KR102422462B1 - Release film for manufacturing ceramic green sheet - Google Patents

Abstract

[Problem] To provide an excellent release film for manufacturing a ceramic green sheet capable of preventing pinholes and partial thickness fluctuations, and reducing unwinding charging, even when the ceramic green sheet is thinned. [Solutions] 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 area surface average roughness (Sa) of the 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, and the lubricating coating is applied. A release film for manufacturing a ceramic green sheet having a Martens hardness (HM) of 150 N/mm 2 or more and an elastic deformation work rate (ηit) of 28% or more of a mixed composition of a resin and a crosslinking agent of the layer.

Description

Release film for manufacturing ceramic green sheet

The present invention relates to a release film for manufacturing a ceramic green sheet. More particularly, 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, since this prior art has a large protrusion on the back side, there is a problem that a pin hole or partial thickness variation occurs.

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

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

This invention was made|formed against the subject of such prior art. 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. A polyester film substantially free of inorganic particles is used as a base material, and has a release coating layer on one surface of the base material, and a lubricity coating layer containing particles on the other surface, and a lubricity coating layer The area surface average roughness (Sa) of 1 nm or more and 25 nm or less, the maximum protrusion height (P) of 60 nm or more and 500 nm or less, and the average length (RSm) of the roughness curve element is 10 µm or less, and the A release film for manufacturing a ceramic green sheet having a Martens hardness (HM) of 150N/mm 2 or more and an elastic deformation work rate (ηit) of 28% or more of a single film of a mixture composition of a resin and a crosslinking agent.

2. The release film for producing a ceramic green sheet according to 1 above, 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.

3. The release film for manufacturing a ceramic green sheet according to 1 or 2, wherein the lubricating coating layer has a thickness of 0.001 µm or more and 2 µm or less.

4. The manufacturing method of a ceramic green sheet using the release film for manufacturing a ceramic green sheet in any one of said 1-3.

5. The method for producing a ceramic green sheet according to 4 above, wherein the thickness of the ceramic green sheet to be manufactured is 0.2 µm or more and 2.0 µm or less.

6. The manufacturing method of a ceramic capacitor which employ|adopts the manufacturing method of the ceramic green sheet of said 4 or 5.

ADVANTAGE OF THE INVENTION According to this invention, even when a ceramic green sheet is thinned, it becomes possible to provide the excellent release film for ceramic green sheet manufacture which can be equipped with both prevention of pinholes, partial thickness fluctuations, etc., and reduction of 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, may simply be referred to as a release film) has a release coating layer on one side of a biaxially oriented polyester film, which is a base film, and a release coating layer on the other side containing particles. is a release film having

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

In the present invention, as the lubricating coating layer, the Martens hardness (HM) of the mixed composition single film of the resin and the crosslinking agent of the lubricating coating layer is 150N/mm 2 or more, and the elastic deformation work rate (ηit) is 28% or more. The hardness of the layer is appropriately increased, and the deformation of the lubricity coating layer that occurs when the lubricity coating layer comes into contact with the release coating layer is immediately restored when the pressure is weakened.

A high Martens hardness contributes to becoming difficult to generate|occur|produce the deformation|transformation of the lubricating coating layer at the time of winding up after mold release coating layer coating.

When the elastic deformation work rate (ηit) is high, the ratio of elastic deformation is large compared to the plastic deformation among the applied work, and when the pressure with the release application layer is weakened, the lubricity coating layer deformed by contact with the release coating layer This means that the deformation is restored immediately. The present inventors discovered that not only the Martens hardness indicating hardness, but also the elastic deformation work rate, which is an index indicating whether the deformation is recovered immediately, affects the unwinding charging when the film roll is unwound.

When the film roll diameter becomes small during unwinding of the film roll, the deformation of the lubricating coating layer is recovered from the state of the roll before unwinding, and the contact area between the lubricating coating layer and the release layer at the time of unwinding becomes small, contributing to the reduction of unwinding charging I'm thinking of doing it.

In general, it is known that the larger the contact area of two things in contact, the larger the electrification at the time of peeling the two things. When the amount of deformation of the release film roll is small and the recovery of the deformation is fast, the contact area between the release film roll and the release layer when the release film roll is unwound is small, so that unwinding charging when the release film roll is unwound can be suppressed. desirable.

It is preferable that there is little unwinding charging because it is possible to prevent the quality abnormality of the ceramic capacitor|condenser by adhesion of environmental foreign material to the mold release surface. In the recent trend of thinning ceramic sheets, even the adhesion of 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 the average length (RSm) of the roughness curve elements of the lubricating coating layer is added to fall within a specific range.

(base film)

A film used as a preferred substrate in the present invention 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 is preferred. 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 most preferable from the balance of physical properties and cost.

In addition, the said polyester film may be a single layer or a multilayer may be sufficient as it. Moreover, 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.

(Moisture coating layer)

The release film of this invention has a release 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 lubricity coating layer at least.

In the present invention, it is preferable that the Martens hardness (HM) of the mixed composition single film of the resin and the crosslinking agent of the lubricating coating layer is 150N/mm 2 or more. The Martens hardness (HM) is more preferably 200 N/mm 2 or more. When the Martens hardness (HM) of the mixed composition single film of the resin and the crosslinking agent of the lubricating coating layer is 150N/mm 2 or more, the hardness of the lubricating coating layer is suitably increased, which is preferable.

In the present invention, it is preferable that the Martens hardness (HM) of the mixed composition of the resin and the crosslinking agent of the lubricating coating layer is 600 N/mm 2 or less. The Martens hardness (HM) is more preferably 500 N/mm 2 or less. If the Martens hardness (HM) of the single film of the mixed composition of the resin and the crosslinking agent of the release coating layer is 600 N/mm 2 or less, it is preferable that the surface of the release coating layer is not damaged such as scratches or dents.

In the present invention, it is preferable that the elastic deformation work rate (ηit) of the mixed composition of the resin and the crosslinking agent of the lubricating coating layer is 28% or more. The elastic deformation work rate (ηit) is more preferably 30% or more. When the elastic deformation rate (ηit) of the single film of the mixed composition of the resin and the crosslinking agent of the lubricity coating layer is 28% or more, the lubricity coating layer deformation that occurs when the lubricity coating layer comes into contact with the release coating layer is the pressure during unwinding of the film roll. As it becomes smaller, it recovers immediately. Since the contact area of the lubricating application layer and the mold release layer at the time of unwinding a film roll becomes small by a deformation|transformation recovery|recovery, since unwinding charging at the time of unwinding a release film roll can be suppressed, it is preferable.

In the present invention, it is preferable that the elastic deformation work rate (ηit) of the mixed composition of the resin and the crosslinking agent of the lubricating coating layer is 90% or less. The elastic deformation work rate (ηit) is more preferably 80% or less. If the elastic deformation work rate (ηit) of the single film of the mixed composition of the resin and the crosslinking agent of the lubricity coating layer is 90% or less, the friction coefficient with the release layer is too low because the plastic deformation of the lubricity coating layer is appropriate, and winding misalignment occurs, etc. It is preferable because the concern of

(Binder resin in the lubricating coating layer)

The binder resin constituting the lubricating coating layer in the present invention is not particularly limited, and specific examples of the polymer include polyester resins, acrylic resins, urethane resins, polyvinyl resins (such as polyvinyl alcohol), polyalkylene glycols, Polyalkylene imine, methyl cellulose, hydroxy cellulose, starch, etc. are mentioned. Among these, it is preferable to use a polyester resin and an acrylic resin from the point which can achieve the above-mentioned Martens hardness and elastic deformation uniformity. Among these, it is preferable to use an acrylic resin especially. 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. Among them, 2-hydroxyethyl (meth)acrylate is preferable from the viewpoint of not impairing water solubility. In addition, these may use 2 or more types together.

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 a carboxyl group such as (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid, and monomers containing an acid anhydride group such as maleic anhydride and itaconic anhydride.

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 a lubricating 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 too high 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 ease of use, it is preferable to use an amine compound as a neutralizing agent. 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 liquid, 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 coating layer do not extremely interact 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. If the glass transition temperature of the acrylic resin is 50° C. or higher, the hardness of the lubricating coating layer is appropriately increased, which 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 alkylesters, 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, and caproic acid. Vinyl, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, vinyl pivalate, vinyl octylate, vinyl monochloroacetate , vinyl esters such as 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 Can be used.

It is preferable that the monomer for Tg adjustment determines the appropriate amount of a hydroxyl-containing monomer and a carboxyl-group-containing monomer, and then sets it as the remainder. Tg of a copolymer is calculated|required from the formula of following Fox.

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

Tg _n : homopolymer Tg(K) of each monomer

As a monomer to be copolymerized for Tg adjustment, a component that reduces surface free energy such as a long-chain alkyl group may be introduced. As an acrylic resin into which the long-chain alkyl group was introduce|transduced, it is preferable to have a C8-20 alkyl group in the side chain of an acrylic resin. Moreover, it is a polymer which has (meth)acrylic acid ester as a main repeating unit, The copolymer which contains the C8-20 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. When it is 50 mol% or less, Tg of the coating film obtained does not become too low with respect to a suitable range, and since the hardness of a coating film can be maintained high, it is preferable. In the present invention, the amount of the monomer having a long-chain alkyl group may be 0 mol% as long as the Tg can maintain a suitable range, but if it is 5 mol% or more, the effect of adjusting the Tg of the acrylic resin becomes clear, which 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 preferable 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. If 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-based resins (such as polyvinyl alcohol), polyalkylene glycol, polyalkylene imine, 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 become small 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 a carbodiimide-based crosslinking agent, the adhesion with 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 Unwinding electrification at the time of unwinding a roll can be suppressed. Another crosslinking agent may be used in combination, and specific crosslinking agents that can be used in combination include urea-based, epoxy-based, melamine-based, isocyanate-based, and silanol-based crosslinking agents. 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, a polymerizable unsaturated monomer having an oxazoline group is obtained by copolymerizing a polymerizable unsaturated monomer having an oxazoline group, if necessary, with other polymerizable unsaturated monomers 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, and the like. These may be used individually and may use 2 or more types together.

As another polymerizable unsaturated monomer, For example, 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; 2-hydroxyethyl (meth)acryl hydroxyalkyl esters having 2 to 8 carbon atoms of (meth)acrylic acid such as lactate 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 uses the obtained crosslinking agent having an oxazoline group as a water-soluble crosslinking agent, and is preferably a hydrophilic monomer from the viewpoint of improving compatibility with other resins, wettability, crosslinking reaction efficiency, and the like. 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 2,2,4 - Aliphatic diisocyanate, such as trimethyl hexamethylene diisocyanate, is mentioned. From the viewpoint of yellowing, aromatic aliphatic diisocyanates, alicyclic diisocyanates and aliphatic diisocyanates are preferable.

Moreover, even if the said diisocyanate uses the compound which reacts with terminal isocyanates, such as monoisocyanate, controlling a molecule|numerator to an appropriate polymerization degree, and using it, there is no hindrance. 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 -NH2 group, a COOH group, and an SO3H 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 above mono- or polycarbodiimide compound is preferably maintained in a uniformly dispersed state when blended with an aqueous coating material. It is preferable to add a hydrophilic segment to the molecular structure of , and mix it with the paint in the form of a self-emulsion or self-dissolved product.

Examples of the carbodiimide-based crosslinking agent used in the present invention include water dispersibility and water solubility. It has good compatibility with other water-soluble resins, and water solubility is preferable from the viewpoint of 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 dialkylaminoalcohols 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 ionicity 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. If it is 5 mass % or more, since the crosslinking density of resin of an application layer does not fall, it is preferable. If it is 80 mass % or less, since the amount of carboxyl groups of the acrylic resin which is the object to be crosslinked 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, zinc sulfate Inorganic particles, such as 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, melamine organic particles such as polycarbonate-based, urea-based, epoxy-based, urethane-based, phenol-based, diallylphthalate-based, and polyester-based particles are mentioned. It is preferably used.

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 that 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 can also be used in the area surface average roughness (Sa) and maximum protrusion height (P), which will be described later. It is preferable to reduce the average length (RSm) of the roughness curve element while keeping it small, and to achieve both slidability and smoothness, particularly preferably small particles of 30 nm or more and 250 nm or less, and an average particle diameter of 350 to Large particles of 600 nm are used together. When mixing small particles and large particles, it is preferable to make the mass content of small particles larger than the mass content of large particles with respect to the entire solid content of the coating layer.

The average particle diameter of the particles was measured by observing the film cross-section particles 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. .

The shape of particle|grains will not be specifically limited if the objective of this invention is satisfied, Spherical particle|grains and non-spherical particle|grains of an irregular shape can be used. An irregular particle diameter can be calculated as an equivalent circle diameter. The equivalent circle diameter is a value obtained by dividing the area of the observed particle by pi, calculating the square root, and doubling it.

It is preferable that the ratio of particle|grains with respect to the total solid of the lubricating coating layer 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 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 of particle|grains with respect to the total solid of the lubricating coating layer 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 the lubricity coating layer is taken out by drying. 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, the mass % of the particle|grains contained in the 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 of the grade which does not impair the coating appearance. As said additive, a fluorescent dye, an optical brightening agent, a plasticizer, a ultraviolet absorber, a pigment dispersing agent, a foam suppressing agent, an antifoamer, antiseptic|preservative etc. are mentioned, for example.

The lubricating coating layer can also contain surfactant for the purpose of improving the leveling properties at the time of application and defoaming the coating liquid. The surfactant may be any of cationic, anionic, and nonionic, but silicone, acetylene glycol or fluorine surfactants are preferred. It is preferable to make an application layer contain these surfactants 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 forming the polyester base film, can be applied, but the in-line coating method is more preferable because it is efficient do.

Any known method can be used as the method for applying the coating liquid to the polyethylene terephthalate (hereinafter, sometimes abbreviated as PET) film as the coating method. For example, the reverse roll coat method, the gravure coat method, the kiss coat method, the die coater method, the roll brush method, the spray coat method, the air knife coating method, the wire bar coat method, the pipe doctor method, the impregnation coat method, the curtain coat method , and the like. These methods are applied individually 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 organic solvents such as toluene, water, or a mixed system of water and a water-soluble organic solvent, but preferably water alone or a so-called water-based solvent obtained by mixing water with a water-soluble organic solvent in view of environmental problems. desirable.

Although the solid content concentration of the lubricating coating liquid varies depending on the kind of binder resin, the kind of solvent, etc., it is preferably 0.5 mass % or more, and more preferably 1 mass % or more. It is preferable that the 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 the 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 equal to or higher than 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 the polyester film used as a base film may be a uniaxially stretched film or a biaxially stretched film, 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. If the thickness is 5 µm or more, wrinkles are difficult to enter at the time of conveyance of a film, 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, or you may apply to the uniaxially-stretched film before extending|stretching in the horizontal direction after extending|stretching in the longitudinal direction. When coating before extending|stretching of 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 a 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-formability 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 in a roll shape 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. 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 too 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 protrusion 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 increases, the pressure applied per one 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 element is more preferably 5 µm or less, still more preferably 3 µm or less. However, if the average length (RSm) of the roughness curve element is too small, it is related to the content of particles in the lubricating coating layer being too large. Since it is also related to becoming large, 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 too large, and RSm is preferably adjusted to a predetermined range.

(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. may 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 is a resin having a silicone structure in a molecule, and includes curable silicone, silicone graft resin, and modified silicone resin such as alkyl modification, but It is preferable to use a reactive cured silicone resin from a viewpoint. As the reactive cured silicone resin, an addition-reaction-based one, a condensation-reactive-based one, or an ultraviolet or electron beam curing-based resin can be used. More preferably, those of a low-temperature curable addition reaction system that can be processed at a low temperature and those of an ultraviolet or electron beam curing system are good. By using these things, it can process at low temperature at the time of the coating process with respect to a polyester film. Therefore, there is little heat damage to the polyester film during processing, and a polyester film with high planarity 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 into the terminal or side chain, and hydrodiene siloxane 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 it can be processed at a low temperature. Examples include: Toray Dow Corning's 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.) 561, BY24-562, etc.), solvent addition + UV curing type manufactured 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, photocuring by introducing an unsaturated group, decomposing an onium salt with UV light to generate a strong acid, Crosslinking by cleaving an epoxy group, crosslinking by addition reaction of thiol to vinylsiloxane, etc. are mentioned. 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., Momentive Performance. UV curing silicone (TPR6502, TPR6501, TPR6500, UV9300, UV9315, XS56-A2982, UV9430, etc.) manufactured by Materials Corporation, UV curing silicone manufactured by Arakawa Chemical (silicorice UV POLY200, POLY215, POLY201, KF-) UV265AM, etc.).

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

As examples of other resins used, alkyd resins, acrylic resins or methylated melamines, alkyd resins and acrylic resins obtained by stearyl-modified, lauryl-modified or the like are also suitable.

As aminoalkyd resin obtained by the reaction of the said methylation melamine, etc., Tessefine 303, Tessefine 305, Tessefine 314 manufactured by Hitachi Chemical Co., Ltd. are mentioned. As aminoacrylic resin obtained by reaction of a methylated melamine etc., the Hitachi Chemical Co., Ltd. Tessefine 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 particles or the like that form protrusions such as particles from the viewpoint of pinhole generation.

Additives, such as a close_contact|adherence improving agent and an antistatic agent, etc. may be added 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. to the polyester film surface before providing a release coating layer.

In the present invention, the thickness of the release coating layer may be set according to the intended 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 the release coating layer is 0.005 µm 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 occurrence of uneven thickness 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 that the resin constituting the release coating layer may aggregate 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, since it does not cause defects in the ceramic green sheet to be coated and molded thereon; It is preferable that the area|region surface average roughness Sa is 5 nm or less, and the maximum processus|protrusion height P is 30 nm or less. Furthermore, the area|region surface average roughness is 5 nm or less, and the maximum processus|protrusion height 20 nm or less is more preferable. When the region surface roughness is 5 nm or less and the maximum protrusion height is 30 nm or less, defects such as pinholes do not occur 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, contaminants derived from foreign substances or contaminants adhering to lines and devices in the raw material resin or film manufacturing process may peel off and mix into 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 resin having a release property is dissolved or dispersed is applied to one side of the polyester film of the substrate or the like, and the solvent is dried by drying. After removal, 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. In the case of 180 degrees C or less, the flatness of a film is maintained, and there is little possibility of raising the thickness nonuniformity 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 making 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, the bump 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 Conventionally known methods, such as the 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 surface. 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 is manufactured 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 obtained 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. . The mother laminate is divided into a plurality of parts, and a raw ceramic body is produced. A ceramic body is obtained by firing a 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 Formula of Fox.

[Renewal Aptitude]

In order to evaluate the stretching aptitude of the acrylic polyol itself, the synthesized acrylic polyols (1) to (12) 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 manufacturing the solution of a single acrylic polyol, the solution was apply|coated with Mayer bar #5 on the surface of the polyester film which performed only longitudinal stretching. 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 predried. Next, the sample was set in the manual stretching apparatus (made by Toyobo Engineering Co., Ltd.), put in 100 degreeC hot air circulation oven, and extending|stretching operation was performed slowly. Extending operation was performed until it became length 4 times of 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 the cracking by extending|stretching was judged according to the following reference|standard.

(circle): A crack is not seen at all.

(triangle|delta): A crack is seen slightly (1 to 4).

x: 5 or more cracks, or a crack is seen in the whole 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 of the roughness curve element (RSm) was taken as an average value of 5 measurements, and the maximum projection height (P) was the maximum value of 5 measurements.

(Measuring conditions)

・Measurement mode: WAVE mode

·Objective lens: 50x

·0.5×Tube lens

・Measurement area 187 × 139 μm (Sa, P measurement)

・Measured length (Lr: reference length): 187 μm (RSm measurement)

(2) Evaluation of particle dispersibility of the lubricating coating layer

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

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

○Δ: The maximum projection height P is greater than 0.2 μm and smaller than 0.3 μm.

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

(3) Measurement of Martens hardness and elastic deformation work rate of resin and crosslinking agent mixed composition single film of lubricating coating layer

Resin and crosslinking agent mixed composition used as a sample were adjusted with the mixed solvent (25 degreeC) of 30 mass % of isopropanol and 70 mass % of water so that solid content concentration might be set to 12 mass %. On the surface of the slide glass, the solution was applied with Mayer bar #28. Next, the slide glass sample on which the application layer (thickness 5.0 micrometers) was formed was left still in the hot-air circulation oven set to the temperature of 80 degreeC for 5 minutes, Then, it predried by taking out the film sample from the oven. Next, after leaving the sample still for 2 minutes in the hot-air circulation oven set to the temperature of 230 degreeC, it heat-processed by taking out a film sample from oven.

The surface of the obtained sample piece was subjected to a load-unload test using a dynamic ultrafine hardness tester (DUH-211S, manufactured by Shimadzu Corporation). From this measurement, Martens hardness (HM) and elastic deformation work rate (ηit) were calculated|required using the following formula (average value of n=10).

HM = F/(26.43×h ² )(N/㎟)

(F: load (N), h: press-in depth (mm))

Wtotal = Wplast + Welast(N m)

(Wtotal = total deformation work (N m), Wplast = plastic deformation work (N m), Welast = elastic deformation work (N m))

ηit = (Welast/Wplast)×100(%)

(Measuring conditions)

(1) Indenter used: Diamond equilateral triangular weight indenter (ridge angle: 115°)

(2) Measuring mode: load-unload test

(3) Test force: 0.5 mN

(4) Minimum test force: 0.002 mN

(5) Load speed: 0.025mN/sec

(6) Load holding time: 2sec

(7) unloading holding time: 0sec

(8) Measurement atmosphere: 25±1℃, 65±5%RH

(9) Number of measurement n: 10

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

○: Less than ±3 kV

○△: ±3kV or more, less than 5kV

△: ±5kV or more, less than 10kV

×: ±10 kV or more

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

The composition containing the following materials was stirred and mixed, and it 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.

22.5% by mass of toluene

Ethanol 22.5% by mass

50% by mass of barium titanate (HPBT-1 manufactured by Fuji Titanium)

5% by mass of polyvinyl butyral

(Sekisui Chemical Co., Ltd. S-Rec BH-3)

Then, using an applicator to the release surface of the release film sample, apply the dried slurry to a thickness of 0.5 μm, and after drying at 90° C. for 1 minute, the slurry surface and the smoothing coated layer surface are overlapped, and the weight of 1 kg/cm 2 is applied for 10 minutes. After hanging, 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 was irradiated from the opposite side of the coated surface of the ceramic slurry in a range of 25 cm 2 , the state of occurrence of pinholes visible through light transmission was observed, and visually judged according to the following criteria did.

○: No pinhole occurrence, no problem in thickness fluctuation

(triangle|delta): generation|occurrence|production of a pinhole exists very little, and thickness fluctuation|variation is seen slightly.

x: There is a little generation|occurrence|production of a pinhole, and thickness fluctuation|variation is 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 stirrer, 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. It was continuously supplied to the 1st esterification reaction can, and it was made to react at 255 degreeC with an average residence time of 4 hours at normal pressure. Next, the reaction product in the first esterification reaction can is continuously taken out of the system and supplied to the second esterification reaction can, and EG distilled off from the first esterification can is produced in the second esterification reaction can by 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 TMPA (trimethyl phosphate) in an amount such that the P atom is 40 ppm with respect to the produced PET. The EG 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 and supplied to the third esterification reaction can, and is 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 after dispersing treatment in 5 passes of treatment, and 0.4 mass % of synthetic calcium carbonate having an average particle diameter of 0.6 μm in which 1% by mass of ammonium salt of polyacrylic acid is adhered per calcium carbonate , each was added as a 10% EG slurry, and the reaction was carried out at 260°C with an average residence time of 0.5 hours at atmospheric pressure. The esterification reaction product produced in the third esterification reaction can is continuously supplied to a three-stage continuous polycondensation reaction unit to perform 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 is laminated in a sheet shape of 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, after heating this unstretched sheet|seat with an infrared heater, it extended|stretched 3.5 times longitudinally by the speed difference between rolls at the roll temperature of 80 degreeC. 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, 2.3% relaxation treatment was performed at 170°C in the transverse direction to obtain a biaxially stretched polyethylene terephthalate film Z having a thickness of 31 µm. Sa of the release surface side layer of the obtained film Z was 2 nm, and Sa of the semi-release surface 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) And 490 mass parts of isopropyl alcohol (IPA) was 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 2, 2- azobis-2-methyl-N-2-hydroxyethyl propionamide was added to the 0.5 mass part flask after that. After nitrogen substitution was performed while heating up the inside of the flask to 120°C, the mixture was stirred at 120°C for 2 hours.

Then, 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. Then, 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% by mass (A -1) was obtained. Table 1 lists the composition ratio, Tg, stretching aptitude, and acid value of the acrylic polyol (A-1) by NMR measurement.

(Preparation of acrylic polyols (A-2) to (A-12))

As shown in Table 1, except for changing the amount of MMA, St, SMA, HEMA, MAA, AA, IPA at the time of input, and IPA at the time of dilution, in the same manner as in the production of acrylic polyol 1, the solid content concentration was 20% by mass. Acrylic polyols (A-2) to (A-12) were obtained. The composition ratio, Tg, stretching aptitude, and acid value by NMR measurement of the acrylic polyols (A-2) to (A-12) were written together in Table 1. In addition, the composition ratio is MMA, St (styrene), SMA (stearyl methacrylate), respectively, l-1, 1-2, 1-3 (unit), HEMA is m (unit), MAA, AA (acrylic acid) ) as n (unit).

(Polymerization of polyester resin B0-1)

To a stainless steel autoclave equipped 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 was carried out at a temperature of 160°C to 220°C over 4 hours. Then, it heated up to 255 degreeC and pressure-reduced the reaction system gradually, it was made to react under reduced pressure of 30 Pa for 1 hour and 30 minutes, and co-polyester resin (B0-1) was obtained. 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 aqueous dispersion B-1)

In a reactor equipped with a stirrer, a thermometer, and a reflux device, 30 parts by mass of a 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 resin melt|dissolved completely, it added gradually, stirring 55 mass parts of water to the polyester solution. After addition, it cooled to room temperature, stirring a liquid, and the milky white polyester aqueous dispersion (B-1) of 30 mass % of solid content was produced.

(Polymerization of polyester resin B0-2)

To a stainless steel autoclave equipped 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 acid and 203 mass parts of sebacic acid were added, it heated up from 200 degreeC to 220 degreeC over 1 hour, and esterification was performed. Then, after heating up to 255 degreeC and pressure-reducing the reaction system gradually, it was made to react under reduced pressure of 29 Pa for 1 hour and 30 minutes, and hydrophobic copolymerization polyester resin (B0-2) was obtained. The obtained hydrophobic copolymerized polyester resin (B0-2) was pale yellow and transparent.

(Preparation of polyester aqueous 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 into a reactor equipped with a stirrer, thermometer, reflux device and quantitative dropping device for producing the graft resin. , heated and stirred at 65°C to dissolve the resin. After resin melt|dissolved completely, 24 mass parts of maleic anhydride was added to the polyester solution.

Next, the solution which melt|dissolved 16 mass parts of styrene and 1.5 mass parts of azobisdimethylvaleronitriles in 19 mass parts of methyl ethyl ketone was dripped at 0.1 ml/min in 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 with a uniform 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-based graft copolymer was 68°C.

(Polyester Aqueous Dispersion B-3)

Toyobo Co., Ltd., Vironal (trademark) MD1500, Tg=77 degreeC, and solid content concentration of 30 mass % were used.

(Preparation of polyurethane aqueous dispersion C-1)

To a four-neck flask equipped with a stirrer, a Dimroth cooler, a nitrogen inlet tube, a silica gel drying tube and a thermometer, 43.75 parts by mass of 4,4-dicyclohexylmethane diisocyanate, 12.85 parts by mass of dimethylolbutanoic acid, and polyhexa having a number average molecular weight of 2000 153.41 parts by mass of methylene 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 reached a predetermined amine equivalent. confirmed that Subsequently, after this reaction liquid was temperature-fallen 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., 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 manufactured by removing a part of acetone and water under reduced pressure. The glass transition point 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 the stirrer, the reflux condenser, the nitrogen introduction pipe, and the thermometer, and it heated at 80 degreeC, flowing nitrogen gas gently. 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 dripped over 2 hours from a dropping funnel, respectively, and was made to react, and dripped 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)

In the same manner as in the synthesis of the resin (D-1) having an oxazoline group, a resin (D-2) having an oxazoline group having a different solid content concentration of 10% of the composition (oxazoline group amount and molecular weight) 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 26 parts by mass of 4'-dicyclohexylmethane diisocyanate and 3.8 parts by mass of 3-methyl-1-phenyl-2-phosphoene-1-oxide (2% by mass relative to all isocyanates) as a carbodiimidization catalyst was added, and the mixture was stirred at 185° C. under a nitrogen stream for another 5 hours. The infrared spectrum of the reaction solution was measured, and it was confirmed that absorption at a wavelength of 2200 to 2300 cm ^-1 disappeared. 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 (manufactured by Asahi Kasei Chemicals, Duranate TPA) having an isocyanurate structure using 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) of 75 mass % of solid content was obtained.

(Silica particle G-1)

Colloidal silica (manufactured by Nissan Chemical, trade name MP2040, average particle size 200 nm, solid content concentration 40 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 100 nm, solid content concentration 40% by mass)

(Silica particles G-4)

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

(Acrylic Particles G-5)

Acrylic particle water dispersion (manufactured by Nippon Shokubai, trade name MX100W, average particle size 150 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, 60 mass % solid) and 1.2 parts by mass of p-toluenesulfonic acid (Hitachi Chemical Co., Ltd., dryer 900, solid content 50 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 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, 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 liquid 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

(20% by mass of solid content concentration)

Oxazoline-based crosslinking agent D-1 (solid content concentration of 25% by mass) 5.68 parts by mass

0.59 mass parts of silica particle G-1

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

Surfactant H-1 (fluorine-based, solid content concentration 10% by mass) 0.30 parts 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 substantially free of particles were subjected to a reduced pressure of 133 Pa. and dried at 135°C for 6 hours. Then, it was supplied to an extruder, it melt-extruded in the sheet form at about 280 degreeC, it was made to solidify by rapid cooling on the rotation cooling metal roll maintained at the surface temperature of 20 degreeC, and the unstretched PET sheet was obtained.

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

Next, 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, with 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% width direction relaxation treatment 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, with hot air at 130° C. for 30 seconds. By drying, a release coating layer was formed, and a release film for producing an ultra-thin ceramic green sheet was obtained. It was excellent in process passability, handling property, such as winding property, 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 was used 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). 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

(20% by mass of solid content concentration)

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

(40% by mass of solid content concentration)

0.59 mass parts of silica particle G-1

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

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

(Example 3)

Except for using the lubricating coating solution 3 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), it was carried out in the same manner as in Example 1 for producing an ultra-thin ceramic green sheet 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

(10% by mass of solid content concentration)

0.59 mass parts of silica particle G-1

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

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

(Example 4)

Except having changed the lubricating coating liquid 1 to the following lubricating coating liquid 4, it carried out similarly to Example 1, and obtained the release film for ultra-thin ceramic green sheet manufacture.

(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

(25 mass % of solid content concentration)

0.59 mass parts of silica particle G-1

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

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

(Example 5)

Except having changed the lubricating coating liquid 1 to the following lubricating coating liquid 5, it carried out similarly to Example 1, and obtained the release film for ultra-thin ceramic green sheet manufacture.

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

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

(Example 6)

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-2 (solid content concentration of 20 mass%), and the ultra-thin ceramic The release film for green sheet manufacture was obtained.

(Example 7)

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-3 (solid content concentration of 20 mass%). 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)

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 solution 1 used in Example 1 was changed to acrylic polyol A-5 (solid content concentration: 20 mass%) The release film for green sheet manufacture was obtained.

(Example 10)

Ultra-thin ceramics were carried out 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-6 (solid content concentration of 20 mass%). The release film for green sheet manufacture was obtained.

(Example 11)

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-7 (solid content concentration of 20 mass%). 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: 20 mass%) in the lubricating coating solution 1 used in Example 1 was changed to acrylic polyol A-8 (solid content concentration: 20 mass%), and ultra-thin ceramic The release film for green sheet manufacture was obtained.

(Example 13)

Ultra-thin ceramics were carried out 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-9 (solid content concentration of 20 mass%). The release film for green sheet manufacture was obtained.

(Example 14)

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-10 (solid content concentration of 20 mass%). The release film for green sheet manufacture was obtained.

(Example 15)

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-11 (solid content concentration of 20 mass%), and the ultra-thin ceramic 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 solution 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 liquid 1 to the following lubricating coating liquid 17, it carried out similarly to Example 1, and obtained the release film for ultra-thin ceramic green sheet manufacture.

(Oticulus 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 (solid content concentration of 25% by mass) 5.68 parts by mass

0.59 mass parts of silica particle G-1

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

Silica particle G-4 0.12 parts by mass

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

Surfactant H-1 (fluorine-based, solid content concentration 10% by mass) 0.30 parts 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 (solid content concentration of 25% by mass) 5.68 parts by mass

1.18 parts by mass of silica particle G-2

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

Silica particle G-4 0.12 parts by mass

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

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

(Example 19)

Except having changed the lubricating coating liquid 1 to the following lubricating coating liquid 19, it carried out similarly to Example 1, and obtained the release film for ultra-thin ceramic green sheet manufacture.

(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

(25 mass % of solid content concentration)

1.18 parts by mass of silica particle G-3

(average particle size of 100 nm, solid content concentration of 40% by mass)

Surfactant H-1 (fluorine-based, solid content concentration 10% by mass) 0.30 parts 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 (solid content concentration of 25% by mass) 5.68 parts by mass

Acrylic particle G-5 2.37 mass parts

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

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

To the obtained inline coated polyester film, the release agent solution X-2 was applied with a reverse gravure coater so that the thickness after drying became 0.1 μm, and then dried with hot air at 90° C. for 30 seconds, and immediately after an electrodeless lamp (manufactured by Fusion Corporation) H valve) was irradiated with ultraviolet rays (300 mJ/cm 2 ) to form a release coating layer and obtain a release film for producing an ultra-thin ceramic green sheet.

(Example 22)

Except having changed the lubricating coating liquid 1 to the following lubricating coating liquid 21, it carried out similarly to Example 1, and obtained the release film for ultra-thin ceramic green sheet manufacture.

(Liquid coating solution 21)

47.39 parts by mass of water

35.00 parts by mass of isopropyl alcohol

11.04 parts by mass of polyester aqueous dispersion B-3

(Toyobo Co., Ltd., Vironal (registered trademark) MD1500, Tg=77°C, solid content concentration 30% by mass)

Oxazoline-based crosslinking agent D-1 (solid content concentration of 25% by mass) 5.68 parts by mass

0.59 mass parts of silica particle G-1

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

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

(Comparative Example 1)

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.

(Moisture coating solution 22)

48.33 parts by mass of water

35.00 parts by mass of isopropyl alcohol

15.78 parts by mass of polyester aqueous dispersion B-1

(30 mass % of solid content concentration)

0.59 mass parts of silica particle G-1

(Average particle size 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 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)

45.18 parts by mass of water

35.00 parts by mass of isopropyl alcohol

Polyester aqueous dispersion B-2 18.93 mass parts

(25 mass % of solid content concentration)

0.59 mass parts of silica particle G-1

(average particle size 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 to the following lubricating coating liquid 24, it carried out similarly to Example 1, and obtained the release film for ultra-thin ceramic green sheet manufacture.

(Acoustic coating solution 24)

51.32 parts by mass of water

35.00 parts by mass of isopropyl alcohol

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

(Solid content concentration 37% by mass)

0.59 mass parts of silica particle G-1

(Average particle size 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 to the following lubricating coating liquid 25, it carried out similarly to Example 1, and obtained the release film for ultra-thin ceramic green sheet manufacture.

(Oticulus coating solution 25)

47.39 parts by mass of water

35.00 parts by mass of isopropyl alcohol

Polyester aqueous dispersion B-1 (solid content concentration of 30% by mass) 11.04 parts by mass

Oxazoline-based crosslinking agent D-1 (solid content concentration of 25% by mass) 5.68 parts by mass

0.59 mass parts of silica particle G-1

(Average particle size 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 to the following lubricating coating liquid 26, it carried out similarly to Example 1, and obtained the release film for ultra-thin ceramic green sheet manufacture.

(Moisture coating solution 26)

49.51 parts by mass of water

35.00 parts by mass of isopropyl alcohol

11.04 parts by mass of polyester aqueous dispersion B-1

(30 mass % of solid content concentration)

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

(40% by mass of solid content concentration)

0.59 mass parts of silica particle G-1

(Average particle size 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 to the following lubricating coating liquid 27, it carried out similarly to Example 1, and obtained the release film for ultra-thin ceramic green sheet manufacture.

(Moisture coating liquid 27)

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 size 200 nm, solid content concentration 40 mass %)

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

(Comparative Example 7)

Except having changed the lubricating coating liquid 1 to the following lubricating coating liquid 28, it carried out similarly to Example 1, and obtained the release film for ultra-thin ceramic green sheet manufacture.

(Moisture coating solution 28)

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 mass parts of isocyanate crosslinking agent F-1 (solid content concentration of 75 mass %)

0.59 mass parts of silica particle G-1

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

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

(Comparative Example 8)

As a film for forming a release coating layer, instead of the in-line coating film having a lubricity coating layer on one surface produced in Example 1, it was changed to E5000-25 μm (manufactured by Toyobo) and used in the same manner as in Example 1 to obtain a release film for manufacturing an ultra-thin ceramic green sheet. E5000 contained particles inside the film, and the Sa on both surfaces was 0.031 μm.

(Comparative Example 9)

Ultra-thin ceramic green in the same manner as in Example 1, except that the laminated film Z was used instead of the in-line coating film having a lubricating coating layer on one surface produced in Example 1 as a film for forming the release coating layer. The release film for sheet manufacture was obtained. A release coating layer was provided on the surface (layer not containing particles) from which PET(II) pellets of the laminated film Z were discharged.

Table 2 shows the evaluation results of Examples and Comparative Examples.

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, particle, 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, The mass percentage in the total solid content in the lubricity coating layer of surfactant can be calculated|required.

In Examples 1 to 22, when the roll was unwound after the release processing, the unwinding charge was low and environmental foreign matter was difficult to adhere. A release film, comprising 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, and Since the Martens hardness (HM) of the single film of the mixed composition of the resin and the crosslinking agent of the coating layer is 150 N/mm 2 or more, the crosslinking density of the lubricating coating layer is high, and the amount of deformation of the lubricating coating layer when wound up after release processing is small. In addition, since the elastic deformation work rate (ηit) is 28% or more, the deformation of the lubricating coating layer immediately recovers as the pressure decreases during unwinding of the film roll, and the contact area between the lubricating coating layer and the release layer at the time of unwinding of the film roll is small. Therefore, it is thought that the amount of charge could be suppressed.

On the other hand, in Comparative Examples 1 to 7, since the Martens hardness (HM) and elastic deformation work rate (ηit) of the mixed composition single film of the resin and the crosslinking agent of the lubricating coating layer prescribed in the present invention were not satisfied, mold release processing At the time of peeling of the mold release coating layer at the time of unwinding the used film roll, and a lubrication coating layer, a contact area became large, and it is thought that unwinding charging became large. Moreover, in Comparative Examples 8 and 9, although unwinding charging was low, it did not have the lubricating coating layer prescribed|regulated by this invention, and since the surface roughness of the lubricating surface was large, pinholes generate|occur|produced in the ceramic sheet.

According to the present invention, even when the ceramic green sheet is thinned, it is possible to provide a release film for manufacturing a ceramic green sheet capable of both preventing pinholes and partial thickness fluctuations and preventing adhesion of environmental foreign substances due to charging. . In addition, by using the release film for producing 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 (6)

A polyester film substantially free of inorganic particles is used as a base material, and has a release coating layer on one surface of the base material, and a lubricity coating layer containing particles on the other surface, and the region of the lubricity coating layer The surface average roughness (Sa) 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, and the resin and A release film for manufacturing a ceramic green sheet having a Martens hardness (HM) of 150N/mm 2 or more and an elastic deformation work rate (ηit) of 28% or more of a single film of a mixture composition of a crosslinking agent. The release film for producing a ceramic green sheet according to claim 1, wherein 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 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 1-3. The method for manufacturing a ceramic green sheet according to claim 4, 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 4.