KR102337032B1 - Release Film for Ceramic Green Sheet Manufacturing - Google Patents

Abstract

[Problem] To provide an excellent release film for manufacturing a ceramic green sheet capable of both preventing pinholes and partial thickness fluctuations and reducing unwinding charging, even when the ceramic green sheet is thinned. [Solution] Using a polyester film substantially free of inorganic particles as a base material, a release coating layer having a release coating layer on one surface of the base material, and a release coating layer containing particles on the other surface, A release film for producing a ceramic green sheet, wherein the lubricating coating layer is cured of a composition containing an acrylic resin and at least one crosslinking agent selected from an oxazoline-based crosslinking agent or a carbodiimide-based crosslinking agent.

Description

Release Film for Ceramic Green Sheet Manufacturing

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

Conventionally, when the release film for ceramic green sheet production is stored in a wound state by relatively roughening the surface roughness of the surface (rear surface) opposite to the surface on which the release agent layer is provided, the front and back sides of the release film for ceramic green sheet production are affixed. A technique for solving problems such as (blocking) is disclosed (for example, refer to Patent Document 1). However, this prior art has a problem that, since the protrusions are large, pinholes and partial thickness fluctuations occur.

Therefore, in order to reduce the height of the projections, there is disclosed a technique for preventing the occurrence of pinholes or partial thickness variations in the ceramic green sheet by embedding the projections on the back surface with an application layer (for example, Patent Document 2) Reference). However, according to this prior art, although the protrusion height is low, since the protrusion density is low, the pressure applied to the protrusions is high, and when the ceramic green sheet is further thinned, there is a problem that pinholes are generated.

Japanese Patent Laid-Open No. 2003-203822 Japanese Patent Laid-Open No. 2014-144636

The present invention has been made against the background of these prior art problems. That is, an object of the present invention is to provide an excellent release film for manufacturing a ceramic green sheet, which can prevent pinholes and partial thickness fluctuations, and reduce unwinding charging, even when the ceramic green sheet is thinned. .

MEANS TO SOLVE THE PROBLEM This inventor came to completion of this invention, as a result of earnestly examining in order to achieve this objective. That is, this invention includes the following structures.

1. Using a polyester film substantially free of inorganic particles as a base material, having a release coating layer on one surface of the base material, and a release coating layer containing particles on the other surface, A release film for producing a ceramic green sheet, wherein the lubricating coating layer is obtained by curing a composition containing an acrylic resin and at least one crosslinking agent selected from an oxazoline-based crosslinking agent or a carbodiimide-based crosslinking agent.

2. The release film for ceramic green sheet manufacture as described in said 1 whose glass transition temperature of an acrylic resin is 50 degreeC or more and 110 degrees C or less.

3. The release film for manufacturing a ceramic green sheet according to the first or second aspect, wherein the acrylic resin has an acid value of 40 mgKOH/g or more and 400 mgKOH/g or less.

4. The area surface average roughness (Sa) of the lubricating 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 ceramic green sheet manufacture in any one of 3.

5. The release film for manufacturing a ceramic green sheet according to any one of the first to fourth above, wherein the lubricity coating layer has a thickness of 0.001 µm or more and 2 µm or less.

6. The manufacturing method of a ceramic green sheet using the release film for ceramic green sheet manufacture in any one of said 1-5.

7. The method for producing a ceramic green sheet according to the sixth aspect, wherein the thickness of the ceramic green sheet to be manufactured is 0.2 µm or more and 2.0 µm or less.

8. The manufacturing method of a ceramic capacitor which employ|adopts the manufacturing method of the ceramic green sheet of said 6th or 7th.

According to the present invention, even when the ceramic green sheet is thinned, it is possible to provide an excellent release film for manufacturing a ceramic green sheet capable of preventing pinholes and partial thickness fluctuations and reducing unwinding charging.

Hereinafter, the present invention will be described in detail.

The release film for manufacturing a ceramic green sheet of the present invention (hereinafter sometimes simply referred to as a release film) is a release coating layer on one side of a biaxially oriented polyester film, which is a base film, and a release coating layer containing particles on the other side. It is a release film having

The present inventors propose a release film that can cope with the recent thinning of green sheets by making the average length (RSm) of the roughness curve elements of the lubricating surface to be within a specific range in order to increase the protrusion density of the lubricious surface (International Application No. PCT /JP2017/017354). With this technique, by increasing the projection density, it is preferable because good winding performance and prevention of pinholes and partial thickness fluctuations can be further provided while keeping the projection height low.

In the present invention, since the lubricity coating layer is formed by curing a composition containing an acrylic resin and at least one crosslinking agent selected from an oxazoline-based crosslinking agent or a carbodiimide-based crosslinking agent, the hardness of the lubricating coating layer is It becomes suitably high, and the deformation|transformation of the lubrication coating layer at the time of winding up after mold release coating layer coating becomes difficult to occur. In general, it is known that the larger the contact area of two being in contact, the greater the charging when the two are peeled off. When the amount of deformation of the lubricity coating layer is small, the contact area between the lubricity coating layer and the mold release layer is small, and thus unwinding charging when the release film roll is unwound can be suppressed, which is preferable. It is preferable that there is little unwinding charging because it can prevent the quality abnormality of a ceramic capacitor by adhesion to the mold release surface of an environmental foreign material. In the recent trend of thinning ceramic sheets, a release film having a composition of a lubricating coating layer as stipulated in the present invention is effective in that even the adhesion of a minute environmental foreign matter to the release surface, which has not been a problem in the past, becomes a problem, It is more preferable if it is added that the average length (RSm) of the roughness curve elements of the lubricating coating layer falls within a specific range.

(base film)

In the present invention, the film preferably used as the substrate is a film composed of a polyester resin, and mainly contains at least one selected from polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. A polyester film to do is preferable. Moreover, as a part of the dicarboxylic acid component or diol component of the above polyester, the film containing the polyester in which the 3rd component monomer was copolymerized may be sufficient. Among these polyester films, a polyethylene terephthalate film is the most preferable from the balance of a physical property and cost.

In addition, a single layer may be sufficient as the said polyester film, and a multilayer may be sufficient as it. In addition, as long as it exists in the range which exhibits the desired effect in this invention, each of these layers can be made to contain various additives in a polyester resin as needed. As an additive, antioxidant, a light resistance agent, antigelling agent, an organic wetting agent, an antistatic agent, a ultraviolet absorber etc. are mentioned, for example.

(Easy coating layer)

The release film of this invention has a lubricity coating layer on one surface of the base film made from the above polyester. It is preferable that the binder resin and particle|grains are contained in the lubricating coating layer at least.

(Binder resin in the lubricating coating layer)

It is preferable that an acrylic resin is contained as binder resin which comprises the lubricating coating layer in this invention. It is preferable that an acrylic resin is an acrylic resin which has a hydroxyl group and a carboxyl group in a molecule|numerator. As for the structural unit which has a hydroxyl group, it is more preferable that 20-90 mol% is contained in 100 mol% of all the structural units. It is preferable that the water solubility of an acrylic resin can be maintained suitably that the structural unit which has a hydroxyl group is 20 mol% or more. On the other hand, when it is 90 mol% or less, it is preferable that the hydroxyl group of the acrylic resin and the particles contained in the lubricating coating layer do not extremely interact, and the particles are uniformly dispersed.

In order to introduce a hydroxyl group into the acrylic resin, a monomer having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; - A ring-opening adduct of γ-butyrolactone or ε-caprolactone to hydroxyethyl (meth)acrylate may be used as a copolymerization component. Especially, 2-hydroxyethyl (meth)acrylate is preferable at the point which does not impair water solubility. In addition, these may use 2 or more types together. Needless to say, the acrylic resin as used in the present invention includes a methacrylic resin.

It is preferable that the hydroxyl value of an acrylic resin is 2 mgKOH/g or more, More preferably, it is 5 mgKOH/g or more, More preferably, it is 10 mgKOH/g or more. The water solubility of an acrylic resin becomes favorable that the hydroxyl value of an acrylic resin is 2 mgKOH/g or more, and it is preferable.

It is preferable that the hydroxyl value of an acrylic resin is 250 mgKOH/g or less, More preferably, it is 230 mgKOH/g or less, More preferably, it is 200 mgKOH/g or less. When the hydroxyl 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 lubricating coating layer do not cause an extreme interaction and the particles are uniformly dispersed.

It is preferable that the acrylic resin used by this invention is resin which has a carboxyl group in addition to a hydroxyl group. By having a carboxyl group, it becomes possible to form a crosslinked structure with a crosslinking agent, and to provide water solubility easily. Examples include monomers containing carboxyl groups such as (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid, and monomers containing acid anhydride groups such as maleic anhydride and itaconic anhydride.

4 mol% or more is preferable in 100 mol% of all the structural units of an acrylic resin, and, as for the monomer which has a carboxyl group, 10 mol% or more is more preferable. If it is 4 mol% or more, it becomes easy to form a crosslinked structure in an lubricity coating layer, and to provide water solubility, and it is preferable. 65 mol% or less is preferable and, as for the monomer which has a carboxyl group, 50 mol% or less is more preferable. If it is 65 mol% or less, Tg of the coating film obtained does not become high too much with respect to the suitable range mentioned later, film formability and the extending|stretching titration in in-line coating are favorable, and it is preferable.

In order to express favorable water solubility, it is preferable to neutralize the carboxyl group introduce|transduced into an acrylic resin by copolymerization of 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. For this purpose, it is preferable to use an amine compound as a neutralizing agent. Among them, ammonia is most preferable in that agglomeration of particles does not occur. Moreover, as a neutralization rate, it is preferable that they are 30 mol% - 95 mol%, More preferably, they are 40 mol% - 90 mol%. When the neutralization ratio is 30 mol% or more, the water solubility of the acrylic resin is sufficient, the acrylic resin is easily dissolved during the preparation of the coating solution, and there is no fear of whitening of the coated film surface after drying, which is preferable. On the other hand, if the neutralization rate is 95 mol% or less, the water solubility is not too high, and mixing of alcohol or the like becomes easy in the preparation of the coating liquid, which is preferable.

It is preferable that the acid value of an acrylic resin is 40 mgKOH/g or more, More preferably, it is 50 mgKOH/g or more, More preferably, it is 60 mgKOH/g or more. Since the crosslinking point with an oxazoline crosslinking agent or carbodiimide crosslinking agent increases that the acid value of an acrylic resin is 40 mgKOH/g or more, since a firm coating film with higher crosslinking density is obtained, it is preferable.

It is preferable that the acid value of an acrylic resin is 400 mgKOH/g or less, More preferably, it is 350 mgKOH/g or less, More preferably, it is 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 lubricating layer do not cause an extreme interaction and the particles are uniformly dispersed. When the dispersibility of the particles is good, coarse projections do not occur on the lubricating surface and pinholes in the ceramic sheet do not occur, which is preferable.

It is preferable that the glass transition temperature (Tg) of an acrylic resin is 50 degreeC or more, More preferably, it is 55 degreeC or more, More preferably, it is 60 degreeC or more. When the glass transition temperature of an acrylic resin is 50 degreeC or more, the hardness of a lubricating coating layer becomes high moderately, and it is preferable.

It is preferable that the glass transition temperature (Tg) of an acrylic resin is 110 degrees C or less, More preferably, it is 105 degrees C or less, More preferably, it is 100 degrees C or less. When the glass transition temperature of the acrylic resin is 110° C. or less, it is preferable in the stretching step after coating the lubricating coating layer, since cracks do not occur in the coating film and the coating film is stretched uniformly.

As a monomer for Tg adjustment copolymerized in order to make Tg into the said range, a (meth)acrylic-type monomer and a non-acrylic-type 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, n- Amyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, (meth)acrylic acid alkyl esters, such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and stearyl (meth)acrylate; nitrogen-containing acrylic monomers such as (meth)acrylamide, diacetoneacrylamide, n-methylolacrylamide, and (meth)acrylonitrile; Vinyl methacrylate etc. are mentioned, These can use 1 type, or 2 or more types.

Examples of the non-acrylic vinyl monomer include styrene-based monomers such as styrene, α-methylstyrene, vinyltoluene (a mixture of m-methylstyrene and p-methylstyrene), and chlorostyrene; Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, blood vinyl esters such as vinyl valerate, vinyl octylate, vinyl monochloroacetate, divinyl adipate, vinyl crotonate, vinyl sorbate, vinyl benzoate, and vinyl cinnamate; halogenated vinyl monomers such as vinyl chloride and vinylidene chloride; one type or two or more types may be used.

It is preferable to set it as the remainder, after determining the appropriate amount of a monomer for Tg adjustment of a hydroxyl-containing monomer and a carboxyl-group containing monomer. Tg of a copolymer is calculated|required by the following Fox formula.

W _n : mass fraction of each monomer (mass %)

Tg _n : Tg (K) of the homopolymer of each monomer

As a monomer to be 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 an acrylic resin into which the long-chain alkyl group was introduce|transduced, what has a C8-20 alkyl group in the side chain of an acrylic resin is preferable. Moreover, it is a polymer which has (meth)acrylic acid ester as a main repeating unit, and the copolymer which contains the C8-C20 long-chain alkyl group in the transesterified part can also be used suitably.

50 mol% or less is preferable in 100 mol% of all the structural units of an acrylic resin, and, as for the monomer which has a long-chain alkyl group in the monomer copolymerized for Tg adjustment, 40 mol% or less is more preferable. If it is 50 mol% or less, Tg of the coating film obtained does not become low too much with respect to a suitable range, and since the hardness of a coating film can be maintained high, it is preferable. In this invention, 0 mol% of a monomer which has a long-chain alkyl group may be sufficient as long as Tg is a thing which can maintain a suitable range, However, If it is 5 mol% or more, the effect of Tg adjustment of an acrylic resin becomes clear and it is preferable.

The acrylic resin used by this invention can be obtained by well-known radical polymerization. All of emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, etc. are employable. From the point 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. , ethyl solosolve, ethyl carbitol, butyl carbitol, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and the like. You may use these by mixing with water.

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

As for the mass average molecular weight (Mw) of an acrylic resin, about 10,000-200,000 are preferable. A more preferred range is 20,000 to 150,000. When Mw is 10,000 or more, there is no fear of thermal decomposition in a tenter, and it is preferable. When Mw is 200,000 or less, there is no significant increase in the viscosity of the coating liquid, and coatability is good, which is preferable.

As a binder of the lubricating coating layer in this invention, you may use together other binder resin other than an acrylic resin. Examples of other binder resins include polyester resins, urethane resins, polyvinyl resins (such as polyvinyl alcohol), polyalkylene glycol, polyalkyleneimine, methyl cellulose, hydroxycellulose, and starch.

As content in the lubricity coating layer of an acrylic resin, 20 mass % or more and 95 mass % or less are preferable in total solid. More preferably, they are 30 mass % or more and 90 mass % or less. If it is 20 mass % or more, since the carboxyl group which is a crosslinking component does not decrease too much and a crosslinking density does not become low, it is preferable. If it is 95 mass % or less, since the quantity of the crosslinking agent which is a crosslinking object does not decrease too much and a crosslinking density does not become low, it is preferable.

(crosslinking agent)

In the present invention, in order to form a crosslinked structure in the lubricating coating layer, the lubricating coating layer preferably contains at least one crosslinking agent selected from an oxazoline-based crosslinking agent or a carbodiimide-based crosslinking agent. By containing an oxazoline-based crosslinking agent or carbodiimide-based crosslinking agent, the adhesion to the PET substrate is improved, and the coating film strength of the lubricating layer can be improved by promoting crosslinking with the carboxyl group of the acrylic resin, and as a result, the release film roll Unwinding electrification when unwinding can be suppressed. Moreover, you may use another crosslinking agent together, As a specific crosslinking agent which can be used together, a urea type, an epoxy type, a melamine type, an isocyanate type, a silanol type, etc. are mentioned. Moreover, in order to accelerate|stimulate a crosslinking reaction, a catalyst etc. can be used suitably as needed.

As a crosslinking agent having an oxazoline group, for example, obtained by copolymerizing a polymerizable unsaturated monomer having an oxazoline group with other polymerizable unsaturated monomers as necessary by a conventionally known method (eg solution polymerization, emulsion polymerization, etc.) The polymer etc. which have an oxazoline group are mentioned.

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, 2- Isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, etc. are mentioned. These may be used independently and may use 2 or more types together.

Examples of other polymerizable unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclo C1-C24 alkyl or cycloalkyl ester of (meth)acrylic acid, such as hexyl (meth)acrylate, lauryl (meth)acrylate, and isobornyl (meth)acrylate; C2-C8 hydroxyalkyl ester of (meth)acrylic acid, such as 2-hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate; vinyl aromatic compounds such as styrene and vinyltoluene; Adducts of (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate and amines; polyethylene glycol (meth) acrylate; N-vinylpyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, vinyl acetate, (meth)acrylonitrile, etc. are mentioned. These may be used independently and may use 2 or more types together.

The other polymerizable unsaturated monomer is preferably a hydrophilic monomer from the viewpoint of improving compatibility with other resins, wettability, crosslinking reaction efficiency, etc. by using the obtained crosslinking agent having an oxazoline group as a water-soluble crosslinking agent. Examples of the hydrophilic monomer include a monomer having a polyethylene glycol chain, such as 2-hydroxyethyl (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, a monoester compound of (meth) acrylic acid and polyethylene glycol, 2-aminoethyl ( Meth)acrylate and its salts, (meth)acrylamide, N-methylol (meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide, (meth)acrylonitrile, sodium styrenesulfonate, etc. can be heard Among these, the monomer which has a polyethyleneglycol chain|strand, such as methoxy polyethyleneglycol (meth)acrylate with high solubility with respect to water, and the monoester compound of (meth)acrylic acid and polyethyleneglycol, is preferable.

It is preferable that the oxazoline group content of the crosslinking agent which has an oxazoline group is 3.0-9.0 mmol/g. More preferably, it exists in the range of 4.0-8.0 mmol/g. If it exists in the range of 4.0-8.0 mmol/g, since an appropriate crosslinked structure can be formed, it is preferable.

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

Examples of the diisocyanate as a raw material for synthesis of the polycarbodiimide compound include isomers of toluylene diisocyanate, aromatic diisocyanates such as 4,4-diphenylmethane diisocyanate, and aromatic aliphatic diisocyanates such as xylylene diisocyanate. alicyclic diisocyanates such as isophorone diisocyanate and 4,4-dicyclohexylmethane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, hexamethylene diisocyanate, and 2,2; Aliphatic diisocyanate, such as 4-trimethyl hexamethylene diisocyanate, is mentioned. From the problem of yellowing, aromatic aliphatic diisocyanates, alicyclic diisocyanates and aliphatic diisocyanates are preferable.

In addition, the said diisocyanate uses a compound which reacts with terminal isocyanate, such as monoisocyanate, even if it controls a molecule|numerator to an appropriate polymerization degree, and uses it, it does not interfere. As monoisocyanate for controlling the polymerization degree by sealing the terminal of polycarbodiimide in this way, for example, phenyl isocyanate, toluylene isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, naphthyl isocyanate, etc. are mentioned. . In addition, a compound having an OH group, a —NH ₂ group, a COOH group, and an SO ₃ H group can be used as the terminal blocker.

The condensation reaction involving decarbonization of diisocyanate proceeds in the presence of a carbodiimidization catalyst. Examples of the catalyst include 1-phenyl-2-phosphorene-1-oxide, 3-methyl-2-phosphorene-1-oxide, 1-ethyl-2-phosphorene-1-oxide, 3- and phosphorene oxides such as methyl-1-phenyl-2-phosphoene-1-oxide and 3-phosphoene isomers thereof, and 3-methyl-1-phenyl-2-phosphorus in terms of reactivity. Forene-1-oxide is preferred. In addition, the usage-amount of the said catalyst can be made into the catalytic amount.

The mono- or polycarbodiimide compound is preferably maintained in a uniformly dispersed state when blended with an aqueous paint, and for this purpose, it is emulsified using an appropriate emulsifier to be used as an emulsion, or a polycarbodiimide compound It is preferable to add a hydrophilic segment to the molecular structure of the , and mix it with the paint in the form of a self-emulsion or self-dissolved product.

The carbodiimide-based crosslinking agent used in the present invention includes water dispersibility and water solubility. Water solubility is preferable in terms of good compatibility with other water-soluble resins and improving the crosslinking reaction efficiency of the lubricating coating layer. In order to make the carbodiimide compound water-soluble, it can be prepared by synthesizing an isocyanate-terminated polycarbodiimide by a condensation reaction involving decarbonization of isocyanate, and then adding a hydrophilic moiety having a functional group having reactivity with an isocyanate group. can

Examples of the hydrophilic moiety include (1) quaternary ammonium salts of dialkylamino alcohols and quaternary ammonium salts of dialkylaminoalkylamines, (2) alkylsulfonates having at least one reactive hydroxyl group, and (3) alkoxy group terminals Blocked poly(ethylene oxide), a mixture of poly(ethylene oxide) and poly(propylene oxide), etc. are mentioned. When the above-mentioned hydrophilic moiety is introduced, the carbodiimide compound becomes (1) cationic, (2) anionic, and (3) nonionic. Among them, nonionic properties that can be compatible with each other regardless of the ionic properties of other water-soluble resins are preferable.

As content in the lubricity coating layer of a crosslinking agent, 5 mass % or more and 80 mass % or less are preferable in total solid. More preferably, they are 10 mass % or more and 70 mass % or less. It is preferable at the point that the crosslinking density of resin of an application layer does not fall that it is 5 mass % or more. If it is 80 mass % or less, since the quantity of the carboxyl group of the acrylic resin which is a crosslinking object does not decrease too much, and a crosslinking density does not become low, it is preferable.

(Particles in the lubricating coating layer)

The lubricating coating layer preferably contains lubricating agent particles in order to impart slidability to the surface. The particles may be inorganic particles or organic particles, and are not particularly limited, but (1) silica, kaolinite, talc, light calcium carbonate, ground calcium carbonate, zeolite, alumina, barium sulfate, carbon black, zinc oxide, sulfuric acid Inorganic particles, such as zinc, zinc carbonate, zirconium oxide, titanium dioxide, satin white, aluminum silicate, diatomaceous earth, calcium silicate, aluminum hydroxide, hydrolyzate halloysite, calcium carbonate, magnesium carbonate, calcium phosphate, magnesium hydroxide, barium sulfate, (2 ) Acrylic or methacrylic, vinyl chloride, vinyl acetate, nylon, styrene/acrylic, styrene/butadiene, polystyrene/acrylic, polystyrene/isoprene, polystyrene/isoprene, methyl methacrylate/butyl methacrylate and organic particles such as melamine, polycarbonate, urea, epoxy, urethane, phenol, diallyl phthalate and polyester. Silica is particularly preferably used in order to impart moderate slipperiness to the coating layer.

It is preferable that the average particle diameter of particle|grains is 10 nm or more, More preferably, it is 20 nm or more, More preferably, it is 30 nm or more. If the average particle diameter of the particles is 10 nm or more, it is difficult to aggregate, and sliding properties can be ensured, which is preferable.

It is preferable that the average particle diameter of particle|grains is 1000 nm or less, More preferably, it is 800 nm or less, More preferably, it is 600 nm or less. It is preferable that transparency is maintained as the average particle diameter of particle|grains is 1000 nm or less, and particle|grains do not fall off.

Also, for example, mixing small particles having an average particle diameter of about 10 to 270 nm and large particles having an average particle diameter of about 300 to 1000 nm also reduces the area surface average roughness (Sa) and the maximum protrusion height (P), which will be described later. While maintaining, it is preferable to reduce the average length (RSm) of the roughness curve elements to achieve both sliding properties and smoothness, particularly preferably small particles of 30 nm or more and 250 nm or less, and large particles having an average particle diameter of 350 to 600 nm. it will be combined When mixing small particles and large particles, it is preferable to set the mass content rate of the small particles larger than the mass content ratio of the large particles with respect to the entire solid content of the coating layer.

It is also particularly preferable to use organic particles from the viewpoint of preventing the particles from falling off from the lubricating coating layer. By using organic particle|grains, interaction with the binder and crosslinking agent component of a lubricating coating layer becomes strong, and it becomes easy to prevent fall-off|omission, and it is preferable. Among organic particles, acrylic resin particles and/or methacrylic resin particles having a similar chemical structure to the acrylic resin present in the lubricating coating layer are particularly preferable in terms of preventing the particles from falling off from the lubricating coating layer. These organic particles are preferably contained as particles having a relatively large average particle diameter, in which drop-off of the particles from the lubricating coating layer is likely to become a problem, for example, it is preferable to contain them as particles having an average particle diameter of 300 to 1000 nm. More preferably, it is contained as particle|grains whose average particle diameter is 350-600 nm. Of course, it is a particularly preferable aspect that the organic particles having the average particle diameter are acrylic resin particles and/or methacrylic resin particles.

The average particle diameter of the particles is measured by observing the particles in the cross section of the film after processing with a transmission electron microscope or a scanning electron microscope, observing 100 non-agglomerated particles, and taking the average value as the average particle diameter. did

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

It is preferable that the ratio with respect to the total solid of the lubricating coating layer of particle|grains is 50 mass % or less, More preferably, it is 40 mass % or less, More preferably, it is 30 mass % or less. When the ratio of the particles to the total solid content of the lubricating coating layer is 50% by mass or less, transparency is maintained and the drop-off of the particles from the lubricating coating layer does not occur remarkably, which is preferable.

It is preferable that the ratio with respect to the total solid of the lubricating coating layer of particle|grains is 1 mass % or more, More preferably, it is 1.5 mass % or more, More preferably, it is 2 mass % or more. If the ratio of the particles to the total solid content of the lubricating coating layer is 1% by mass or more, sliding properties can be ensured, which is preferable.

As a method of measuring the content rate of the particle|grains contained in an lubricating coating layer, when resin of an organic component and inorganic particle are contained in an lubricating coating layer, the following method can be used, for example. First, the lubricity coating layer provided on the processed film is extracted from the processed film using a solvent or the like and dried to remove the lubricating coating layer. Next, heat is applied to the obtained lubricating coating layer, and only an inorganic component can be obtained by burning and distilling the organic component contained in the lubricating coating layer with heat. By measuring the weight of the obtained inorganic component and the lubricating coating layer before combustion distillation removal, the mass % of the particle|grains contained in an lubricating coating layer can be measured. At this time, it can measure with high precision by using a commercially available simultaneous differential heat and thermogravimetric measurement apparatus. In addition, the ratio of the said particle|grains in the total solid of the lubricating coating layer means the ratio of the total amount of multiple types, when multiple types of particle|grains exist.

(Additive in the lubricating coating layer)

In order to provide other functionality to the lubricating coating layer, you may make it contain various additives in the range which does not impair the coating appearance. As said additive, a fluorescent dye, a fluorescent whitening agent, a plasticizer, a ultraviolet absorber, a pigment dispersing agent, a foam suppressing agent, an antifoaming agent, antiseptic|preservative etc. are mentioned, for example.

The lubricating coating layer can also contain surfactant for the purpose of improving the leveling property at the time of application|coating and defoaming a coating liquid. The surfactant may be any of cationic, anionic, nonionic, and the like, but a silicone-based, acetylene glycol-based, or fluorine-based surfactant is preferable. It is preferable to make an application layer contain these surfactant in the range of the grade which does not generate|occur|produce abnormality of an application|coating external appearance by adding excessively.

As a coating method, both the so-called in-line coating method, which is applied at the same time as the polyester base film is formed, and the so-called off-line coating method, which is applied with a separate coater after the polyester base film is formed, can be applied, but the inline coating method is more efficient and more preferably.

Any well-known method can be used for the method for apply|coating a coating liquid to a polyethylene terephthalate (Hereinafter, it may abbreviate as PET) film as a coating method. 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 and the like. These methods are applied alone or in combination.

In this invention, as a method of providing a lubricating coating layer on a polyester film, the method of apply|coating and drying the coating liquid containing a solvent, particle|grains and resin to a polyester film is 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, preferably water alone or a so-called aqueous solvent obtained by mixing water with a water-soluble organic solvent from the viewpoint of environmental problems. do.

Although the solid content concentration of the lubricating coating liquid varies depending on the type of binder resin, the type of solvent, etc., it is preferably 0.5 mass % or more, and more preferably 1 mass % or more. It is preferable that solid content concentration of a coating liquid is 35 mass % or less, More preferably, it is 20 mass % or less.

The drying temperature after application also varies depending on the type of binder resin, the type of solvent, the presence or absence of a crosslinking agent, the solid content concentration, etc., but is preferably 70°C or higher, and preferably 250°C or lower.

(Production of polyester film)

In this invention, the polyester film used as a base film can be manufactured according to the manufacturing method of a general polyester film. For example, the polyester resin is melted and the unoriented polyester extruded into a sheet is stretched in the longitudinal direction using the speed difference of the rolls at a temperature above the glass transition temperature, and then in the transverse direction by a tenter. The method of extending|stretching and heat-processing is mentioned. Moreover, the method of biaxially extending|stretching longitudinally and horizontally simultaneously in a tenter is also mentioned.

In this invention, although a uniaxially stretched film may be sufficient as the polyester film used as a base film, and a biaxially stretched film may be sufficient, it is preferable that it is a biaxially stretched film.

It is preferable that the thickness of a polyester film base material is 5 micrometers or more, More preferably, it is 10 micrometers or more, More preferably, it is 15 micrometers or more. As for thickness, it is difficult to produce wrinkles at the time of conveyance of a film as it is 5 micrometers or more, and it is preferable.

It is preferable that the thickness of a polyester film base material is 50 micrometers or less, More preferably, it is 45 micrometers or less, More preferably, it is 40 micrometers or less. Since the cost per unit area falls that thickness is 40 micrometers or less, it is preferable.

In the case of an in-line coat, you may apply to the unstretched film before extending|stretching in the longitudinal direction, and you may apply to the uniaxially stretched film after extending|stretching in the longitudinal direction and before extending|stretching in the transverse direction. When coating before extending|stretching in a longitudinal direction, it is preferable to provide a drying process before roll extending|stretching. When coating to the uniaxially stretched film before extending|stretching in the lateral direction, since it can serve also as a drying process in the film heating process in a tenter, it is not necessarily necessary to provide a drying process separately. Moreover, it is the same also when carrying out simultaneous biaxial stretching.

It is preferable that the film thickness of a lubricating coating layer is 0.001 micrometer or more, More preferably, it is 0.01 micrometer or more, More preferably, it is 0.02 micrometer or more, Especially preferably, it is 0.03 micrometer or more. Since the film-forming property of a coating film is maintained as the film thickness of an application layer is 0.001 micrometer or more, and a uniform coating film is obtained, it is preferable.

It is preferable that the film thickness of a lubricating coating layer is 2 micrometers or less, More preferably, it is 1 micrometer or less, More preferably, it is 0.8 micrometer or less, Especially preferably, it is 0.5 micrometer or less. If the film thickness of the application layer is 2 µm or less, there is no fear of blocking, which is preferable.

A ceramic green sheet to be coated and molded on a release coating layer to be described later is wound up into a roll together with a release film after application and molding. At this time, the ceramic green sheet is wound in a state in which the lubricating coating layer of the release film is in contact with the surface of the ceramic green sheet. In order not to generate defects on the surface of the ceramic green sheet, the outer surface of the lubricating coating layer (the surface of the lubricating coating layer of the entire coating film not in contact with the polyester film) must be suitably flat, and the area surface average roughness (Sa ) is preferably 1 nm or more and 25 nm or less, and the maximum projection height P is 60 nm or more and 500 nm or less.

If the area surface average roughness (Sa) of the outer surface of the lubricating layer is 1 nm or more and the maximum projection height (P) is 60 nm or more, the lubricating surface does not become too smooth and moderate slidability can be maintained, which is preferable. If the area surface average roughness (Sa) is 25 nm or less and the maximum protrusion height (P) is 500 nm or less, it is preferable that the lubricating surface does not become excessively rough and defects of the ceramic green sheet due to the protrusions do not occur.

In the present invention, in addition to making the region surface average roughness Sa and the maximum projection height P within the above ranges, it is preferable that the average length RSm of the roughness curve elements is 10 µm or less. By controlling the average length RSm of the roughness curve element to be 10 μm or less, the number of protrusions per unit area is increased. When the number of protrusions is increased, the pressure applied per protrusion is dispersed and small, so that generation of pinholes can be effectively suppressed, which is preferable. The average length (RSm) of the roughness curve elements is more preferably 5 µm or less, still more preferably 3 µm or less. However, when the average length (RSm) of the roughness curve element is too small, the area surface average roughness (Sa) is increased, and the maximum protrusion height (P) is increased in relation to the excessively large content of particles in the lubricating coating layer. Since it is also related to a thing, it is preferable that it is 0.1 micrometer or more, 0.5 micrometer or more may be sufficient, and 1 micrometer or more may be sufficient.

In the present invention, in order to make the average length (RSm) of the roughness curve elements within a predetermined range, it is preferable that the average particle diameter of the particles contained in the lubricating coating layer is 1000 nm or less. More preferably, it is 800 nm or less, More preferably, it is 600 nm or less. When the particle diameter is 1000 nm or less, the distance between particles does not become excessively large, and RSm is preferably adjusted to a predetermined range.

It is preferable that it is 45 mJ/m<2> or less, and, as for the surface free energy of an lubricating coating layer, it is more preferable that it is 40 mJ/m<2> or less. When the surface free energy of the lubricating coating layer is 45 mJ/m 2 or less, it becomes difficult to attach environmental foreign substances in the process, and it becomes difficult for foreign substances to adhere to the release surface, and pinholes due to environmental foreign substances in the ceramic green sheet are less likely to occur. It is preferable that it becomes difficult.

(Releasable coating layer)

The resin constituting the release coating layer in the present invention is not particularly limited, and silicone resins, fluororesins, alkyd resins, various waxes, aliphatic olefins, etc. can be used, and each resin may be used alone or in combination of two or more. .

As the release coating layer in the present invention, for example, a silicone resin refers to a resin having a silicone structure in a molecule, and includes a cured silicone, a silicone graft resin, and a modified silicone resin such as an alkyl-modified resin. It is preferable to use a reactive hardening silicone resin from a viewpoint, etc. As a reactive curable silicone resin, the thing of an addition reaction system, the thing of a condensation reaction system, the thing of an ultraviolet-ray or electron beam curing system, etc. can be used. More preferably, it is good that it is a low-temperature curable addition-reaction system which can be processed at low temperature, and it is good that it is an ultraviolet-ray or electron beam hardening system. By using these, at the time of the coating process to a polyester film, it can process at low temperature. Therefore, there is little thermal damage to the polyester film during processing, a polyester film with high flatness is 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. have.

As an addition-reaction type silicone resin, polydimethylsiloxane which introduce|transduced the vinyl group in the terminal or side chain, and hydrogensiloxane are made to react using a platinum catalyst, and hardening is mentioned, for example. In this case, it is more preferable to use a resin that can be cured at 120° C. within 30 seconds because processing at a low temperature is possible. For example, low temperature addition curing type (LTC1006L, LTC1056L, LTC300B, LTC303E, LTC310, LTC314, LTC350G, LTC450A, LTC371G, LTC750A, LTC755, LTC760A, etc.) and thermal UV curing type (LTC851, BY24-510, BY24-510, etc.) manufactured by Toray Dow Corning. 561, BY24-562, etc.), solvent addition + UV curing type made by Shin-Etsu Chemical (X62-5040, X62-5065, X62-5072T, KS5508, etc.), dual cure curing type (X62-2835, X62-2834, X62- 1980, etc.) and the like.

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

As the UV-curable silicone resin, for example, as the most basic type, using the same radical reaction as that of normal silicone rubber crosslinking, photo-curing by introducing an unsaturated group, decomposing an onium salt with UV light to generate a strong acid, thereby generating an epoxy group and crosslinking by cleavage, crosslinking by addition reaction of thiol to vinylsiloxane, and the like. In addition, an electron beam can also be used instead of the said ultraviolet-ray. Since electron beams have stronger energy than ultraviolet rays, it is possible to carry out a crosslinking reaction by radicals without using an initiator as in the case of ultraviolet curing. Examples of the resin to be used include UV-curable silicone (X62-7028A/B, X62-7052, X62-7205, X62-7622, X62-7629, X62-7660, etc.) manufactured by Shin-Etsu Chemical Co., Ltd. UV-curable silicone (TPR6502, TPR6501, TPR6500, UV9300, UV9315, XS56-A2982, UV9430, etc.) manufactured by Materials Corporation, UV-curable silicone manufactured by Arakawa Chemical (Silicoris UV POLY200, POLY215, POLY201, KF-UV265AM, etc.) ) can be mentioned.

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

As examples of other resins used, alkyd resins or acrylic resins subjected to stearyl modification, lauryl modification, etc., or alkyd resins or acrylic resins obtained by reaction of methylated melamine, etc. are also suitable.

As aminoalkyd resin obtained by the said reaction of said methylated melamine, etc., the Hitachi Chemical Co., Ltd. Tespine 303, Thespine 305, Tespine 314, etc. are mentioned. As aminoacrylic resin obtained by reaction of a methylated melamine, etc., the Hitachi Chemical company Tespine 322 etc. are mentioned.

When using the said resin for the mold release application layer in this invention, you may use by 1 type, and may mix and use 2 or more types. Moreover, in order to adjust peeling force, it is also possible to mix additives, such as a light peeling additive and a heavy peeling additive.

Although the release coating layer in the present invention may contain particles having a particle diameter of 1 µm or less, it is preferable not to substantially contain those that form projections such as particles from the viewpoint of pinhole generation.

You may add additives, such as a close_contact|adherence improving agent and an antistatic agent, etc. to the mold release coating layer in this invention. Moreover, in order to improve adhesiveness with a base material, it is also preferable to pre-process anchor coat, corona treatment, plasma treatment, atmospheric pressure plasma treatment, etc. on the polyester film surface before providing a release application 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 in the range of 0.005 to 2.0 µm. If the thickness of a mold release coating layer is 0.005 micrometer or more, peeling performance is maintained and it is preferable. In addition, if 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 fear of causing a thickness unevenness of the ceramic green sheet due to a decrease in the planarity of the release film, which is preferable. Further, since the curing time does not become too long, there is no fear of aggregation of the resin constituting the release coating layer and there is no fear of forming projections, which is preferable because pinhole defects of the ceramic green sheet are unlikely to occur.

The outer surface of the film on which the release coating layer is formed (the surface of the entire application film that is not in contact with the polyester film) is preferably flat in order not to cause defects in the ceramic green sheet to be coated and molded on it, It is preferable that the area|region surface average roughness Sa is 5 nm or less, and that the maximum processus|protrusion height P is 30 nm or less. Furthermore, the area|region surface average roughness of 5 nm or less and 20 nm or less of maximum processus|protrusion height are more preferable. When the area surface average roughness is 5 nm or less and the maximum protrusion height is 30 nm or less, defects such as pinholes do not occur at the time of forming the ceramic green sheet, and the yield is good, which is preferable. Although it can be said that it is so preferable that the area|region surface average roughness Sa is small, 0.1 nm or more may be sufficient and 0.3 nm or more may be sufficient as it. Although it can be said that it is so preferable that the maximum processus|protrusion height P is also small, 1 nm or more may be sufficient and 3 nm or more may be sufficient as it.

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 addition, "substantially free of inorganic particles" in the present invention is defined as 50 ppm or less when quantitative analysis of elements derived from particles by fluorescence X-ray analysis for both the base film and the release coating layer. and preferably 10 ppm or less, and most preferably below the detection limit. This is because, even if particles are not actively added to the base film, contaminant components derived from foreign matter or contaminants adhering to lines and devices in the raw material resin or film manufacturing process may peel off and mix in the film. .

In the present invention, the method for forming the release coating layer is not particularly limited, and a coating solution in which a release resin is dissolved or dispersed is applied to one side of the polyester film of the substrate or the like, and the solvent is removed by drying. Then, a method of heat drying, heat curing or UV curing is used. At this time, as for the drying temperature at the time of solvent drying and thermosetting, it is preferable that it is 180 degrees C or less, It is more preferable that it is 150 degrees C or less, It is most preferable that it is 120 degrees C or less. 30 second or less is preferable and, as for the heating time, 20 second or less is more preferable. When it is 180 degrees C or less, the flatness of a film is maintained, and there is little possibility of raising the thickness non-uniformity of a ceramic green sheet, and it is preferable. If it is 120 degrees C or less, since it can process without impairing the planarity of a film, and the possibility of raising the thickness non-uniformity of a ceramic green sheet further falls, it is especially preferable.

In this invention, although the surface tension of the coating liquid at the time of apply|coating a mold release coating layer is not specifically limited, It is preferable that it is 30 mN/m or less. By carrying out surface tension as mentioned above, the wettability after coating can improve and the unevenness|corrugation of the coating-film surface after drying can be reduced.

In this invention, although it does not specifically limit to the coating liquid at the time of apply|coating a mold release coating layer, It is preferable to add the solvent of 90 degreeC or more of boiling points. By adding the solvent with a boiling point of 90 degreeC or more, bumpiness at the time of drying can be prevented, a coating film can be leveled, and the smoothness of the coating film surface after drying can be improved. As the addition amount, it is preferable to add about 10-80 mass % with respect to the whole coating liquid.

As the coating method of the coating solution, any known coating method can be applied. 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, and a spray coating method , a conventionally known method such as an air knife coating method can be used.

(Ceramic Green Sheet and Ceramic Capacitor)

In general, a multilayer ceramic capacitor has a rectangular parallelepiped ceramic body. Inside the ceramic body, first internal electrodes and second internal electrodes are alternately provided along the thickness direction. The first internal electrode is exposed on the first end surface of the ceramic body. A first external electrode is provided on the first end face. The first internal electrode is electrically connected to the first external electrode on the first end surface. The second internal electrode is exposed on the second end surface of the ceramic body. A second external electrode is provided on the second end face. The second internal electrode is electrically connected to the second external electrode on the second end surface.

The release film for ceramic green sheet manufacture of this invention is used in order to manufacture such a multilayer ceramic capacitor. For example, it manufactures as follows. First, using the release film of the present invention as a carrier film, a ceramic slurry for constituting a ceramic body is applied and dried. On the coated and dried ceramic green sheet, a conductive layer for constituting the first or second internal electrode is printed. A mother laminate is formed by appropriately laminating and pressing a ceramic green sheet, a ceramic green sheet on which a conductive layer for constituting the first internal electrode is printed, and a ceramic green sheet on which a conductive layer for constituting the second internal electrode is printed. get The mother laminate is divided into a plurality of parts, and a raw ceramic body is produced. A ceramic body is obtained by firing the raw ceramic body. Thereafter, the multilayer ceramic capacitor can be completed by forming the first and second external electrodes.

Example

Next, although this invention is demonstrated in detail using an Example and a comparative example, this invention is not limited to a following example of course. In addition, the evaluation method used by this invention is as follows.

[NMR measurement]

The ratio of the copolymerization component introduced into the acrylic polyol was ^{confirmed using nuclear magnetic resonance spectroscopy (1} H-NMR, ¹³ C-NMR: Varian Unity 400, manufactured by Agilent). The measurement was performed by dissolving the dried product in deuterated chloroform after removing the solvent in the synthesized acrylic polyol with a vacuum dryer. From the obtained NMR spectrum, the peak of the chemical shift δ (ppm) attributed to the site of each group was identified. The integral intensity of each obtained peak was calculated|required, and the composition ratio (mol%) of the copolymerization component introduce|transduced into acrylic polyol was confirmed from the hydrogen number and integral intensity of the site|part of each group.

[Confirmation of Tg]

Tg of each acrylic polyol was calculated|required from the composition ratio of the copolymerization component calculated|required by the said NMR measurement, and said Fox formula.

[Renewal Aptitude]

In order to evaluate the stretching aptitude of the acrylic polyol itself, synthesized acrylic polyols (1) to (13) were placed in a mixed solvent (25° C.) of 30 mass % isopropanol and 70 mass % water so that the solid content concentration was 12 mass %. After injecting|throwing-in and preparing the acrylic polyol single-piece|unit solution, the solution was apply|coated to the surface of the polyester film which performed only the transverse stretching with Mayer bar #5. Next, the film sample on which the application layer (thickness 6.5 micrometers) was formed was left still in the hot-air circulation oven set to the temperature of 60 degreeC for 30 second, Then, the film sample was taken out from the oven and predrying was performed. Next, the sample was set in the manual stretching apparatus (made by Toyobo Engineering Co., Ltd.), it put in 100 degreeC hot-air circulation oven, and extending|stretching operation was performed slowly. Extending operation was performed until it became the length of 4 times the length before extending|stretching, and the extending|stretching apparatus was taken out from the hot-air circulation oven. Then, the coating film after extending|stretching was observed with the optical microscope (magnification: 200 times), and the presence or absence of cracking by extending|stretching was judged according to the following reference|standard.

○: No cracks are seen at all

△: cracks are slightly seen (1 to 4)

×: 5 or more cracks, or cracks are seen on the entire surface

(1) Surface properties of the coated film

It is a value measured under the following conditions using the non-contact surface shape measurement system (VertScan R550H-M100). The average value of the area surface average roughness (Sa) and the average length (RSm) of the roughness curve elements were obtained from 5 measurements, and the maximum projection height (P) was the maximum value from 5 measurements.

(Measuring conditions)

ㆍMeasurement mode: WAVE mode

ㆍObjective lens: 50x

ㆍ0.5×Tube lens

ㆍMeasurement area 187 × 139㎛ (Sa, P measurement)

ㆍMeasurement length (Lr: reference length): 187㎛ (RSm measurement)

(2) Evaluation of particle dispersibility of the lubricating coating layer (narrow field of view, VertScan measurement field of 187 × 139 μm)

The value of the maximum protrusion height (P) measured in (1) was determined based on the following criteria.

○: The maximum protrusion height (P) is 0.2㎛ or less

○△: The maximum protrusion height (P) is greater than 0.2㎛ and smaller than 0.3㎛

△: the maximum protrusion height (P) is 0.3㎛ or more

(3) Evaluation of particle dispersibility of the lubricating coating layer (wide field of view, visual field, measurement field of view 600mm×420mm)

In a dark room, using an LED light (manufactured by LED LENSER, LED LENSER P5R.2), four peeling films for producing A4 size green sheets were observed, and white recognizable particle aggregates were marked, as shown below. It was judged on the basis of

(double-circle): No particle agglomeration

○: 1 to 3 particle aggregates

△: 4 or more particle aggregates

(4) Powder fall resistance

A peeling film for green sheet production (3 cm (film width direction) × 20 cm (film length direction))) was installed on a friction fastness tester (Die Chemical Seiki Seisakusho Co., Ltd., RT-200) so that the lubricating coating layer was on the top side. Then, using an aluminum foil (thickness 80 μm, arithmetic mean surface roughness 0.03 μm) in the contact portion between the load head portion (2 cm × 2 cm, 200 g) and the sample film, a distance of 10 cm was performed at a speed of 2 seconds for one round trip. reciprocated. The obtained film was placed on the black base, and it was visually confirmed whether the powder fell.

○: powder fall cannot be confirmed on the black ground

△: A slight drop of powder can be confirmed as a whole on the black ground

(5) surface free energy

Water (1.8 µL of droplet) and diiodo on the release surface of the release film using a contact angle meter (manufactured by Kyowa Kaimen Chemical Co., Ltd.: fully automatic contact angle meter DM-701) under conditions of 25°C and 50% RH Droplets of methane (droplet amount: 0.9 µL) and ethylene glycol (droplet amount: 0.9 µL) were prepared, and the contact angle was measured. The contact angle employ|adopted the contact angle 10 second after dripping each liquid to the release film. The contact angle data of water, diiodomethane, and ethylene glycol obtained by the above method are calculated from the "Kitazaki-Hata" theory to obtain the dispersion component γsd, the polar component γsp, and the hydrogen bonding component γsh of the surface free energy of the release film, each The sum of the components was defined as the surface free energy γs. This calculation was performed using the calculation software in this contact angle meter software (FAMAS).

(6) Unwinding and charging of the release film roll

The peeling film for green sheet manufacture obtained by each Example and each comparative example was wound up in roll shape of width 400mm and length 5000m, and the peeling film roll was obtained. After storing this peeling film roll for 30 days in 40 degreeC and an environment of 50% or less of humidity, the charge amount at the time of rewinding at 100 m/min was measured using "KSD-0103" manufactured by Kasuga Electric Corporation. The charge amount was measured for every 500M unwinding length at a location 100 mm immediately after unwinding, and the average value was calculated.

○: Less than ±3kV

○△: ±3kV or more and less than 5kV

△: ±5kV or more and less than 10kV

×: ±10kV or more

(7) Evaluation of pinhole and thickness variation of ceramic green sheet

The composition containing the following materials was stirred and mixed, and it was disperse|distributed for 2 hours using the paint shaker which uses 2.0 mm of glass beads as a dispersion medium, and the ceramic slurry was obtained.

Toluene 22.5% by mass

Ethanol 22.5% by mass

50% by mass of barium titanate

(HPBT-1 made by Fuji Titanium)

5% by mass of polyvinyl butyral

(Srek BH-3 made by Sekisui Chemical)

Then, using an applicator on the release surface of the release film sample, the dried slurry was applied to a thickness of 0.5 μm, dried at 90° C. for 1 minute, and the slurry surface and the smoothing coated layer surface were overlapped for 10 minutes, 1 kg/cm 2 weighted After adding, the release film was peeled off to obtain a ceramic green sheet.

In the central region in the film width direction of the obtained ceramic green sheet, light is irradiated from the opposite side of the coated surface of the ceramic slurry in a range of 25 cm 2 , the occurrence of pinholes through which light can be seen is observed, and visually judged according to the following criteria did

(double-circle): No pinhole generation, especially good thickness fluctuation

○: No pinhole generation, no problem in thickness fluctuation

△: Very little occurrence of pinholes and slight variation in thickness

x: There is little occurrence of pinholes, and the thickness fluctuations are slightly conspicuous.

(Preparation of polyethylene terephthalate pellets (PET(I)))

As the esterification reaction apparatus, a continuous esterification reaction apparatus including a three-stage complete mixing tank having a stirring device, a dust separator, a raw material inlet and a product outlet was used. TPA (terephthalic acid) is 2 tons/hour, EG (ethylene glycol) is 2 moles per 1 mole of TPA, and antimony trioxide is used in an amount such that the Sb atom is 160 ppm with respect to the produced PET, and these slurries are used in the esterification reaction apparatus. It was continuously supplied to the first esterification reaction can, and the reaction was carried out at 255°C with an average residence time of 4 hours at atmospheric pressure. Then, 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 EG distilled off from the first esterification can in the second esterification reaction can is produced in PET. EG solution containing magnesium acetate tetrahydrate in an amount such that the Mg atom is 65 ppm with respect to the produced PET, and containing TMPA (trimethyl phosphate) in an amount of 40 ppm with respect to the produced PET. The solution was added, and the reaction was carried out at 260°C with an average residence time of 1 hour at atmospheric pressure. Next, the reaction product of the second esterification reaction can is continuously taken out of the system, supplied to the third esterification reaction can, and averaged at a pressure of 39 MPa (400 kg/cm 2 ) using a high-pressure disperser (manufactured by Nippon Seiki Co., Ltd.) 0.2 mass % of porous colloidal silica having an average particle diameter of 0.9 μm, subjected to dispersion treatment in 5 passes, and 0.4 mass % of synthetic calcium carbonate having an average particle diameter of 0.6 μm in which 1 mass % of an ammonium salt of polyacrylic acid is adhered per calcium carbonate; While adding each as a 10% EG slurry, the reaction was carried out at 260°C with an average residence time of 0.5 hours at normal pressure. The esterification reaction product produced in the third esterification reaction can is continuously supplied to a three-stage continuous polycondensation reaction apparatus for polycondensation, and is filtered through a filter obtained by sintering stainless steel fibers with a 95% cut diameter of 20 µm. after performing ultrafiltration, extruding in water, and cutting into chips after cooling to obtain PET chips having an intrinsic viscosity of 0.60 dl/g (hereinafter, abbreviated as PET(I)). The lubricant content in the PET chip was 0.6 mass%.

(Preparation of polyethylene terephthalate pellets (PET(II)))

Meanwhile, 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 or silica was obtained (hereinafter, abbreviated as PET(II)).

(Preparation of laminated film Z)

After drying these PET chips, they are melted at 285°C, melted at 290°C by a separate melt extruder, and a filter obtained by sintering stainless steel fibers having a 95% cut diameter of 15 μm, and a 95% cut diameter of 15 μm Two-stage filtration of a filter in which stainless steel particles are sintered is performed, merged in a feed block, PET (I) is laminated so as to be a semi-release side layer, and PET (II) is a release side layer, and the sheet is 45 m/ It was extruded (cast) at a speed of 1 minute, and was electrostatically adhered and cooled on a casting drum at 30°C by an electrostatic adhesion method to obtain an unstretched polyethylene terephthalate sheet having an intrinsic viscosity of 0.59 dl/g. The layer ratio was adjusted so that it might become PET(I)/(II)=60%/40% by the discharge amount calculation of each extruder. Next, this unstretched sheet was heated with an infrared heater, and then stretched 3.5 times in the longitudinal direction at a roll temperature of 80°C by the speed difference between the rolls. Then, it guide|induced with the tenter, and it extended|stretched 4.2 times in the transverse direction at 140 degreeC. Next, in the heat setting zone, it heat-processed at 210 degreeC. Thereafter, a 2.3% relaxation treatment was performed in the transverse direction at 170°C to obtain a 31 µm-thick biaxially stretched polyethylene terephthalate film Z. Sa of the release side layer of the obtained film Z was 2 nm, and Sa of the semi-release side layer was 28 nm.

(Preparation of acrylic polyol A-1)

To a four-neck flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen suction tube, 77 parts by mass of methyl methacrylate (MMA), 100 parts by mass of hydroxyethyl methacrylate (HEMA), 33 parts by mass of methacrylic acid (MAA) 490 mass parts of parts and isopropyl alcohol (IPA) were thrown in, and the inside of the flask was heated up to 80 degreeC, stirring. Stirring was performed for 3 hours, maintaining the inside of a flask at 80 degreeC, and 0.5 mass parts of 2, 2- azobis-2-methyl-N-2-hydroxyethyl propionamide was added to the flask after that. After nitrogen substitution was performed while heating the inside of the flask to 120°C, the mixture was stirred at 120°C for 2 hours.

Next, the pressure reduction operation of 1.5 kPa was performed at 120 degreeC, the unreacted raw material and solvent were removed, and the acrylic polyol was obtained. The inside of a flask was returned to atmospheric pressure, it cooled to room temperature, and 840 mass parts of IPA aqueous solution (water content 50 mass %) was added and mixed. Thereafter, using a dropping funnel while stirring, triethylamine is added, the acrylic polyol is neutralized until the pH of the solution is in the range of 5.5 to 7.5, and the acrylic polyol having a solid content concentration of 20 mass% (A -1) was obtained. Table 1 lists the composition ratio, Tg, drawability, and acid value of acrylic polyol (A-1) by NMR measurement.

(Preparation of acrylic polyols (A-2) to (A-13))

As shown in Table 1, except that MMA, St, SMA, HEMA, MAA, AA, IPA at the time of input, the amount of 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 A-1, solid content concentration Acrylic polyols (A-2) to (A-13) of which are 20 mass% were obtained. Table 1 lists the composition ratio, Tg, drawability, and acid value of the acrylic polyols (A-2) to (A-13) by NMR measurement. In addition, the composition ratio is MMA, St (styrene), SMA (stearyl methacrylate) 1-1, 1-2, 1-3 (unit), HEMA m (unit), MAA, AA (acrylic acid) is expressed as n (unit).

(Polymerization of polyester resin B0-1)

To a stainless steel autoclave provided with a stirrer, a thermometer, and a partial reflux cooler, 194.2 parts by mass of dimethyl terephthalate, 184.5 parts by mass of dimethyl isophthalate, 14.8 parts by mass of dimethyl-5-sodium sulfoisophthalate, 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 added, and transesterification reaction was performed at a temperature of 160°C to 220°C over 4 hours. Subsequently, the temperature was raised to 255° C. and the reaction system was gradually reduced in pressure, and then reacted under a reduced pressure of 30 Pa for 1 hour and 30 minutes to obtain a copolymerized polyester resin (B0-1). The obtained co-polyester resin (B0-1) was pale yellow and transparent. When the reduced viscosity of the copolymerized polyester resin (B0-1) was measured, it was 0.60 dl/g. The glass transition temperature by DSC was 65°C.

(Preparation of polyester water dispersion B-1)

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

(Polymerization of polyester resin B0-2)

To a stainless steel autoclave provided with a stirrer, a thermometer and a partial reflux cooler, 163 parts by mass of dimethyl terephthalate, 163 parts by mass of dimethyl isophthalate, 169 parts by mass of 1,4-butanediol, 324 parts by mass of ethylene glycol, and tetra-n- 0.5 mass parts of butyl titanate was thrown in, and the transesterification reaction was performed from 160 degreeC to 220 degreeC over 4 hours.

Next, 14 mass parts of fumaric acids and 203 mass parts of sebacic acids were added, it heated up from 200 degreeC to 220 degreeC over 1 hour, and esterification was performed. Subsequently, the temperature was raised to 255°C and the reaction system was gradually reduced in pressure, followed by a reaction 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.

(Preparation of polyester water dispersion B-2)

Next, 60 parts by mass of this copolymerized polyester resin (B0-2), 45 parts by mass of methyl ethyl ketone, and 15 parts by mass of isopropyl alcohol were put in a reactor equipped with a stirrer, thermometer, reflux device and quantitative dropping device for producing the graft resin. , 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.

Next, the solution obtained 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 at 0.1 ml/min to the polyester solution, and stirring was continued for 2 hours. After sampling for analysis from the reaction solution, 8 mass parts of methanol was added. Next, 300 mass parts of water and 24 mass parts of triethylamine were added to the reaction solution, and it stirred for 1 hour.

Thereafter, the internal temperature of the reactor was raised to 100° C., and methyl ethyl ketone, isopropyl alcohol, and excess triethylamine were distilled off by distillation to obtain a pale yellow transparent polyester resin, uniform with a solid content concentration of 25% by mass. A water-dispersible polyester-based graft copolymer dispersion (B-2) was prepared. The glass transition temperature of the obtained polyester graft copolymer was 68 degreeC.

(Preparation of polyurethane water dispersion C-1)

43.75 parts by mass of 4,4-dicyclohexylmethane diisocyanate, 12.85 parts by mass of dimethylolbutanoic acid, and a number average molecular weight of 2000 in a four-neck flask equipped with a stirrer, a Dimroth cooler, a nitrogen inlet tube, a silica gel drying tube and a thermometer 153.41 parts by mass of polyhexamethylene carbonate diol, 0.03 parts by mass of dibutyltin dilaurate, and 84.00 parts by mass of acetone as a solvent were added, and stirred under a nitrogen atmosphere at 75° C. for 3 hours, and the reaction solution had a predetermined amine equivalent was confirmed to have reached. Subsequently, after temperature-falling this reaction liquid to 40 degreeC, 8.77 mass parts of triethylamines were added and the polyurethane prepolymer solution was obtained. Then, in a reaction vessel equipped with a homodisper capable of high-speed stirring, 450 g of water was added, adjusted to 25° C., ^{and stirred and mixed at 2000 min −1} , and a polyurethane prepolymer solution was added and dispersed in water. Then, the water-soluble polyurethane resin solution C-1 of 37 mass % of solid content was prepared by removing a part of acetone and water under reduced pressure. The glass transition temperature of the obtained polyurethane resin was -30 degreeC.

(Preparation of oxazoline-based crosslinking agent D-1)

460.6 parts of isopropyl alcohol was thrown into the flask provided with a stirrer, a reflux condenser, a nitrogen introduction pipe, and a thermometer, and it heated at 80 degreeC, flowing nitrogen gas slowly. A monomer mixture containing 126 parts of methyl methacrylate, 210 parts of 2-isopropenyl-2-oxazoline, and 84 parts of methoxypolyethylene glycol acrylate prepared therein, and 2,2'-azobis as a polymerization initiator An initiator solution containing 21 parts (2-methylbutyronitrile) ("ABN-E" manufactured by Nippon Hydrazine Kogyo Co., Ltd.) and 189 parts of isopropyl alcohol was added dropwise over 2 hours in a dropping funnel, respectively, to react, and the mixture was added dropwise After completion, the reaction was continued for 5 hours. During the reaction, nitrogen gas was continuously flowed, and the temperature in the flask was maintained at 80±1°C. Then, the reaction liquid was cooled and resin (D-1) which has an oxazoline group with a solid content concentration of 25% was obtained. The amount of oxazoline groups of the obtained resin (D-1) having an oxazoline group was 4.3 mmol/g, and the number average molecular weight measured by GPC (gel permeation chromatography) was 20000.

(Preparation of oxazoline-based crosslinking agent D-2)

By the method similar to the synthesis|combination of the said resin (D-1) which has an oxazoline group, resin (D-2) which has an oxazoline group of 10% of solid content concentration from which a composition (oxazoline group amount and molecular weight) differs was obtained. The amount of oxazoline groups of the obtained resin (D-2) having an oxazoline group was 7.7 mmol/g, and the number average molecular weight measured by GPC was 40000.

(Preparation of carbodiimide crosslinking agent E-1)

168 parts by mass of hexamethylene diisocyanate and 220 parts by mass of polyethylene glycol monomethyl ether (M400, average molecular weight 400) were put into a flask equipped with a stirrer, a thermometer, and a reflux cooling tube, stirred at 120 ° C. for 1 hour, and further 4,4 26 parts by mass of '-dicyclohexylmethane diisocyanate and 3.8 parts by mass of 3-methyl-1-phenyl-2-phosphoene-1-oxide as a carbodiimidization catalyst (2% by mass relative to all isocyanates) was added and stirred at 185° C. under a nitrogen stream for an additional 5 hours. By measuring the infrared spectrum of the reaction solution, it was confirmed that absorption at a ^{wavelength of 2200 to 2300 cm -1 was lost.} It stood to cool to 60 degreeC, 567 mass parts of ion-exchange water was added, and the carbodiimide water-soluble resin (E-1) of 40 mass % of solid content was obtained.

(Preparation of isocyanate crosslinking agent F-1)

100 parts by mass of a polyisocyanate compound having an isocyanurate structure (manufactured by Asahi Kasei Chemicals, Duranate TPA) containing hexamethylene diisocyanate as a raw material in a flask equipped with a stirrer, a thermometer and a reflux cooling tube, propylene glycol monomethyl ether acetate 55 mass parts and 30 mass parts of polyethyleneglycol monomethyl ether (average molecular weight 750) were thrown in, and it hold|maintained at 70 degreeC in nitrogen atmosphere for 4 hours. Then, the reaction liquid temperature was lowered|hung to 50 degreeC, and 47 mass parts of methyl ethyl ketoximes were dripped. The infrared spectrum of the reaction liquid was measured, it confirmed that absorption of an isocyanate group had lose|disappeared, and the blocked polyisocyanate aqueous dispersion (F-1) with a solid content of 75 mass % was obtained.

(Silica particle G-1)

Colloidal silica (manufactured by Nissan Chemical, trade name MP2040, average particle size 200 nm, solid content concentration 40% by mass)

(Silica particle G-2)

Colloidal silica (manufactured by Nissan Chemical, trade name Snowtex XL, average particle size 40 nm, solid content concentration 40% by mass)

(Silica particle G-3)

Colloidal silica (manufactured by Nissan Chemical, trade name Snowtex ZL, average particle size of 100 nm, solid content concentration of 40% by mass)

(Silica particles G-4)

Colloidal silica (manufactured by Nissan Chemical, trade name MP4540M, average particle size of 450 nm, solid content concentration of 40% by mass)

(Acrylic particle G-5)

Acrylic particle water dispersion (made 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 (made by Nippon Shokubai, trade name MX200W, average particle diameter 350 nm, solid content concentration 10 mass %)

(Acrylic particle G-7)

Acrylic particle aqueous dispersion (made by Nippon Shokubai, trade name MX300W, average particle size 450 nm, solid content concentration 10% by mass)

(Release agent solution X-1)

100 parts by mass of thermosetting aminoalkyd resin (Tespine 314 manufactured by Hitachi Chemical Corporation, solid content 60% by mass) and 1.2 parts by mass of p-toluenesulfonic acid (manufactured by Hitachi Chemical Co., Ltd., dryer 900, solid content 50% by mass) as a curing catalyst, toluene/ It diluted with the methyl ethyl ketone/heptane (=3:5:2) solution, and the mold release agent solution of 2 mass % of solid content was prepared.

(Release agent solution X-2)

100 parts by mass of a UV curable silicone resin (UV9300 manufactured by Momentive, 100% by mass of solid content) and 1 part by mass of curing catalyst bis(alkylphenyl)iodonium hexafluoroantimonate, toluene/methylethylketone/heptane (=3 :5:2) solution was diluted, and the mold release agent solution of 2 mass % of solid content was prepared.

(Example 1)

(Adjustment of lubricating coating solution 1)

The lubricating coating solution 1 of the following composition was adjusted.

(Moisture coating solution 1)

41.86 parts by mass of water

35.00 parts by mass of isopropyl alcohol

Acrylic polyol resin A-1 16.57 parts by mass

(Solid content concentration 20% by mass)

Oxazoline-based crosslinking agent D-1 5.68 parts by mass

(Solid content concentration of 25% by mass)

0.59 mass parts of silica particle G-1

(Average particle diameter 200 nm, solid content concentration 40 mass %)

0.30 parts by mass of surfactant H-1 (fluorine-based, solid content concentration of 10% by mass)

(Production 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 containing substantially no particles were subjected to a reduced pressure of 133 Pa. and dried at 135°C for 6 hours. Thereafter, it was supplied to an extruder, melt-extruded into a sheet at about 280°C, and solidified by rapid cooling on a rotating 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 difference in circumferential speed to obtain a uniaxially stretched PET film.

Then, the lubricating coating solution was applied to one side of the PET film with a bar coater, and then dried at 80° C. for 15 seconds. Moreover, it adjusted so that the application amount after final extending|stretching and drying might be set to 0.1 micrometer. Then, in a tenter, stretched 4.0 times in the width direction at 150° C., in a state in which the length of the film in the width direction was fixed, heated at 230° C. for 0.5 second, and further, 3% relaxation treatment in the width direction at 230° C. for 10 seconds to obtain an in-line coated polyester film having a thickness of 31 µm.

(Formation of release coating layer)

The release agent solution X-1 was applied to the inline coated polyester film obtained above with a reverse gravure coater so that the thickness after drying was 0.1 μm on the surface opposite to the lamination surface of the lubrication coating layer, and then dried with hot air at 130° C. for 30 seconds. By doing so, a release coating layer was formed to obtain a release film for producing an ultra-thin ceramic green sheet. The winding property, etc., process passability, and handling property were excellent without a problem in particular. After winding as a roll, the unwinding charge when unwinding again for ceramic sheet coating was low, and adhesion of environmental foreign matter could be suppressed, and a high-quality ceramic capacitor could be produced without degrading the yield of the ceramic capacitor.

(Example 2)

Ultra-thin ceramic green sheet in the same manner as in Example 1 except that the lubricating coating solution 2 in which the crosslinking agent in the lubricating coating solution 1 used in Example 1 was changed to the carbodiimide-based crosslinking agent E-1 (solid content concentration of 40% by mass) was used. A release film for production was obtained.

(Moisture coating solution 2)

43.99 parts by mass of water

35.00 parts by mass of isopropyl alcohol

Acrylic polyol resin A-1 16.57 parts by mass

(Solid content concentration 20% by mass)

3.55 parts by mass of carbodiimide-based crosslinking agent E-1

(solid content concentration 40% by mass)

0.59 mass parts of silica particle G-1

(Average particle size 200 nm, solid content concentration 40 mass %)

0.30 parts by mass of surfactant H-1 (fluorine-based, solid content concentration of 10% by mass)

(Example 3)

For production of ultra-thin ceramic green sheet in the same manner as in Example 1, except that the lubricating coating solution 3 was used in which the crosslinking agent in the lubricating coating solution 1 used in Example 1 was changed to the oxazoline-based crosslinking agent D-2 (solid content concentration of 10% by mass). A release film was obtained.

(Moisture coating solution 3)

33.34 parts by mass of water

35.00 parts by mass of isopropyl alcohol

Acrylic polyol resin A-1 16.57 parts by mass

(Solid content concentration 20% by mass)

Oxazoline-based crosslinking agent D-2 14.20 parts by mass

(solid content concentration 10% by mass)

0.59 mass parts of silica particle G-1

(Average particle diameter 200 nm, solid content concentration 40 mass %)

0.30 parts by mass of surfactant H-1 (fluorine-based, solid content concentration of 10% by mass)

(Example 4)

Except having changed the lubricating coating liquid 1 into the following lubricating coating liquid 4, it carried out similarly to Example 1, and obtained the polyester film.

(Moisture coating solution 4)

43.28 parts by mass of water

35.00 parts by mass of isopropyl alcohol

Acrylic polyol resin A-1 9.47 parts by mass

(Solid content concentration 20% by mass)

11.36 parts by mass of oxazoline-based crosslinking agent D-1

(Solid content concentration of 25% by mass)

0.59 mass parts of silica particle G-1

(Average particle diameter 200 nm, solid content concentration 40 mass %)

0.30 parts by mass of surfactant H-1 (fluorine-based, solid content concentration of 10% by mass)

(Example 5)

Except having changed the lubricating coating liquid 1 into the following lubricating coating liquid 5, it carried out similarly to Example 1, and obtained the polyester film.

(Liquid coating solution 5)

41.15 parts by mass of water

35.00 parts by mass of isopropyl alcohol

Acrylic polyol resin A-1 20.12 parts by mass

(Solid content concentration 20% by mass)

2.84 parts by mass of oxazoline-based crosslinking agent D-1

(Solid content concentration of 25% by mass)

0.59 mass parts of silica particle G-1

(Average particle diameter 200 nm, solid content concentration 40 mass %)

0.30 parts by mass of surfactant H-1 (fluorine-based, solid content concentration of 10% by mass)

(Example 6)

Ultra-thin ceramics in the same manner as in Example 1 except that the acrylic polyol A-1 (solid content concentration: 20 mass%) in the lubricating coating liquid 1 used in Example 1 was changed to acrylic polyol A-2 (solid content concentration: 20 mass%) The release film for green sheet manufacture was obtained.

(Example 7)

The same procedure as in Example 1 was followed except that the acrylic polyol A-1 (solid content concentration of 20 mass%) in the lubricating coating solution 1 used in Example 1 was changed to acrylic polyol A-3 (solid content concentration of 20 mass%), and ultra-thin ceramic The release film for green sheet manufacture was obtained.

(Example 8)

Ultra-thin ceramics in the same manner as in Example 1 except that the acrylic polyol A-1 (solid content concentration of 20 mass%) in the lubricating coating solution 1 used in Example 1 was changed to acrylic polyol A-4 (solid content concentration of 20 mass%). The release film for green sheet manufacture was obtained.

(Example 9)

The same procedure as in Example 1 was followed except that the acrylic polyol A-1 (solid content concentration of 20 mass%) in the lubricating coating liquid 1 used in Example 1 was changed to acrylic polyol A-5 (solid content concentration of 20 mass%), and ultra-thin ceramic The release film for green sheet manufacture was obtained.

(Example 10)

The same procedure as in Example 1 was followed except that the acrylic polyol A-1 (solid content concentration of 20 mass%) in the lubricating coating solution 1 used in Example 1 was changed to acrylic polyol A-6 (solid content concentration of 20 mass%), and ultra-thin ceramic The release film for green sheet manufacture was obtained.

(Example 11)

The same procedure as in Example 1 was followed except that the acrylic polyol A-1 (solid content concentration of 20 mass%) in the lubricating coating solution 1 used in Example 1 was changed to acrylic polyol A-7 (solid content concentration of 20 mass%), and ultra-thin ceramic The release film for green sheet manufacture was obtained.

(Example 12)

The same procedure as in Example 1 was followed except that the acrylic polyol A-1 (solid content concentration of 20 mass%) in the lubricating coating solution 1 used in Example 1 was changed to acrylic polyol A-8 (solid content concentration of 20 mass%), and ultra-thin ceramic The release film for green sheet manufacture was obtained.

(Example 13)

Ultra-thin ceramics in the same manner as in Example 1 except that the acrylic polyol A-1 (solid content concentration of 20 mass%) in the lubricating coating liquid 1 used in Example 1 was changed to acrylic polyol A-9 (solid content concentration of 20 mass%). The release film for green sheet manufacture was obtained.

(Example 14)

The same procedure as in Example 1 was followed except that the acrylic polyol A-1 (solid content concentration of 20 mass%) in the lubricating coating liquid 1 used in Example 1 was changed to acrylic polyol A-10 (solid content concentration of 20 mass%), and ultra-thin ceramic The release film for green sheet manufacture was obtained.

(Example 15)

Ultra-thin ceramics in the same manner as in Example 1, except that the acrylic polyol A-1 (solid content concentration of 20 mass%) in the lubricating coating liquid 1 used in Example 1 was changed to acrylic polyol A-11 (solid content concentration of 20 mass%). The release film for green sheet manufacture was obtained.

(Example 16)

The same procedure as in Example 1 was followed except that the acrylic polyol A-1 (solid content concentration of 20 mass%) in the lubricating coating liquid 1 used in Example 1 was changed to acrylic polyol A-12 (solid content concentration of 20 mass%), and the ultra-thin ceramic The release film for green sheet manufacture was obtained.

(Example 17)

Except having changed the lubricating coating solution 1 to the following lubricating coating solution 17, it carried out similarly to Example 1, and obtained the release film for ultra-thin ceramic green sheet manufacture.

(Oticulous coating solution 17)

41.74 parts by mass of water

35.00 parts by mass of isopropyl alcohol

Acrylic polyol resin A-10 16.57 parts by mass

(Solid content concentration 20% by mass)

Oxazoline-based crosslinking agent D-1 5.68 parts by mass

(Solid content concentration of 25% by mass)

0.59 mass parts of silica particle G-1

(Average particle diameter 200 nm, solid content concentration 40 mass %)

Silica particle G-4 0.12 parts by mass

(Average particle diameter of 450 nm, solid content concentration of 40 mass%)

0.30 parts by mass of surfactant H-1 (fluorine-based, solid content concentration of 10% by mass)

(Example 18)

Except having changed the lubricating coating liquid 1 to the following lubricating coating liquid 18, it carried out similarly to Example 1, and obtained the release film for ultra-thin ceramic green sheet manufacture.

(Moisture coating solution 18)

41.15 parts by mass of water

35.00 parts by mass of isopropyl alcohol

Acrylic polyol resin A-10 16.57 parts by mass

(Solid content concentration 20% by mass)

Oxazoline-based crosslinking agent D-1 5.68 parts by mass

(Solid content concentration of 25% by mass)

1.18 parts by mass of silica particle G-2

(Average particle diameter 40 nm, solid content concentration 40 mass %)

Silica particle G-4 0.12 parts by mass

(Average particle diameter of 450 nm, solid content concentration of 40 mass%)

0.30 parts by mass of surfactant H-1 (fluorine-based, solid content concentration of 10% 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 lubricating coating solution 1 was changed to the following lubricating coating solution 19.

(Oticulous coating solution 19)

41.27 parts by mass of water

35.00 parts by mass of isopropyl alcohol

Acrylic polyol resin A-10 16.57 parts by mass

(Solid content concentration 20% by mass)

Oxazoline-based crosslinking agent D-1 5.68 parts by mass

(Solid content concentration of 25% by mass)

1.18 parts by mass of silica particle G-3

(Average particle diameter of 100 nm, solid content concentration of 40 mass %)

0.30 parts by mass of surfactant H-1 (fluorine-based, solid content concentration of 10% by mass)

(Example 20)

Except having changed the lubricating coating liquid 1 to the following lubricating coating liquid 20, it carried out similarly to Example 1, and obtained the release film for ultra-thin ceramic green sheet manufacture.

(Moisture coating solution 20)

40.09 parts by mass of water

35.00 parts by mass of isopropyl alcohol

Acrylic polyol resin A-10 16.57 parts by mass

(Solid content concentration 20% by mass)

Oxazoline-based crosslinking agent D-1 5.68 parts by mass

(Solid content concentration of 25% by mass)

Acrylic particle G-5 2.37 mass parts

(Average particle diameter 150 nm, solid content concentration 10 mass %)

0.30 parts by mass of surfactant H-1 (fluorine-based, solid content concentration of 10% by mass)

(Example 21)

Except having formed the release coating layer as follows, it carried out similarly to Example 1, and obtained the release film for ultra-thin ceramic green sheet manufacture.

(Formation of release coating layer)

The release agent solution X-2 was applied to the in-line coated polyester film obtained above with a reverse gravure coater so that the thickness after drying became 0.1 μm, and then dried with hot air at 90° C. UV irradiation (300 mJ/cm 2 ) was performed with H Bulb manufactured by Corporation, to form a release coating layer and obtain a release film for producing an ultra-thin ceramic green sheet.

(Example 22)

Ultra-thin ceramics in the same manner as in Example 1 except that the acrylic polyol A-1 (solid content concentration of 20 mass%) in the lubricating coating liquid 1 used in Example 1 was changed to acrylic polyol A-13 (solid content concentration of 20 mass%). The release film for green sheet manufacture was obtained.

(Example 23)

Except having changed the lubricating coating liquid 1 to the following lubricating coating liquid 22, it carried out similarly to Example 1, and obtained the release film for ultra-thin ceramic green sheet manufacture.

(Oticulus coating solution 22)

41.39 parts by mass of water

35.00 parts by mass of isopropyl alcohol

Acrylic polyol resin A-13 16.57 parts by mass

(Solid content concentration 20% by mass)

Oxazoline-based crosslinking agent D-1 5.68 parts by mass

(Solid content concentration of 25% by mass)

0.59 mass parts of silica particle G-1

(Average particle size 200 nm, solid content concentration 40 mass %)

Acrylic particle G-6 0.47 mass part

(Average particle diameter of 350 nm, solid content concentration of 10 mass %)

0.30 parts by mass of surfactant H-1 (fluorine-based, solid content concentration of 10% by mass)

(Example 24)

Except having changed the lubricating coating liquid 1 to the following lubricating coating liquid 23, it carried out similarly to Example 1, and obtained the release film for ultra-thin ceramic green sheet manufacture.

(Oticulous coating solution 23)

41.39 parts by mass of water

35.00 parts by mass of isopropyl alcohol

Acrylic polyol resin A-13 16.57 parts by mass

(Solid content concentration 20% by mass)

Oxazoline-based crosslinking agent D-1 5.68 parts by mass

(Solid content concentration of 25% by mass)

0.59 mass parts of silica particle G-1

(Average particle diameter 200 nm, solid content concentration 40 mass %)

Acrylic particle G-7 0.47 mass part

(Average particle size of 450 nm, solid content concentration of 10% by mass)

0.30 parts by mass of surfactant H-1 (fluorine-based, solid content concentration of 10% by mass)

(Example 25)

Except having changed the lubricating coating solution 1 to the following lubricating coating solution 24, it carried out similarly to Example 1, and obtained the release film for ultra-thin ceramic green sheet manufacture.

(Acoustic coating solution 24)

39.62 parts by mass of water

35.00 parts by mass of isopropyl alcohol

Acrylic polyol resin A-13 16.57 parts by mass

(Solid content concentration 20% by mass)

Oxazoline-based crosslinking agent D-1 5.68 parts by mass

(Solid content concentration of 25% by mass)

Acrylic particle G-5 2.37 mass parts

(average particle size 150 nm, solid content concentration 10 mass%)

Acrylic particle G-7 0.47 mass part

(Average particle size of 450 nm, solid content concentration of 10% by mass)

0.30 parts by mass of surfactant H-1 (fluorine-based, solid content concentration of 10% by mass)

(Comparative Example 1)

Except having changed the lubricating coating liquid 1 into the following lubricating coating liquid 25, it carried out similarly to Example 1, and obtained the polyester film.

(Oticulus coating solution 25)

48.33 parts by mass of water

35.00 parts by mass of isopropyl alcohol

Polyester water dispersion B-1 15.78 parts by mass

(solid content concentration of 30% by mass)

0.59 mass parts of silica particle G-1

(Average particle diameter 200 nm, solid content concentration 40 mass %)

Surfactant (fluorine-based, solid content concentration 10% by mass) 0.30 parts by mass

(Comparative Example 2)

Except having changed the lubricating coating liquid 1 into the following lubricating coating liquid 26, it carried out similarly to Example 1, and obtained the polyester film.

(Moisture coating solution 26)

45.18 parts by mass of water

35.00 parts by mass of isopropyl alcohol

Polyester water dispersion B-2 18.93 parts by mass

(Solid content concentration of 25% by mass)

0.59 mass parts of silica particle G-1

(Average particle diameter 200 nm, solid content concentration 40 mass %)

Surfactant (fluorine-based, solid content concentration 10% by mass) 0.30 parts by mass

(Comparative Example 3)

Except having changed the lubricating coating liquid 1 into the following lubricating coating liquid 27, it carried out similarly to Example 1, and obtained the polyester film.

(Moisture coating liquid 27)

51.32 parts by mass of water

35.00 parts by mass of isopropyl alcohol

12.79 parts by mass of polyurethane resin water dispersion C-1

(Solid content concentration 37% by mass)

0.59 mass parts of silica particle G-1

(Average particle diameter 200 nm, solid content concentration 40 mass %)

Surfactant (fluorine-based, solid content concentration 10% by mass) 0.30 parts by mass

(Comparative Example 4)

Except having changed the lubricating coating liquid 1 into the following lubricating coating liquid 28, it carried out similarly to Example 1, and obtained the polyester film.

(Moisture coating solution 28)

47.39 parts by mass of water

35.00 parts by mass of isopropyl alcohol

11.04 parts by mass of polyester water dispersion B-1

(solid content concentration of 30% by mass)

Oxazoline-based crosslinking agent D-1 5.68 parts by mass

(Solid content concentration of 25% by mass)

0.59 mass parts of silica particle G-1

(Average particle diameter 200 nm, solid content concentration 40 mass %)

Surfactant (fluorine-based, solid content concentration 10% by mass) 0.30 parts by mass

(Comparative Example 5)

Except having changed the lubricating coating liquid 1 into the following lubricating coating liquid 29, it carried out similarly to Example 1, and obtained the polyester film.

(Moisture coating solution 29)

49.51 parts by mass of water

35.00 parts by mass of isopropyl alcohol

11.04 parts by mass of polyester water dispersion B-1

(solid content concentration of 30% by mass)

3.55 parts by mass of carbodiimide-based crosslinking agent E-1

(solid content concentration 40% by mass)

0.59 mass parts of silica particle G-1

(Average particle diameter 200 nm, solid content concentration 40 mass %)

Surfactant (fluorine-based, solid content concentration 10% by mass) 0.30 parts by mass

(Comparative Example 6)

Except having changed the lubricating coating liquid 1 into the following lubricating coating liquid 30, it carried out similarly to Example 1, and obtained the polyester film.

(Moisture coating solution 30)

40.44 parts by mass of water

35.00 parts by mass of isopropyl alcohol

Acrylic polyol resin A-1 23.67 parts by mass

(Solid content concentration 20% by mass)

0.59 mass parts of silica particle G-1

(Average particle diameter 200 nm, solid content concentration 40 mass %)

0.30 parts by mass of surfactant H-1 (fluorine-based, solid content concentration of 10% by mass)

(Comparative Example 7)

Except having changed the lubricating coating liquid 1 into the following lubricating coating liquid 31, it carried out similarly to Example 1, and obtained the polyester film.

(Moisture coating solution 31)

45.65 parts by mass of water

35.00 parts by mass of isopropyl alcohol

Acrylic polyol resin A-1 16.57 parts by mass

(Solid content concentration 20% by mass)

1.89 parts by mass of isocyanate crosslinking agent F-1

(Solid content concentration 75% by mass)

0.59 mass parts of silica particle G-1

(Average particle diameter 200 nm, solid content concentration 40 mass %)

0.30 parts by mass of surfactant H-1 (fluorine-based, solid content concentration of 10% by mass)

(Comparative Example 8)

As a film for forming a release coating layer, in place of the in-line coating film having a lubricity coating layer on one surface created in Example 1, it was changed to E5000-25 μm (manufactured by Toyobo) and used as in Example 1 A release film for manufacturing a ceramic green sheet was obtained by this method. E5000 contained particles inside the film, and the Sa on both surfaces was 0.031 µm.

(Comparative Example 9)

Ceramic green sheet in the same manner as in Example 1, except that the laminated film Z was used instead of the inline coating film having a lubricating coating layer on one surface prepared in Example 1 as a film for forming the release coating layer. A release film for production was obtained. A release coating layer was provided on the surface (layer not containing particles) from which PET(II) pellets of 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, with respect to the resin, crosslinking agent, particles, and surfactant in the lubricating coating solution, the respective compositions are described as parts by mass of the solid content, and the solid content of the resin, crosslinking agent, particles, and surfactant present in the lubricating coating solution is The total of the mass parts becomes the mass part of the total solid content of the lubricating coating layer, and for the resin, crosslinking agent, particles, and surfactant, the mass part of each solid content is divided by the mass part of the total solid content of the lubricating coating layer, and the resin, crosslinking agent, particles, and interface The mass percentage in the total solid content in the lubricating coating layer of an activator can be calculated|required.

In Examples 1 to 25, when the roll is unwound after release processing, the unwinding charge is low, and environmental foreign substances are difficult to adhere to. there was. A release film comprising a polyester film substantially free of inorganic particles as a base material, a release coating layer having a release coating layer on one surface of the base material, and a release coating layer containing particles on the other surface; Since the lubricating coating layer is formed by curing a composition containing an acrylic resin and at least one crosslinking agent selected from an oxazoline-based crosslinking agent or a carbodiimide-based crosslinking agent, the lubricating coating layer has a high crosslinking density and thus the lubricating coating layer the amount of deformation is reduced. Since the contact area becomes small at the time of peeling of the mold release layer and the lubricity layer at the time of unwinding the film roll on which mold release processing has been completed, it is thought that the amount to be charged could be suppressed.

On the other hand, in Comparative Examples 1 to 7, the lubricity coating layer formed by curing the composition containing the acrylic resin as stipulated in the present invention and at least one crosslinking agent selected from an oxazoline-based crosslinking agent or a carbodiimide-based crosslinking agent is not Therefore, the crosslinking density of the lubricating coating layer becomes low, and the deformation amount of the lubricating coating layer becomes large. Since the contact area becomes large at the time of peeling of the mold release layer and the lubricity layer at the time of unwinding the film roll in which mold release processing has been completed, it is thought that unwinding electrification became large. Moreover, in Comparative Examples 8 and 9, although unwinding charging was low, the ceramic sheet did not have the lubricating coating layer prescribed|regulated by this invention, and the surface roughness of the lubricating surface was large, so that pinholes were generated in the ceramic sheet.

ADVANTAGE OF THE INVENTION According to this invention, even when a ceramic green sheet is thinned, it becomes possible to provide the release film for ceramic green sheet manufacture which can prevent pinholes, partial thickness fluctuations, etc., and prevention of adhesion of environmental foreign material due to charging. . In addition, by using the release film for manufacturing a ceramic green sheet of the present invention, an ultra-thin ceramic green sheet can be obtained, and a minute ceramic capacitor can be efficiently manufactured.

Claims (8)

A polyester film substantially free of inorganic particles is used as a base material, and a release coating layer is provided on one surface of the base material, and a lubricity coating layer containing particles is provided on the other surface of the base material. The layer is formed by curing a composition containing an acrylic resin and at least one crosslinking agent selected from an oxazoline-based crosslinking agent or a carbodiimide-based crosslinking agent, and the glass transition temperature of the acrylic resin is 50°C or more and 110°C or less. Release film for green sheet production. The release film for manufacturing a ceramic green sheet according to claim 1, wherein the acrylic resin has an acid value of 40 mgKOH/g or more and 400 mgKOH/g or less. The method according to claim 1, wherein the area surface average roughness (Sa) of the lubricating 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 of the roughness curve element (RSm) is 10 µm or less, Release film for the manufacture of ceramic green sheets. The release film for manufacturing a ceramic green sheet according to claim 1, wherein the lubricating coating layer has a thickness of 0.001 μm or more and 2 μm or less. The manufacturing method of a ceramic green sheet using the release film for ceramic green sheet manufacture in any one of Claims 1-4. The method for manufacturing a ceramic green sheet according to claim 5, wherein the thickness of the ceramic green sheet to be manufactured is 0.2 µm or more and 2.0 µm or less. The manufacturing method of a ceramic capacitor which employ|adopts the manufacturing method of the ceramic green sheet of Claim 5. delete