal directions can be mentioned.

In the present invention, the polyester film to be the base film may be a uniaxially stretched film or a biaxially stretched film, but a biaxially stretched film is preferable.

The thickness of the polyester film base material is preferably 5 μm or more, more preferably 10 μm or more, still more preferably 15 μm or more. When the thickness is 5 μm or more, wrinkles are less likely to occur during transportation of the film, which is preferable.

The thickness of the polyester film base material is preferably 50 μm or less, more preferably 45 μm or less, and further preferably 40 μm or less. When the thickness is 40 μm or less, the cost per unit area is reduced, which is preferable.

In the case of an in-line coat, it may be applied to an unstretched film before stretching in the vertical direction, or may be applied to a uniaxially stretched film after stretching in the vertical direction and before stretching in the horizontal direction. When coating is applied before stretching in the vertical direction, it is preferable to provide a drying step before stretching the roll. When coating on a uniaxially stretched film before stretching in the lateral direction, the drying step can also be combined with the film heating step in the tenter, so it is not always necessary to provide a separate drying step. The same applies to the case of simultaneous biaxial stretching.

The film thickness of the slippery coating layer is preferably 0.001 μm or more, more preferably 0.01 μm or more, still more preferably 0.02 μm or more, and particularly preferably 0.03 μm or more. When the film thickness of the coating layer is 0.001 μm or more, the film-forming property of the coating film is maintained and a uniform coating film can be obtained, which is preferable.

The film thickness of the slippery coating layer is preferably 2 μm or less, more preferably 1 μm or less, still more preferably 0.8 μm or less, and particularly preferably 0.5 μm or less. When the film thickness of the coating layer is 2 μm or less, blocking may not occur, which is preferable.

The ceramic green sheet coated and molded on the release coating layer described later is wound into a roll together with the release film after coating and molding. At this time, the easy-slip coating layer of the release film is wound in contact with the surface of the ceramic green sheet. The outer surface of the easy-slip coating layer (the surface of the easy-slip coating layer of the entire coating film that is not in contact with the polyester film) needs to be moderately flat in order to prevent defects on the surface of the ceramic green sheet. It is preferable that the surface average roughness (Sa) is 1 nm or more and 25 nm or less and the maximum protrusion height (P) is 60 nm or more and 500 nm or less.

If the region surface average roughness (Sa) of the outer surface of the easy-slip coated layer is 1 nm or more and the maximum protrusion height (P) is 60 nm or more, the easy-slip coated surface does not become too smooth and moderate slipperiness is maintained. It is preferable because it can be done. When the region surface average roughness (Sa) is 25 nm or less and the maximum protrusion height (P) is 500 nm or less, the easy-slip coated surface does not become too rough and defects of the ceramic green sheet due to protrusions do not occur, which is preferable.

In the present invention, in addition to setting the region surface average roughness (Sa) and the maximum protrusion height (P) within the above ranges, it is preferable that the average length (RSm) of the roughness curve element is 10 μm or less. By controlling the average length (RSm) of the roughness curve element to 10 μm or less, the number of protrusions per unit area increases. When the number of protrusions increases, the pressure applied to each protrusion is dispersed and becomes smaller, which is preferable because the generation of pinholes can be effectively suppressed. The average length (RSm) of the roughness curve element is more preferably 5 μm or less, still more preferably 3 μm or less. However, if the average length (RSm) of the roughness curve element is too small, it is related to the content of particles in the easy-to-slip coating layer being too large, and the region surface average roughness (Sa) becomes large. In addition, since it is related to the increase in the maximum protrusion height (P), it is preferably 0.1 μm or more, and may be 0.5 μm or more, or 1 μm or more.

In the present invention, in order to keep the average length (RSm) of the roughness curve element within a predetermined range, the average particle size of the particles contained in the slippery coating layer is preferably 1000 nm or less. It is more preferably 800 nm or less, still more preferably 600 nm or less. When the particle diameter is 1000 nm or less, the distance between the particles does not become too large, and RSm is adjusted to a predetermined range, which is preferable.

The surface free energy of the slippery coating layer is preferably 45 mJ / m ² or less, and more preferably 40 mJ / m ² or less. When the surface free energy of the easy-slip coating layer is 45 mJ / m ² or less, it becomes difficult for foreign matter to adhere to the mold release surface in the process, and it becomes difficult for foreign matter to adhere to the mold release surface. It is preferable that pinholes are less likely to occur.

(Release coating layer)
The resin constituting the release coating layer in the present invention is not particularly limited, and silicone resin, fluororesin, alkyd resin, various waxes, aliphatic olefins and the like can be used, and each resin may be used alone or in combination of two or more. You can also do it.

As the release coating layer in the present invention, for example, the silicone resin is a resin having a silicone structure in the molecule, and examples thereof include curable silicone, silicone graft resin, and modified silicone resin such as alkyl-modified. From the viewpoint of properties and the like, it is preferable to use a reactive cured silicone resin. As the reactive cured silicone resin, an addition reaction type resin, a condensation reaction type resin, an ultraviolet ray or electron beam curing type resin, and the like can be used. More preferably, a low-temperature curable addition reaction system that can be processed at a low temperature, and an ultraviolet or electron beam curable system are preferable. By using these materials, it is possible to process at a low temperature when the polyester film is coated. Therefore, there is little heat damage to the polyester film during processing, a polyester film with high flatness can be obtained, and defects such as pinholes can be reduced even when manufacturing an ultra-thin ceramic green sheet having a thickness of 0.2 to 2.0 μm. Can be done.

Examples of the addition reaction type silicone resin include those in which polydimethylsiloxane having a vinyl group introduced at the terminal or side chain and hydroxydienesiloxane are reacted with each other using a platinum catalyst to be cured. At this time, it is more preferable to use a resin that can be cured at 120 ° C. within 30 seconds because it can be processed at a low temperature. Examples include low temperature add-curing types manufactured by Toray Dow Corning (LTC1006L, LTC1056L, LTC300B, LTC303E, LTC310, LTC314, LTC350G, LTC450A, LTC371G, LTC750A, LTDC755, LTC245A, etc.) -510, BY24-561, BY24-562, etc.), Shin-Etsu Chemical's solvent-added + UV curable type (X62-5040, X62-5065, X62-5072T, KS5508, etc.), Dual cure curable type (X62-2835, X62, etc.) -2834, X62-1980, etc.) and the like.

As the silicone resin of the condensation reaction system, for example, a polydimethylsiloxane having an OH group at the terminal and a polydimethylsiloxane having an H group at the terminal are subjected to a condensation reaction using an organic tin catalyst to form a three-dimensional crosslinked structure. Can be mentioned.

As the ultraviolet curable silicone resin, for example, the most basic type is one that uses the same radical reaction as ordinary silicone rubber crosslinks, one that is photocured by introducing an unsaturated group, and one that decomposes onium salts with ultraviolet rays. Examples thereof include those that generate a strong acid and thereby cleave the epoxy group to crosslink it, and those that crosslink by the addition reaction of thiol to vinylsiloxane. Further, an electron beam can be used instead of the ultraviolet rays. The electron beam has stronger energy than ultraviolet rays, and it is possible to carry out a radical cross-linking reaction without using an initiator as in the case of ultraviolet curing. Examples of the resin used are UV curable silicones manufactured by Shin-Etsu Chemical Co., Ltd. (X62-7028A / B, X62-7052, X62-7205, X62-7622, X62-7629, X62-7660, etc.), Momentive Performance Materials. UV curable silicone manufactured by Materials (TPR6502, TPR6501, TPR6500, UV9300, UV9315, XS56-A2982, UV9430, etc.), UV curable silicone manufactured by Arakawa Chemical Co., Ltd. ).

As the above-mentioned ultraviolet curable silicone resin, acrylate-modified or glycidoxy-modified polydimethylsiloxane can also be used. Good mold release performance can also be obtained by mixing these modified polydimethylsiloxanes with a polyfunctional acrylate resin, epoxy resin, or the like and using them in the presence of an initiator.

As other examples of the resin to be used, an alkyd resin or an acrylic resin modified with stearyl or lauryl, or an alkyd resin or an acrylic resin obtained by a reaction with methylated melamine is also suitable.

Examples of the aminoalkyd resin obtained by the reaction of methylated melamine include Tessfine 303, Tessfine 305, and Tessfine 314 manufactured by Hitachi Kasei Co., Ltd. Examples of the aminoacrylic resin obtained by the reaction of methylated melamine include Tessfine 322 manufactured by Hitachi Kasei Co., Ltd.

When the above resin is used for the release coating layer in the present invention, one type may be used, or two or more types may be mixed and used. It is also possible to mix additives such as a light peeling additive and a heavy peeling additive in order to adjust the peeling force.

The release coating layer in the present invention may contain particles having a particle size of 1 μm or less, but it is preferable that the release coating layer does not substantially contain particles or the like that form protrusions such as particles from the viewpoint of pinhole generation.

Additives such as an adhesion improver and an antistatic agent may be added to the release coating layer in the present invention. Further, in order to improve the adhesion to the substrate, it is also preferable to perform pretreatment such as anchor coating, corona treatment, plasma treatment, and atmospheric pressure plasma treatment on the surface of the polyester film before providing the release coating layer.

In the present invention, the thickness of the release coating layer may be set according to the purpose of use, and is not particularly limited, but preferably, the thickness of the release coating layer after curing is 0.005 to 2.0 μm. The range is good. When the thickness of the release coating layer is 0.005 μm or more, the peeling performance is maintained, which is preferable. Further, when the thickness of the release coating layer is 2.0 μm or less, the curing time does not become too long, and there is no possibility that the thickness of the ceramic green sheet becomes uneven due to the deterioration of the flatness of the release film, which is preferable. Further, since the curing time does not become too long, there is no possibility that the resin constituting the release coating layer will aggregate and there is no possibility of forming protrusions, so that pinhole defects of the ceramic green sheet are less likely to occur, which is preferable.

The outer surface of the film on which the release coating layer is formed (the surface of the release coating layer of the entire coating film that is not in contact with the polyester film) is flat so as not to cause defects in the ceramic green sheet coated and molded on it. It is preferable that the region surface average roughness (Sa) is 5 nm or less and the maximum protrusion height (P) is 30 nm or less. Further, it is more preferable that the region surface average roughness is 5 nm or less and the maximum protrusion height is 20 nm or less. When the region surface roughness is 5 nm or less and the maximum protrusion height is 30 nm or less, defects such as pinholes do not occur when the ceramic green sheet is formed, and the yield is good, which is preferable. It can be said that the smaller the region surface average roughness (Sa) is, the more preferable it is, but it may be 0.1 nm or more, or 0.3 nm or more. It can be said that the smaller the maximum protrusion height (P) is, the more preferable it is, but it may be 1 nm or more, or 3 nm or more.

In the present invention, in order to adjust the surface of the film on which the release coating layer is formed to a predetermined roughness range, it is preferable that the PET film contains substantially no inorganic particles. In the present invention, "substantially free of inorganic particles" means that both the base film and the release coating layer are 50 ppm or less when the elements derived from the particles are quantitatively analyzed by fluorescent X-ray analysis. It is defined as being, preferably 10 ppm or less, and most preferably below the detection limit. This means that even if the particles are not actively added to the base film, the contaminant components derived from foreign substances and the stains attached to the raw material resin or the line or device in the manufacturing process of the film are peeled off and mixed in the film. This is because it may be done.

In the present invention, the method for forming the release coating layer is not particularly limited, and a coating liquid in which a releaseable resin is dissolved or dispersed is developed by coating on one surface of a polyester film as a base material, and a solvent is used. After removing the above by drying, a method of heat-drying, thermosetting or ultraviolet curing is used. At this time, the drying temperature at the time of solvent drying and thermosetting is preferably 180 ° C. or lower, more preferably 150 ° C. or lower, and most preferably 120 ° C. or lower. The heating time is preferably 30 seconds or less, more preferably 20 seconds or less. When the temperature is 180 ° C. or lower, the flatness of the film is maintained and the possibility of causing uneven thickness of the ceramic green sheet is small, which is preferable. When the temperature is 120 ° C. or lower, the film can be processed without impairing the flatness of the film, and the possibility of causing uneven thickness of the ceramic green sheet is further reduced, which is particularly preferable.

In the present invention, the surface tension of the coating liquid when the release coating layer is applied is not particularly limited, but is preferably 30 mN / m or less. By setting the surface tension as described above, the coatability after coating can be improved, and the unevenness of the coating film surface after drying can be reduced.

In the present invention, the coating liquid for applying the release coating layer is not particularly limited, but it is preferable to add a solvent having a boiling point of 90 ° C. or higher. By adding a solvent having a boiling point of 90 ° C. or higher, bumping during drying can be prevented, the coating film can be leveled, and the smoothness of the coating film surface after drying can be improved. The amount to be added is preferably about 10 to 80% by mass with respect to the entire coating liquid.

Any known coating method can be applied as the coating method, for example, a roll coating method such as a gravure coating method or a reverse coating method, a bar coating method such as a wire bar, a die coating method, a spray coating method, or an air knife. Conventionally known methods such as the coat method can be used.

(Ceramic green sheet and ceramic capacitor)
Generally, a monolithic ceramic capacitor has a rectangular parallelepiped ceramic prime field. Inside the ceramic prime field, first internal electrodes and second internal electrodes are alternately provided along the thickness direction. The first internal electrode is exposed on the first end face of the ceramic prime field. A first external electrode is provided on the first end face. The first internal electrode is electrically connected to the first external electrode at the first end face. The second internal electrode is exposed on the second end face of the ceramic prime field. A second external electrode is provided on the second end face. The second internal electrode is electrically connected to the second external electrode at the second end face.

The release film for manufacturing a ceramic green sheet of the present invention is used for manufacturing such a multilayer ceramic capacitor. For example, it is manufactured as follows. First, the release film of the present invention is used as a carrier film, and a ceramic slurry for forming a ceramic prime field is applied and dried. A conductive layer for forming the first or second internal electrode is printed on the coated and dried ceramic green sheet. A ceramic green sheet, a ceramic green sheet on which a conductive layer for forming a first internal electrode is printed, and a ceramic green sheet on which a conductive layer for forming a second internal electrode is printed are appropriately laminated and pressed. Thereby, a mother laminated body is obtained. The mother laminate is divided into a plurality of pieces to prepare a raw ceramic prime field. A ceramic prime is obtained by firing a raw ceramic prime. After that, the multilayer ceramic capacitor can be completed by forming the first and second external electrodes.

Next, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is naturally not limited to the following Examples. The evaluation method used in the present invention is as follows.

[NMR measurement]
The ratio of the copolymerization component introduced into the acrylic polyol is nuclear magnetic resonance spectroscopy ( ¹ HN).
Confirmed using MR, ¹³ C-NMR: Varian Unity 400, manufactured by Agilent. The measurement was carried out by removing the solvent in the synthesized acrylic polyol with a vacuum dryer and then dissolving the dry matter in heavy chloroform. From the obtained NMR spectrum, the peak of the chemical shift δ (ppm) attributed to the site of each group was identified. The integrated intensity of each of the obtained peaks was obtained, and the composition ratio (mol%) of the copolymerization component introduced into the acrylic polyol was confirmed from the hydrogen number and the integrated intensity of each group site.

[Confirmation of Tg]
The composition ratio of the copolymerization component obtained by the above NMR measurement and the Tg of each acrylic polyol were obtained from the above-mentioned Fox formula.

[Stretching suitability]
In order to evaluate the stretchability of the acrylic polyol itself, the synthesized acrylic polyols (1) to (13) are mixed with a mixed solvent (25) of 30% by mass of isopropanol and 70% by mass of water so that the solid content concentration is 12% by mass. After the solution was prepared by putting it in (° C.) into a single acrylic polyol, the solution was applied to the surface of the polyester film that had only been longitudinally stretched with Mayer bar # 5. Next, the film sample on which the coating layer (thickness 6.5 μm) was formed was allowed to stand in a hot air circulation oven set at a temperature of 60 ° C. for 30 seconds, and then the film sample was taken out from the oven and pre-dried. Next, the sample was manually rotated and set in a stretching device (manufactured by Toyobo Engineering Co., Ltd.), placed in a hot air circulation oven at 100 ° C., and slowly stretched. The stretching operation was performed until the length became four times the length before stretching, and the stretching device was taken out from the hot air circulation oven. Then, the coating film after stretching was observed with an optical microscope (magnification: 200 times), and the presence or absence of cracking due to stretching was determined according to the following criteria.
◯: No cracks are seen.
Δ: Some cracks are seen (1 to 4).
X: Five or more cracks or cracks are seen on the entire surface.

(1) Surface characteristics of coated film Values measured under the following conditions using a non-contact surface shape measurement system (VertScan R550H-M100). For the region surface average roughness (Sa) and the average length (RSm) of the roughness curve element, the average value of 5 measurements was adopted, and for the maximum protrusion height (P), the maximum value of 5 measurements was adopted.
(Measurement condition)
・ Measurement mode: WAVE mode ・ Objective lens: 50x ・ 0.5 × Tube lens ・ Measurement area 187 × 139μm (Sa, P measurement)
-Measurement length (Lr: reference length): 187 μm (RSm measurement)

(2) Evaluation of particle dispersibility of the easy-to-slip coating layer (narrow field of view, VertScan measurement field of view 187 × 139 μm)
The value of the maximum protrusion height (P) measured in (1) above was used for judgment based on the following criteria.
◯: Maximum protrusion height (P) is 0.2 μm or less ○ Δ: Maximum protrusion height (P) is larger than 0.2 μm and smaller than 0.3 μm.
Δ: Maximum protrusion height (P) is 0.3 μm or more

(3) Evaluation of particle dispersibility of the easy-to-slip coating layer (wide field of view, visual measurement field of view 600 mm x 420 mm)
Using an LED light (LED LENSER P5R.2 manufactured by LED LENSER) visually in a dark room, observe four A4 size green sheet manufacturing release films, mark the particle agglomerates that can be seen white, and mark the following. Judgment was made based on such criteria.
⊚: No particle agglomerates ○: 1 to 3 particle agglomerates.
Δ: 4 or more particle agglomerates.

(4) Powder drop resistance A release film for green sheet manufacturing (3 cm (film width direction) x 20 cm (film longitudinal direction)) is easily slipped onto a friction fastness tester (manufactured by Daiei Kagaku Seiki Seisakusho, RT-200). Attach it so that the layer is on top, and use aluminum foil (thickness 80 μm, arithmetic average surface roughness 0.03 μm) for the contact part between the load head part (2 cm x 2 cm, 200 g) and the sample film, and make one round trip over a distance of 10 cm. It was reciprocated 10 times at a speed of 2 seconds. The obtained film was placed on a black mount, and it was visually confirmed whether the powder had fallen off.
◯: No powder falling can be confirmed on the black mount.
Δ: A slight powder drop can be confirmed on the black mount as a whole.

(5) Water (liquid) on the release surface of the release film using a contact angle meter (manufactured by Kyowa Surface Science Co., Ltd .: fully automatic contact angle meter DM-701) under the condition of surface free energy of 25 ° C. and 50% RH. Droplets of 1.8 μL), diiodomethane (suitable amount of liquid 0.9 μL), and ethylene glycol (suitable amount of 0.9 μL liquid) were prepared and their contact angles were measured. As the contact angle, the contact angle 10 seconds after dropping each liquid on the release film was adopted. The contact angle data of water, diiodomethane, and ethylene glycol obtained by the above method were calculated from the "Kitasaki-Hata" theory to obtain the dispersion component γsd, polar component γsp, and hydrogen bond component γsh of the surface free energy of the release film. The sum of each component was defined as the surface free energy γs. This calculation was performed using the calculation software in the contact angle meter software (FAMAS).

(6) Unwinding Charge of Release Film Roll The release film for producing a green sheet obtained in each Example and each Comparative Example was rolled into a roll having a width of 400 mm and a length of 5000 m to obtain a release film roll. After storing this release film roll in an environment of 40 ° C. and a humidity of 50% or less for 30 days, the amount of charge when rewinding at 100 m / min was measured using "KSD-0103" manufactured by Kasuga Electric Co., Ltd. The amount of charge was measured at 100 mm immediately after unwinding every 500 M unwinding length, and the average value was calculated.
◯: Less than ± 3 kV
○ △: ± 3 kV or more and less than 5 kV △: ± 5 kV or more and less than 10 kV
×: ± 10 kV or more

(7) Evaluation of pinholes and thickness variation of ceramic green sheet The composition consisting of the following materials is stirred and mixed, and dispersed for 2 hours using a paint shaker using 2.0 mm glass beads as a dispersion medium to obtain a ceramic slurry. rice field.
Toluene 22.5% by mass
Ethanol 22.5% by mass
Barium titanate 50% by mass
(HPBT-1 manufactured by Fuji Titanium Industry Co., Ltd.)
Polyvinyl butyral 5% by mass
(Sekisui Chemical Eslek BH-3)
Next, the release surface of the release film sample was coated with an applicator so that the dried slurry had a thickness of 0.5 μm, dried at 90 ° C. for 1 minute, and then the slurry surface and the smoothed coating layer surface were overlapped with each other. After applying a load of 1 kg / cm ² for a minute, the release film was peeled off to obtain a ceramic green sheet.
In the central region of the obtained ceramic green sheet in the film width direction, shine light from the opposite surface of the coated surface of the ceramic slurry within a range of 25 cm ² , observe the occurrence of pinholes through which light can be seen, and use the following criteria. It was judged visually.
⊚: No pinholes, thickness variation is particularly good ○: No pinholes, thickness variation No particular problem Δ: Pinholes are very slight and thickness variation is slightly visible.
X: There are a few pinholes, and the thickness variation is a little noticeable.

(Preparation of polyethylene terephthalate pellets (PET (I)))
As the esterification reaction device, a continuous esterification reaction device consisting of a stirrer, a splitter, a raw material charging port, and a three-stage complete mixing tank having a raw material charging port and a product outlet was used. TPA (terephthalic acid) is 2 tons / hour, EG (ethylene glycol) is 2 mol per 1 mol of TPA, antimony trioxide is made up to 160 ppm of Sb atoms with respect to the PET produced, and these slurrys are esterified. It was continuously supplied to the first esterification reaction can of the chemical reaction apparatus, and reacted at normal pressure with an average residence time of 4 hours and 255 ° C. Next, the reaction product in the first esterification reaction can is continuously taken out of the system and supplied to the second esterification reaction can, and distilled off from the first esterification reaction can in the second esterification reaction can. EG is supplied in an amount of 8% by mass with respect to the produced PET, and an EG solution containing magnesium acetate tetrahydrate in an amount of 65 ppm of Mg atoms with respect to the produced PET and 40 ppm of P atoms with respect to the produced PET. An EG solution containing an amount of TMPA (trimethyl phosphate) was added, and the reaction was carried out at normal pressure for an average residence time of 1 hour and 260 ° C. Next, the reaction product of the second esterification reaction can was continuously taken out of the system and supplied to the third esterification reaction can, and 39 MPa (400 kg / cm ² ) was used using a high-pressure disperser (manufactured by Nippon Seiki Co., Ltd.). 0.2% by mass of porous colloidal silica having an average particle size of 0.9 μm and 1% by mass of ammonium salt of polyacrylic acid attached per calcium carbonate after dispersion treatment with an average number of treatments of 5 passes under the pressure of 0.4% by mass of synthetic calcium carbonate having a diameter of 0.6 μm was added as an EG slurry of 10% each, and the reaction was carried out at normal pressure for an average residence time of 0.5 hours and at 260 ° C. The esterification reaction product produced in the third esterification reaction can was continuously supplied to a three-stage continuous polycondensation reaction apparatus to perform polycondensation, and a stainless steel fiber having a 95% cut diameter of 20 μm was sintered. After filtering with a filter, it was subjected to ultracondensation, extruded into water, cooled, and then cut into chips to obtain PET chips with an intrinsic viscosity of 0.60 dl / g (hereinafter abbreviated as PET (I)). .. The lubricant content in the PET chip was 0.6% by mass.

(Preparation of polyethylene terephthalate pellets (PET (II)))
On the other hand, in the production of the PET chip, a PET chip having an intrinsic viscosity of 0.62 dl / g containing no particles such as calcium carbonate and silica was obtained (hereinafter abbreviated as PET (II)).

(Manufacturing of laminated film Z)
These PET chips are dried, melted at 285 ° C, melted at 290 ° C by a separate melt extruder extruder, and have a filter obtained by sintering stainless steel fibers having a 95% cut diameter of 15 μm, and a 95% cut diameter. Two-stage filtration of a filter obtained by sintering 15 μm stainless steel particles is performed to merge them in a feed block, and PET (I) becomes an anti-separation surface side layer and PET (II) becomes a release surface side layer. It is laminated in such a manner, extruded (casting) into a sheet at a speed of 45 m / min, electrostatically adhered and cooled on a casting drum at 30 ° C. by an electrostatic adhesion method, and has an unstretched intrinsic viscosity of 0.59 dl / g. A polyethylene terephthalate sheet was obtained. The layer ratio was adjusted so that PET (I) / (II) = 60% / 40% in the discharge amount calculation of each extruder. Next, the unstretched sheet was heated with an infrared heater and then stretched 3.5 times in the vertical direction at a roll temperature of 80 ° C. due to the speed difference between the rolls. Then, it was guided to a tenter and stretched 4.2 times in the lateral direction at 140 ° C. Then, in the heat fixing zone, heat treatment was performed at 210 ° C. Then, a 2.3% relaxation treatment was carried out laterally at 170 ° C. to obtain a biaxially stretched polyethylene terephthalate film Z having a thickness of 31 μm. The Sa of the release surface side layer of the obtained film Z was 2 nm, and the Sa of the release surface side layer was 28 nm.

(Manufacturing of acrylic polyol A-1)
77 parts by mass of methyl methacrylate (MMA), 100 parts by mass of hydroxyethyl methacrylate (HEMA), 33 parts by mass of methacrylic acid (MAA) in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blow tube. And 490 parts by mass of isopropyl alcohol (IPA) was charged, and the temperature inside the flask was raised to 80 ° C. with stirring. Stirring was performed for 3 hours while maintaining the inside of the flask at 80 ° C., and then 2,2-azobis-2-methyl-N-2-hydroxyethylpropionamide was added to the flask by 0.5 parts by mass. After nitrogen substitution was performed while raising the temperature in the flask to 120 ° C., the mixture was stirred at 120 ° C. for 2 hours.
Then, a reduced pressure operation of 1.5 kPa was performed at 120 ° C. to remove unreacted raw materials and solvent to obtain an acrylic polyol. The inside of the flask was returned to atmospheric pressure and cooled to room temperature, and 840 parts by mass of an IPA aqueous solution (water content: 50% by mass) was added and mixed. Then, while stirring, triethylamine was added using a dropping funnel to neutralize the acrylic polyol until the pH of the solution was in the range of 5.5 to 7.5, and the acrylic polyol having a solid content concentration of 20% by mass was treated. (A-1) was obtained. The composition ratio, Tg, stretchability, and acid value of the acrylic polyol (A-1) measured by NMR are also shown in Table 1.

(Manufacturing of acrylic polyols (A-2) to (A-13))
As shown in Table 1, MMA, St, SMA, HEMA, MAA, AA, IPA at the time of preparation, the amount of the IPA aqueous solution at the time of dilution, and the neutralizing agent were changed in the same manner as in the production of acrylic polyol 1. Acrylic polyols (A-2) to (A-13) having a solid content concentration of 20% by mass were obtained. Table 1 also shows the composition ratio, Tg, stretchability, and acid value of acrylic polyols (A-2) to (A-13) measured by NMR. The composition ratios are MMA, St (styrene), SMA (stearyl methacrylate), l-1, l-2, l-3 (unit), HEMA m (unit), MAA, AA (acrylic acid), respectively. Was expressed as n (unit).

(Polymerization of polyester resin B0-1)
194.2 parts by mass of dimethylterephthalate, 184.5 parts by mass of dimethylisophthalate, 14.8 parts by mass of dimethyl-5-sodium sulfoisophthalate, in a stainless steel autoclave equipped with a stirrer, thermometer, and partial reflux condenser. 185.1 parts by mass of ethylene glycol, 185.1 parts by mass of neopentyl glycol, and 0.2 parts by mass of tetra-n-butyl titanate were charged, and a transesterification reaction was carried out at a temperature of 160 ° C to 220 ° C for 4 hours. .. Then, the temperature was raised to 255 ° C., the reaction system was gradually reduced in pressure, and then the reaction was carried out under a reduced pressure of 30 Pa for 1 hour and 30 minutes to obtain a copolymerized polyester resin (B0-1). The obtained copolymerized polyester resin (B0-1) was pale yellow and transparent. The reduced viscosity of the copolymerized polyester resin (B0-1) was measured and found to be 0.60 dl / g. The glass transition temperature by DSC was 65 ° C.

(Manufacturing of polyester aqueous dispersion B-1)
30 parts by mass of polyester resin (B0-1) and 15 parts by mass of ethylene glycol-n-butyl ether were placed in a reactor equipped with a stirrer, a thermometer and a reflux device, and heated at 110 ° C. and stirred to dissolve the resin. After the resin was completely dissolved, 55 parts by mass of water was gradually added to the polyester solution with stirring. After the addition, the liquid was cooled to room temperature with stirring to prepare a milky white polyester aqueous dispersion (B-1) having a solid content of 30% by mass.

(Polyester resin B0-2 polymerization)
In a stainless steel autoclave equipped with a stirrer, thermometer, and partial reflux condenser, 163 parts by mass of dimethylterephthalate, 163 parts by mass of dimethylisophthalate, 169 parts by mass of 1,4 butanediol, 324 parts by mass of ethylene glycol, and 0.5 parts by mass of tetra-n-butyl titanate was charged, and a transesterification reaction was carried out from 160 ° C. to 220 ° C. over 4 hours.
Next, 14 parts by mass of fumaric acid and 203 parts by mass of sebacic acid were added, and the temperature was raised from 200 ° C. to 220 ° C. over 1 hour to carry out an esterification reaction. Then, the temperature was raised to 255 ° C., the reaction system was gradually reduced in pressure, and then the reaction was carried out under a reduced pressure of 29 Pa for 1 hour and 30 minutes to obtain a hydrophobic copolymerized polyester resin (B0-2). The obtained hydrophobic copolymerized polyester resin (B0-2) was pale yellow and transparent.

(Manufacturing of polyester aqueous dispersion B-2)
Next, 60 parts by mass of the copolymerized polyester resin (B0-2), 45 parts by mass of methyl ethyl ketone and 15 parts by mass of isopropyl alcohol were added to a reactor equipped with a stirrer for producing a graft resin, a thermometer, a reflux device and a quantitative dropping device. The resin was dissolved by heating and stirring at 65 ° C. After the resin was completely dissolved, 24 parts by mass of maleic anhydride was added to the polyester solution.
Then, a solution prepared by dissolving 16 parts by mass of styrene and 1.5 parts by mass of azobisdimethylvaleronitrile in 19 parts by mass of methyl ethyl ketone was added dropwise to the polyester solution at 0.1 ml / min, and stirring was continued for another 2 hours. After sampling for analysis from the reaction solution, 8 parts by mass of methanol was added. Then, 300 parts by mass of water and 24 parts by mass of triethylamine were added to the reaction solution, and the mixture was stirred for 1 hour.
Then, the internal temperature of the reactor was raised to 100 ° C., methyl ethyl ketone, isopropyl alcohol, and excess triethylamine were distilled off by distillation to obtain a pale yellow transparent polyester resin, and uniform water dispersibility with a solid content concentration of 25% by mass. A polyester-based graft copolymer dispersion liquid (B-2) was prepared. The glass transition temperature of the obtained polyester-based graft copolymer was 68 ° C.

(Manufacturing of polyurethane aqueous dispersion C-1)
In a four-necked flask equipped with a stirrer, Dimroth condenser, nitrogen introduction tube, silica gel drying tube, and thermometer, 43.75 parts by mass of 4,4-dicyclohexylmethane diisocyanate, 12.85 parts by mass of dimethylol butanoic acid, 153.41 parts by mass of polyhexamethylene carbonate diol having a number average molecular weight of 2000, 0.03 parts by mass of dibutyltin dilaurate, and 84.00 parts by mass of acetone as a solvent were added, and the mixture was stirred at 75 ° C. for 3 hours under a nitrogen atmosphere to react. It was confirmed that the liquid reached the predetermined amine equivalent. Next, the reaction solution was cooled to 40 ° C., and then 8.77 parts by mass of triethylamine was added to obtain a polyurethane prepolymer solution. Next, 450 g of water was added to a reaction vessel equipped with a homodisper capable of high-speed stirring, adjusted to 25 ° C., and the polyurethane prepolymer solution was added and water-dispersed while stirring and mixing at 2000 min ^-1 . .. Then, under reduced pressure, acetone and a part of water were removed to prepare a water-soluble polyurethane resin solution C-1 having a solid content of 37% by mass. The glass transition temperature of the obtained polyurethane resin was −30 ° C.

(Manufacturing of Oxazoline-based Crosslinking Agent D-1)
460.6 parts of isopropyl alcohol was placed in a flask equipped with a stirrer, a reflux condenser, a nitrogen introduction tube and a thermometer, and heated to 80 ° C. while gently flowing nitrogen gas. A monomer mixture consisting of 126 parts of methyl methacrylate, 210 parts of 2-isopropenyl-2-oxazoline and 84 parts of methoxypolyethylene glycol acrylate prepared in advance there, and 2,2'-azobis, which is a polymerization initiator. An initiator solution consisting of 21 parts (2-methylbutyronitrile) (“ABN-E” manufactured by Nippon Hydrazin Industry Co., Ltd.) and 189 parts of isopropyl alcohol is dropped from a dropping funnel over 2 hours to react and then dropped. After the end, the reaction was continued for 5 hours. During the reaction, nitrogen gas was continuously flowed to keep the temperature inside the flask at 80 ± 1 ° C. Then, the reaction solution was cooled to obtain a resin (D-1) having an oxazoline group having a solid content concentration of 25%. The obtained resin (D-1) having an oxazoline group had an oxazoline group amount of 4.3 mmol / g, and the number average molecular weight measured by GPC (gel permeation chromatography) was 20000.

(Manufacturing of Oxazoline-based Crosslinking Agent D-2)
By the same method as the synthesis of the resin (D-1) having an oxazoline group, a resin (D-2) having an oxazoline group having a solid content concentration of 10% and having different compositions (the amount of the oxazoline group and the molecular weight) was obtained. The obtained resin (D-2) having an oxazoline group had an oxazoline group amount of 7.7 mmol / g, and the number average molecular weight measured by GPC was 40,000.

(Manufacturing of Carbodiimide Crosslinking Agent E-1)
A flask equipped with a stirrer, a thermometer, and a reflux cooling tube was charged with 168 parts by mass of hexamethylene diisocyanate and 220 parts by mass of polyethylene glycol monomethyl ether (M400, average molecular weight 400), stirred at 120 ° C. for 1 hour, and further 4, Add 26 parts by mass of 4'-dicyclohexylmethane diisocyanate and 3.8 parts by mass of 3-methyl-1-phenyl-2-phosphoren-1-oxide (2% by mass with respect to the total isosianate) as a carbodiimidation catalyst, and 185 under a nitrogen stream. The mixture was further stirred at ° C. for 5 hours. The infrared spectrum of the reaction solution was measured, and it was confirmed that the absorption at a wavelength of 2200 to 2300 cm ^-1 disappeared. After allowing to cool to 60 ° C., 567 parts by mass of ion-exchanged water was added to obtain a carbodiimide water-soluble resin (E-1) having a solid content of 40% by mass.

(Manufacturing of isocyanate cross-linking agent F-1)
100 parts by mass of a polyisocyanate compound (Duranate TPA manufactured by Asahi Kasei Chemicals Co., Ltd.) using hexamethylene diisocyanate as a raw material in a flask equipped with a stirrer, a thermometer, and a reflux cooling tube, 55 parts by mass of propylene glycol monomethyl ether acetate, 30 parts by mass of polyethylene glycol monomethyl ether (average molecular weight 750) was charged and kept at 70 ° C. for 4 hours under a nitrogen atmosphere. Then, the temperature of the reaction solution was lowered to 50 ° C., and 47 parts by mass of methyl ethyl ketooxime was added dropwise. The infrared spectrum of the reaction solution was measured, and it was confirmed that the absorption of the isocyanate group had disappeared, and a blocked polyisocyanate aqueous dispersion (F-1) having a solid content of 75% by mass was obtained.

(Silica particles G-1)
Colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name MP2040, average particle size 200 nm, solid content concentration 40% by mass)

(Silica particles G-2)
Colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex XL, average particle size: 40 nm, solid content concentration: 40% by mass)

(Silica particles G-3)
Colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name Snowtex ZL, average particle size 100 nm, solid content concentration 40% by mass)

(Silica particles G-4)
Colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name MP4540M, average particle size 450 nm, solid content concentration 40% by mass)

(Acrylic particles G-5)
Acrylic particle aqueous dispersion (manufactured by Nippon Shokubai, trade name MX100W, average particle size 150 nm, solid content concentration 10% by mass)

(Acrylic particles G-6)
Acrylic particle aqueous dispersion (manufactured by Nippon Shokubai, trade name MX200W, average particle size 350 nm, solid content concentration 10% by mass)

(Acrylic particles G-7)
Acrylic particle aqueous dispersion (manufactured by Nippon Shokubai, trade name MX300W, average particle size 450 nm, solid content concentration 10% by mass)

(Release agent solution X-1)
Thermo-curable aminoalkyd resin (Tessfine 314 manufactured by Hitachi Kasei Co., Ltd., solid content 60% by mass) and p-toluenesulfonic acid as a curing catalyst (Hitachi Kasei Co., Ltd., dryer 900, solid content 50% by mass) 1. 2 parts by mass was diluted with a toluene / methyl ethyl ketone / heptane (= 3: 5: 2) solution to prepare a release agent solution having a solid content of 2% by mass.

(Release agent solution X-2)
UV curable silicone resin (UV9300 manufactured by Momentive, solid content concentration 100% by mass) 100 parts by mass and curing catalyst bis (alkylphenyl) iodonium hexafluoroantimonate 1 part by mass, toluene / methyl ethyl ketone / heptane (= 3: 5: 2) Dilute with a solution to prepare a release agent solution having a solid content of 2% by mass.

(Example 1)
(Adjustment of easy slip coating liquid 1)
The I Ching coating liquid 1 having the following composition was adjusted.
(Easy-slip coating liquid 1)
Water 41.86 parts by mass Isopropyl alcohol 35.00 parts by mass Acrylic polyol resin A-1 16.57 parts by mass (solid content concentration 20% by mass)
Oxazoline-based cross-linking agent D-1 5.68 parts by mass (solid content concentration 25% by mass)
Silica particles G-1 0.59 parts by mass (average particle size 200 nm, solid content concentration 40% by mass)
Surfactant H-1 (fluorine-based, solid content concentration 10% by mass) 0.30 parts by mass

(Manufacturing of polyester film)
As a film raw material polymer, PET resin pellets (PET (II)) having an intrinsic viscosity (solvent: phenol / tetrachloroethane = 60/40) of 0.62 dl / g and substantially free of particles were used at 133 Pa. It was dried under reduced pressure at 135 ° C. for 6 hours. Then, it was supplied to an extruder, melt-extruded into a sheet at about 280 ° C., and rapidly cooled and adhered and solidified on a rotary cooling metal roll maintained at a surface temperature of 20 ° C. to obtain an unstretched PET sheet.

This unstretched PET sheet was heated to 100 ° C. with a heated roll group and an infrared heater, and then stretched 3.5 times in the longitudinal direction with a roll group having a peripheral speed difference to obtain a uniaxially stretched PET film.

Then, the easy-slip coating liquid was applied to one side of the PET film with a bar coater, and then dried at 80 ° C. for 15 seconds. The coating amount after final stretching and drying was adjusted to 0.1 μm. Subsequently, with a tenter, the film was stretched 4.0 times in the width direction at 150 ° C., and with the length of the film fixed in the width direction, heated at 230 ° C. for 0.5 seconds, and further heated at 230 ° C. for 10 seconds 3 A relaxation treatment in the width direction of% was performed to obtain an in-line coated polyester film having a thickness of 31 μm.

(Formation of mold release coating layer)
The release agent solution X-1 is applied to the in-line coated polyester film obtained above on the surface opposite to the laminated surface of the easy-to-slip coating layer with a reverse gravure coater so that the thickness after drying is 0.1 μm. A mold release coating layer was formed by drying with hot air at 130 ° C. for 30 seconds to obtain a mold release film for producing an ultrathin ceramic green sheet. The process passability and handleability such as take-up property were excellent without any particular problem. After winding up as a roll, the unwinding charge when rewinding for ceramic sheet coating is low, the adhesion of environmental foreign substances can be suppressed, and the yield of ceramic capacitors is not reduced, and high quality ceramic capacitors are created. I was able to.

(Example 2)
Same as Example 1 except that the easy-slip coating liquid 2 in which the cross-linking agent in the easy-slip coating liquid 1 used in Example 1 was changed to the carbodiimide-based cross-linking agent E-1 (solid content concentration 40% by mass) was used. Then, a release film for manufacturing an ultra-thin ceramic green sheet was obtained.
(Easy slip coating liquid 2)
Water 43.99 parts by mass Isopropyl alcohol 35.00 parts by mass Acrylic polyol resin A-1 16.57 parts by mass (solid content concentration 20% by mass)
Carbodiimide-based cross-linking agent E-1 3.55 parts by mass (solid content concentration 40% by mass)
Silica particles G-1 0.59 parts by mass (average particle size 200 nm, solid content concentration 40% by mass)
Surfactant H-1 (fluorine-based, solid content concentration 10% by mass) 0.30 parts by mass

(Example 3)
Same as Example 1 except that the easy-slip coating liquid 3 in which the cross-linking agent in the easy-slip coating liquid 1 used in Example 1 was changed to the oxazoline-based cross-linking agent D-2 (solid content concentration 10% by mass) was used. Then, a release film for manufacturing an ultra-thin ceramic green sheet was obtained.
(Easy-slip coating liquid 3)
Water 33.34 parts by mass Isopropyl alcohol 35.00 parts by mass Acrylic polyol resin A-1 16.57 parts by mass (solid content concentration 20% by mass)
Oxazoline-based cross-linking agent D-2 14.20 parts by mass (solid content concentration 10% by mass)
Silica particles G-1 0.59 parts by mass (average particle size 200 nm, solid content concentration 40% by mass)
Surface active agent H-1 (fluorine-based, solid content concentration 10% by mass) 0.30 parts by mass

(Example 4)
A polyester film was obtained in the same manner as in Example 1 except that the easy-slip coating liquid 1 was changed to the easy-slip coating liquid 4 described below.
(Easy-slip coating liquid 4)
Water 43.28 parts by mass Isopropyl alcohol 35.00 parts by mass Acrylic polyol resin A-1 9.47 parts by mass (solid content concentration 20% by mass)
Oxazoline-based cross-linking agent D-1 11.36 parts by mass (solid content concentration 25% by mass)
Silica particles G-1 0.59 parts by mass (average particle size 200 nm, solid content concentration 40% by mass)
Surfactant H-1 (fluorine-based, solid content concentration 10% by mass) 0.30 parts by mass

(Example 5)
A polyester film was obtained in the same manner as in Example 1 except that the easy-slip coating liquid 1 was changed to the easy-slip coating liquid 5 described below.
(Easy-slip coating liquid 5)
Water 41.15 parts by mass Isopropyl alcohol 35.00 parts by mass Acrylic polyol resin A-1 20.12 parts by mass (solid content concentration 20% by mass)
Oxazoline-based cross-linking agent D-1 2.84 parts by mass (solid content concentration 25% by mass)
Silica particles G-1 0.59 parts by mass (average particle size 200 nm, solid content concentration 40% by mass)
Surfactant H-1 (fluorine-based, solid content concentration 10% by mass) 0.30 parts by mass

(Example 6)
Except that the acrylic polyol A-1 (solid content concentration 20% by mass) in the easy-to-slip coating liquid 1 used in Example 1 was changed to the acrylic polyol A-2 (solid content concentration 20% by mass), the same as in Example 1. In the same manner, a release film for manufacturing an ultrathin ceramic green sheet was obtained.

(Example 7)
Except for changing the acrylic polyol A-1 (solid content concentration 20% by mass) in the easy-to-slip coating liquid 1 used in Example 1 to acrylic polyol A-3 (solid content concentration 20% by mass), the same as in Example 1. In the same manner, a release film for manufacturing an ultrathin ceramic green sheet was obtained.

(Example 8)
Except that the acrylic polyol A-1 (solid content concentration 20% by mass) in the easy-to-slip coating liquid 1 used in Example 1 was changed to the acrylic polyol A-4 (solid content concentration 20% by mass), the same as in Example 1. In the same manner, a release film for manufacturing an ultrathin ceramic green sheet was obtained.

(Example 9)
Except that the acrylic polyol A-1 (solid content concentration 20% by mass) in the easy-to-slip coating liquid 1 used in Example 1 was changed to the acrylic polyol A-5 (solid content concentration 20% by mass), the same as in Example 1. In the same manner, a release film for manufacturing an ultrathin ceramic green sheet was obtained.

(Example 10)
Except that the acrylic polyol A-1 (solid content concentration 20% by mass) in the easy-to-slip coating liquid 1 used in Example 1 was changed to the acrylic polyol A-6 (solid content concentration 20% by mass), the same as in Example 1. Similarly, a release film for manufacturing an ultra-thin ceramic green sheet was obtained.

(Example 11)
Except that the acrylic polyol A-1 (solid content concentration 20% by mass) in the easy-to-slip coating liquid 1 used in Example 1 was changed to the acrylic polyol A-7 (solid content concentration 20% by mass), the same as in Example 1. In the same manner, a release film for manufacturing an ultrathin ceramic green sheet was obtained.

(Example 12)
Except that the acrylic polyol A-1 (solid content concentration 20% by mass) in the easy-to-slip coating liquid 1 used in Example 1 was changed to the acrylic polyol A-8 (solid content concentration 20% by mass), the same as in Example 1. In the same manner, a release film for manufacturing an ultrathin ceramic green sheet was obtained.

(Example 13)
Except that the acrylic polyol A-1 (solid content concentration 20% by mass) in the easy-to-slip coating liquid 1 used in Example 1 was changed to the acrylic polyol A-9 (solid content concentration 20% by mass), the same as in Example 1. In the same manner, a release film for manufacturing an ultrathin ceramic green sheet was obtained.

(Example 14)
Except that the acrylic polyol A-1 (solid content concentration 20% by mass) in the easy-to-slip coating liquid 1 used in Example 1 was changed to the acrylic polyol A-10 (solid content concentration 20% by mass), the same as in Example 1. In the same manner, a release film for manufacturing an ultrathin ceramic green sheet was obtained.

(Example 15)
Except that the acrylic polyol A-1 (solid content concentration 20% by mass) in the easy-to-slip coating liquid 1 used in Example 1 was changed to the acrylic polyol A-11 (solid content concentration 20% by mass), the same as in Example 1. In the same manner, a release film for manufacturing an ultrathin ceramic green sheet was obtained.

(Example 16)
Except that the acrylic polyol A-1 (solid content concentration 20% by mass) in the easy-to-slip coating liquid 1 used in Example 1 was changed to the acrylic polyol A-12 (solid content concentration 20% by mass), the same as in Example 1. In the same manner, a release film for manufacturing an ultrathin ceramic green sheet was obtained.

(Example 17)
A release film for producing an ultrathin ceramic green sheet was obtained in the same manner as in Example 1 except that the easy-slip coating liquid 1 was changed to the following easy-slip coating liquid 17.
(Easy-slip coating liquid 17)
Water 41.74 parts by mass Isopropyl alcohol 35.00 parts by mass Acrylic polyol resin A-10 16.57 parts by mass (solid content concentration 20% by mass)
Oxazoline-based cross-linking agent D-1 5.68 parts by mass (solid content concentration 25% by mass)
Silica particles G-1 0.59 parts by mass (average particle size 200 nm, solid content concentration 40% by mass)
Silica particles G-4 0.12 parts by mass (average particle size 450 nm, solid content concentration 40% by mass)
Surfactant H-1 (fluorine-based, solid content concentration 10% by mass) 0.30 parts by mass

(Example 18)
A release film for producing an ultra-thin ceramic green sheet was obtained in the same manner as in Example 1 except that the easy-slip coating liquid 1 was changed to the following easy-slip coating liquid 18.
(Easy-slip coating liquid 18)
Water 41.15 parts by mass Isopropyl alcohol 35.00 parts by mass Acrylic polyol resin A-10 16.57 parts by mass (solid content concentration 20% by mass)
Oxazoline-based cross-linking agent D-1 5.68 parts by mass (solid content concentration 25% by mass)
Silica particles G-2 1.18 parts by mass (average particle size 40 nm, solid content concentration 40% by mass)
Silica particles G-4 0.12 parts by mass (average particle size 450 nm, solid content concentration 40% by mass)
Surfactant H-1 (fluorine-based, solid content concentration 10% by mass) 0.30 parts by mass

(Example 19)
A release film for producing an ultra-thin ceramic green sheet was obtained in the same manner as in Example 1 except that the easy-slip coating liquid 1 was changed to the following easy-slip coating liquid 19.
(Easy-slip coating liquid 19)
Water 41.27 parts by mass Isopropyl alcohol 35.00 parts by mass Acrylic polyol resin A-10 16.57 parts by mass (solid content concentration 20% by mass)
Oxazoline-based cross-linking agent D-1 5.68 parts by mass (solid content concentration 25% by mass)
Silica particles G-3 1.18 parts by mass (average particle size 100 nm, solid content concentration 40% by mass)
Surfactant H-1 (fluorine-based, solid content concentration 10% by mass) 0.30 parts by mass

(Example 20)
A release film for producing an ultra-thin ceramic green sheet was obtained in the same manner as in Example 1 except that the easy-slip coating liquid 1 was changed to the following easy-slip coating liquid 20.
(Easy-slip coating liquid 20)
Water 40.09 parts by mass Isopropyl alcohol 35.00 parts by mass Acrylic polyol resin A-10 16.57 parts by mass (solid content concentration 20% by mass)
Oxazoline-based cross-linking agent D-1 5.68 parts by mass (solid content concentration 25% by mass)
Acrylic particles G-5 2.37 parts by mass (average particle size 150 nm, solid content concentration 10% by mass)
Surfactant H-1 (fluorine-based, solid content concentration 10% by mass) 0.30 parts by mass

(Example 21)
A mold release film for producing an ultrathin ceramic green sheet was obtained in the same manner as in Example 1 except that the mold release coating layer was formed as described below.
(Formation of mold release coating layer)
The release agent solution X-2 was applied to the obtained in-line coated polyester film with a reverse gravure coater so that the thickness after drying was 0.1 μm, and then dried with hot air at 90 ° C. for 30 seconds, and then immediately absent. Ultraviolet irradiation (300 mJ / cm ² ) was performed with an electrode lamp (H valve manufactured by Heraeus Co., Ltd.) to form a release coating layer, and a release film for producing an ultrathin ceramic green sheet was obtained.

(Example 22)
Except that the acrylic polyol A-1 (solid content concentration 20% by mass) in the easy-to-slip coating liquid 1 used in Example 1 was changed to the acrylic polyol A-13 (solid content concentration 20% by mass), the same as in Example 1. In the same manner, a release film for manufacturing an ultrathin ceramic green sheet was obtained.

(Example 23)
A release film for producing an ultra-thin ceramic green sheet was obtained in the same manner as in Example 1 except that the easy-slip coating liquid 1 was changed to the following easy-slip coating liquid 22.
(Easy-slip coating liquid 22)
Water 41.39 parts by mass Isopropyl alcohol 35.00 parts by mass Acrylic polyol resin A-13 16.57 parts by mass (solid content concentration 20% by mass)
Oxazoline-based cross-linking agent D-1 5.68 parts by mass (solid content concentration 25% by mass)
Silica particles G-1 0.59 parts by mass (average particle size 200 nm, solid content concentration 40% by mass)
Acrylic particles G-6 0.47 parts by mass (average particle size 350 nm, solid content concentration 10% by mass)
Surfactant H-1 (fluorine-based, solid content concentration 10% by mass) 0.30 parts by mass

(Example 24)
A release film for producing an ultra-thin ceramic green sheet was obtained in the same manner as in Example 1 except that the easy-slip coating liquid 1 was changed to the following easy-slip coating liquid 23.
(Easy-slip coating liquid 23)
Water 41.39 parts by mass Isopropyl alcohol 35.00 parts by mass Acrylic polyol resin A-13 16.57 parts by mass (solid content concentration 20% by mass)
Oxazoline-based cross-linking agent D-1 5.68 parts by mass (solid content concentration 25% by mass)
Silica particles G-1 0.59 parts by mass (average particle size 200 nm, solid content concentration 40% by mass)
Acrylic particles G-7 0.47 parts by mass (average particle size 450 nm, solid content concentration 10% by mass)
Surfactant H-1 (fluorine-based, solid content concentration 10% by mass) 0.30 parts by mass

(Example 25)
A release film for producing an ultra-thin ceramic green sheet was obtained in the same manner as in Example 1 except that the easy-slip coating liquid 1 was changed to the following easy-slip coating liquid 24.
(Easy-slip coating liquid 24)
Water 39.62 parts by mass Isopropyl alcohol 35.00 parts by mass Acrylic polyol resin A-13 16.57 parts by mass (solid content concentration 20% by mass)
Oxazoline-based cross-linking agent D-1 5.68 parts by mass (solid content concentration 25% by mass)
Acrylic particles G-5 2.37 parts by mass (average particle size 150 nm, solid content concentration 10% by mass)
Acrylic particles G-7 0.47 parts by mass (average particle size 450 nm, solid content concentration 10% by mass)
Surfactant H-1 (fluorine-based, solid content concentration 10% by mass) 0.30 parts by mass

(Comparative Example 1)
A polyester film was obtained in the same manner as in Example 1 except that the easy-slip coating liquid 1 was changed to the easy-slip coating liquid 25 described below.
(Easy-slip coating liquid 25)
Water 48.33 parts by mass Isopropyl alcohol 35.00 parts by mass Polyester aqueous dispersion B-1 15.78 parts by mass (solid content concentration 30% by mass)
Silica particles G-1 0.59 parts by mass (average particle size 200 nm, solid content concentration 40% by mass)
Surfactant (fluorine-based, solid content concentration 10% by mass) 0.30 parts by mass

(Comparative Example 2)
A polyester film was obtained in the same manner as in Example 1 except that the easy-slip coating liquid 1 was changed to the easy-slip coating liquid 26 described below.
(Easy-slip coating liquid 26)
Water 45.18 parts by mass Isopropyl alcohol 35.00 parts by mass Polyester aqueous dispersion B-2 18.93 parts by mass (solid content concentration 25% by mass)
Silica particles G-1 0.59 parts by mass (average particle size 200 nm, solid content concentration 40% by mass)
Surfactant (fluorine-based, solid content concentration 10% by mass) 0.30 parts by mass

(Comparative Example 3)
A polyester film was obtained in the same manner as in Example 1 except that the easy-slip coating liquid 1 was changed to the following easy-slip coating liquid 27.
(Easy-slip coating liquid 27)
51.32 parts by mass of water Isopropyl alcohol 35.00 parts by mass Polyurethane resin water dispersion C-1 12.79 parts by mass (solid content concentration 37% by mass)
Silica particles G-1 0.59 parts by mass (average particle size 200 nm, solid content concentration 40% by mass)
Surfactant (fluorine-based, solid content concentration 10% by mass) 0.30 parts by mass

(Comparative Example 4)
A polyester film was obtained in the same manner as in Example 1 except that the easy-slip coating liquid 1 was changed to the following easy-slip coating liquid 28.
(Easy-slip coating liquid 28)
47.39 parts by mass of water Isopropyl alcohol 35.00 parts by mass Polyester aqueous dispersion B-1 11.04 parts by mass (solid content concentration 30% by mass)
Oxazoline-based cross-linking agent D-1 5.68 parts by mass (solid content concentration 25% by mass)
Silica particles G-1 0.59 parts by mass (average particle size 200 nm, solid content concentration 40% by mass)
Surfactant (fluorine-based, solid content concentration 10% by mass) 0.30 parts by mass

(Comparative Example 5)
A polyester film was obtained in the same manner as in Example 1 except that the easy-slip coating liquid 1 was changed to the following easy-slip coating liquid 29.
(Easy-slip coating liquid 29)
Water 49.51 parts by mass Isopropyl alcohol 35.00 parts by mass Polyester aqueous dispersion B-1 11.04 parts by mass (solid content concentration 30% by mass)
Carbodiimide-based cross-linking agent E-1 3.55 parts by mass (solid content concentration 40% by mass)
Silica particles G-1 0.59 parts by mass (average particle size 200 nm, solid content concentration 40% by mass)
Surfactant (fluorine-based, solid content concentration 10% by mass) 0.30 parts by mass

(Comparative Example 6)
A polyester film was obtained in the same manner as in Example 1 except that the easy-slip coating liquid 1 was changed to the easy-slip coating liquid 30 described below.
(Easy-slip coating liquid 30)
Water 40.44 parts by mass Isopropyl alcohol 35.00 parts by mass Acrylic polyol resin A-1 23.67 parts by mass (solid content concentration 20% by mass)
Silica particles G-1 0.59 parts by mass (average particle size 200 nm, solid content concentration 40% by mass)
Surfactant H-1 (fluorine-based, solid content concentration 10% by mass) 0.30 parts by mass

(Comparative Example 7)
A polyester film was obtained in the same manner as in Example 1 except that the easy-slip coating liquid 1 was changed to the following easy-slip coating liquid 31.
(Easy-slip coating liquid 31)
Water 45.65 parts by mass Isopropyl alcohol 35.00 parts by mass Acrylic polyol resin A-1 16.57 parts by mass (solid content concentration 20% by mass)
Isocyanate cross-linking agent F-1 1.89 parts by mass (solid content concentration 75% by mass)
Silica particles G-1 0.59 parts by mass (average particle size 200 nm, solid content concentration 40% by mass)
Surfactant H-1 (fluorine-based, solid content concentration 10% by mass) 0.30 parts by mass

(Comparative Example 8)
As a film for forming a release coating layer, it was carried out except that it was changed to E5000-25 μm (manufactured by Toyobo) instead of the in-line coating film having an easy-slip coating layer on one surface prepared in Example 1. A release film for producing a ceramic green sheet was obtained in the same manner as in Example 1. E5000 contained particles inside the film, and Sa on both surfaces was 0.031 μm.

(Comparative Example 9)
As the film forming the release coating layer, the same as in Example 1 except that the laminated film Z was used instead of the in-line coating film having the easy-slip coating layer on one surface prepared in Example 1. A release film for manufacturing a ceramic green sheet was obtained by the above method. A release coating layer was provided on the surface (the layer containing no particles) from which the PET (II) pellets of the laminated film Z were discharged.

The evaluation results of each Example and Comparative Example are shown in Tables 2 and 3.

In Table 2 above, the compositions of the resin, the cross-linking agent, the particles, and the surfactant in the easy-slip coating liquid are described as parts by mass of the solid content, and the resin and the cross-linking agent present in the easy-slip coating liquid are described. , The total mass of the solid content of the particles and the surfactant is the mass part of the total solid content of the easy-to-slip coating layer, and for the resin, the cross-linking agent, the particles and the surfactant, the mass part of each solid content is easily slipped. By dividing by the mass part of the total solid content of the coating layer, the mass percentage of the total solid text of the resin, the cross-linking agent, the particles, and the surfactant in the easy-to-slip coating layer can be obtained.

In Examples 1 to 25, since the unwinding charge when the roll is rewound after the mold release process is low and environmental foreign matter does not easily adhere to the roll, a high-quality ceramic capacitor is produced without reducing the yield of the ceramic capacitor. I was able to. As the release film, a polyester film that does not substantially contain inorganic particles is used as a base material, the release coating layer is provided on one surface of the base material, and particles are contained on the other surface. Since the composition having an easy-slip coating layer and the easy-slip coating layer contains an acrylic resin and at least one cross-linking agent selected from an oxazoline-based cross-linking agent or a carbodiimide-based cross-linking agent is cured, the easy-slip coating layer is formed. The crosslink density of the coating layer is high and the amount of deformation of the easy-to-slip coating layer is small. It is considered that the amount of charge could be suppressed because the contact area became smaller when the release layer and the easy-to-slip layer were peeled off when the release-processed film roll was unwound.
On the other hand, in Comparative Examples 1 to 7, the easy-slip coating is obtained by curing a composition containing the acrylic resin specified in the present invention and at least one cross-linking agent selected from an oxazoline-based cross-linking agent or a carbodiimide-based cross-linking agent. Since it is not a layer, the crosslink density of the easy-slip coating layer is low, and the amount of deformation of the easy-slip coating layer is large. It is probable that the unwinding charge increased because the contact area increased when the release layer and the easy-slip layer were peeled off when the release-processed film roll was unwound. Further, in Comparative Examples 8 and 9, although the unwinding charge is low, the ceramic sheet does not have the easy-slip coating layer specified in the present invention and the surface roughness of the easy-slip surface is large, so that pinholes are generated in the ceramic sheet. did.

According to the present invention, even when the ceramic green sheet is thinned, it is possible to prevent pinholes and partial thickness variations, and to prevent the adhesion of environmental foreign substances due to charging. It becomes possible to provide a film. Further, by using the release film for producing a ceramic green sheet of the present invention, an ultrathin ceramic green sheet can be obtained, and a minute ceramic capacitor can be efficiently produced.

Claims (12)

A coated polyester film for laminating a release coating layer,
The coated polyester film is
A polyester film is used as a base material, and an easy-slip coating layer containing particles is provided on one surface of the base material, and the easy-slip coating layer is selected from an acrylic resin and an oxazoline-based cross-linking agent or a carbodiimide-based cross-linking agent. The composition containing one type of cross-linking agent is cured and becomes
The acid value of the acrylic resin is 40 mgKOH / g or more and 400 mgKOH / g or less.
The surface of the substrate different from the easy-slip coating layer is the surface on which the release coating layer is laminated.
Coated polyester film. The coated polyester film according to claim 1, wherein the acrylic resin is an acrylic resin having a long-chain alkyl group introduced therein. The coated polyester film according to claim 1 or 2, wherein the acrylic resin is neutralized with a basic neutralizing agent. The coated polyester film according to claim 3, wherein the basic neutralizing agent is an amine compound selected from ammonia, trimethylamine, triethylamine and dimethylaminoethanol, or an inorganic basic substance selected from potassium hydroxide and sodium hydroxide. .. The coated polyester film according to any one of claims 1 to 4, wherein the acrylic resin has a glass transition temperature of 50 ° C. or higher and 110 ° C. or lower. Claims that the region surface average roughness (Sa) of the slippery coating layer is 1 nm or more and 25 nm or less, the maximum protrusion height (P) is 60 nm or more and 500 nm or less, and the average length (RSm) of the roughness curve element is 10 μm or less. Item 2. The coated polyester film according to any one of Items 1 to 5. The coated polyester film according to any one of claims 1 to 6, wherein the slippery coating layer has a thickness of 0.001 μm or more and 2 μm or less. The coated polyester film according to any one of claims 1 to 7 for manufacturing a ceramic green sheet. The coated polyester film according to any one of claims 1 to 8, wherein the release coating layer contains a silicone resin, an aminoalkyd resin or an aminoacrylic resin. The coating polyester film according to any one of claims 1 to 9 is used, and the ceramic slurry is applied to the release coating layer surface.
How to manufacture a ceramic green sheet. The method for manufacturing a ceramic green sheet according to claim 10 , wherein the thickness of the ceramic green sheet to be manufactured is 0.2 μm or more and 2.0 μm or less. A method for manufacturing a ceramic capacitor, which employs the method for manufacturing a ceramic green sheet according to claim 10 .