KR20170096963A - Release film for ceramic green sheet manufacturing process and method for manufacturing the same - Google Patents

Abstract

Provided is a release film for a ceramic green sheet manufacturing process, formed by using a peeling agent composition which does not cause clouding, and having excellent smoothness of the peeling surface. The present invention relates to a release film for a ceramic green sheet manufacturing process which includes a substrate (11) and a release agent layer (12) formed on one side of the substrate (11), wherein the release agent layer (12) formed is formed of a release agent composition containing an amino resin, an active energy ray-curable component, polyorganosiloxane, an acid catalyst, and a photopolymerization initiator having a nitrogen atom. The blending amount of the photopolymerization initiator in the release agent composition is 1 part by mass or more and 300 parts by mass or less based on 100 parts by mass of the acid catalyst.

Description

TECHNICAL FIELD [0001] The present invention relates to a release film for a ceramic green sheet manufacturing process, and a method for manufacturing the same. BACKGROUND ART < RTI ID = 0.0 >

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a release film used in a process for producing a ceramic green sheet and a method for manufacturing the same.

Conventionally, in order to produce a multilayer ceramic product such as a multilayer ceramic capacitor or a multilayer ceramic substrate, a ceramic green sheet is formed, and a plurality of the obtained ceramic green sheets are stacked and fired.

The ceramic green sheet is formed by coating a ceramic slurry containing a ceramic material such as barium titanate or titanium oxide on a release film. The peelable film is required to have a peelability that allows the peelable film to be peeled off from a thin ceramic green sheet formed on the peelable film without causing cracking or breakage and by a suitable peel force.

2. Description of the Related Art In recent years, miniaturization and multilayering of multilayer ceramic capacitors and multilayer ceramic substrates have progressed with the miniaturization and high performance of electronic devices, and thinner ceramic green sheets are progressing. When the ceramic green sheet becomes thinner and its thickness after drying becomes, for example, 3 mu m or less, when the ceramic slurry is coated and dried, the ceramic green sheet is subjected to pinholes Defects such as thickness irregularities are likely to occur. Therefore, the peeling agent layer of the peeling film is required to have high smoothness on the surface in contact with the ceramic slurry / ceramic green sheet (hereinafter sometimes referred to as "peeling surface").

Patent Documents 1 and 2 disclose a peeling film in which a layer formed by curing a thermosetting resin between a substrate and a peeling agent layer is formed for the purpose of preventing occurrence of defects such as pinholes and thickness irregularities in a ceramic green sheet Lt; / RTI > In these release films, a layer formed by curing the thermosetting resin is formed for the purpose of reducing the influence of the roughness of the surface of the base material on the smoothness of the release surface of the release agent layer and thereby improving the smoothness of the release surface. In these release films, by forming such a layer, the influence of roughness of the substrate surface on the release surface is reduced to improve the smoothness of the release surface.

Japanese Patent Application Laid-Open No. 2007-69360 Japanese Laid-Open Patent Publication No. 2014-177093

The inventors of the present invention have found out that a release agent composition containing a thermosetting resin and a polyorganosiloxane or a release agent composition containing an active energy ray-curable component and a polyorganosiloxane can be used for the purpose of improving the smoothness, productivity and time- Development of a release film comprising a release agent layer formed using a release agent composition containing a siloxane and a photopolymerization initiator has been underway. Examples of the thermosetting resin include a combination of an amino resin and an acid catalyst.

When a release agent composition containing a thermosetting resin and an active energy ray curing component is used as the release agent composition, a release agent composition containing one of the above-mentioned thermosetting resin and active energy ray curing component is used It is possible to cure the releasing agent composition by suppressing the energy application of the heat and the active energy rays, thereby improving the productivity of the releasing film. In order to form a release agent layer using a release agent composition containing such a thermosetting resin and an active energy ray curing component, a coating liquid containing the release agent composition is applied to one side of the substrate to form a coating layer, By heating, a condensation reaction between the amino resins is caused to form a three-dimensional structure by the amino resin. Subsequently, the coating layer is irradiated with active energy rays to cause a polymerization reaction between the active energy ray-curable components to reinforce the three-dimensional structure.

At this time, the polyorganosiloxane is incorporated into the structure formed by the amino resin or the active energy ray-curable component and is dispersed or ubiquitously present in the obtained releasing agent layer. Further, the acid catalyst promotes the condensation reaction in the amino resin, and the photopolymerization initiator promotes the polymerization reaction of the active energy ray-curable component.

Here, in order to prepare the coating liquid for the exfoliant composition, when the above-mentioned respective components are mixed in the organic solvent, a component which is not dissolved in the organic solvent is generated and the coating liquid sometimes becomes opaque. Since the opaque coating liquid contains a lump of components that are not dissolved in the organic solvent, the coating liquid can not be applied in a uniform thickness. In addition, since the peeling layer formed by using the coating liquid has unevenness due to the agglomeration, the smoothness of the peeling layer becomes very bad.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a release film for a ceramic green sheet manufacturing process which is formed by using a stripper composition which does not cause clouding, .

In order to achieve the above object, first, the present invention is a release film for a ceramic green sheet manufacturing process comprising a substrate and a release agent layer formed on one side of the substrate, wherein the release agent layer comprises an amino resin and an active energy ray- Component and a photopolymerization initiator having a polyorganosiloxane, an acid catalyst and a nitrogen atom, wherein the blending amount of the photopolymerization initiator in the exfoliant composition is 1 to 100 parts by mass of the acid catalyst (Parts by mass) and not more than 300 parts by mass (Invention 1).

In the above invention (Invention 1), when the releasing agent composition contains a photopolymerization initiator having a nitrogen atom in the aforementioned amount, clouding does not occur in the coating solution of the releasing agent composition. Further, since the release agent layer is formed of the coating solution of such a release agent composition, the release surface of the release agent layer exhibits high smoothness.

In the above invention (Invention 1), it is preferable that the blending amount of the photopolymerization initiator in the exfoliant composition is not less than 0.5 parts by mass and not more than 25 parts by mass with respect to 100 parts by mass of the active energy ray-curable component ).

In the above invention (invention 1 or 2), the amino resin is preferably melamine resin (invention 3).

In the above inventions (Invention 1 to 3), the amount of the active energy ray-curable component in the exfoliant composition is preferably 10 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the amino resin 4).

In the invention (Invention 1 to 4), the amount of the polyorganosiloxane to be contained in the exfoliant composition is preferably not less than 0.1 parts by mass and not more than 10 parts by mass with respect to 100 parts by mass of the amino resin (Invention 5 ).

In the invention (Invention 1 to 5), it is preferable that the amount of the acid catalyst to be incorporated in the releasing agent composition is 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the amino resin.

In the above invention (Invention 1 to 6), it is preferable that the active energy ray-curable component has at least one hydroxy group in one molecule (invention 7).

In the above invention (Invention 1 to 7), it is preferable that the polyorganosiloxane has at least one hydroxy group in one molecule (invention 8).

The present invention secondly relates to a method for producing a release film for a ceramic green sheet manufacturing process, comprising a substrate and a release agent layer formed on one side of the substrate, wherein the amino resin, the active energy ray curable component, the polyorganosiloxane and the acid catalyst And a photopolymerization initiator having a nitrogen atom on the side of one side of the substrate to form a coating layer, and a step of heating the coating layer and further irradiating the coating layer with an active energy ray Wherein the amount of the photopolymerization initiator in the exfoliant composition is 1 part by mass or more and 300 parts by mass or less based on 100 parts by mass of the acid catalyst, And a method for producing a release film for a green sheet manufacturing process (Invention 9).

The release film for the ceramic green sheet manufacturing process according to the present invention is formed by using a stripper composition which does not cause clouding, and has excellent smoothness of the release surface.

1 is a sectional view of a release film for a ceramic green sheet manufacturing process according to an embodiment of the present invention.

Hereinafter, an embodiment of the present invention will be described.

[Release film for ceramic green sheet manufacturing process]

1, a release film 1 for a ceramic green sheet manufacturing process according to the present embodiment (hereinafter sometimes simply referred to as "release film 1") comprises a substrate 11, And a release agent layer 12 laminated on one surface (upper surface in FIG.

1. Release material layer

The release agent layer 12 of the release film 1 is formed of a release agent composition containing an amino resin, an active energy ray-curable component, a polyorganosiloxane, an acid catalyst and a photopolymerization initiator having a nitrogen atom. Here, the blending amount of the photopolymerization initiator in the exfoliant composition is 1 part by mass or more and 300 parts by mass or less based on 100 parts by mass of the acid catalyst.

As a result of diligent research conducted by the present inventors, the phenomenon that the coating liquid of the release agent composition is opaque is that, when a compound containing a nitrogen atom as a photopolymerization initiator is used in a predetermined amount, It was presumed to be due to the formation of insoluble or insoluble salts in the solvent. On the other hand, in the release film (1) according to the present embodiment, by using the above-described amount of a photopolymerization initiator having a nitrogen atom, it was confirmed that when the coating liquid for the release agent composition was prepared, Or formation of an insoluble salt is suppressed and the coating liquid is not cloudy. Since the release agent layer 12 is formed using the coating solution, irregularities due to the poorly soluble or insoluble salt are not generated on the release surface, and the release surface exhibits a very high smoothness.

(1) amino resin

In the release film (1) according to the present embodiment, the release agent composition contains an amino resin. When the release agent layer 12 is formed with the release agent composition, since the amino resin undergoes the condensation reaction in the presence of the acid catalyst, a three-dimensional structure of the amino resin is formed in the resulting release agent layer 12. The condensation reaction of the amino resin can be caused, for example, by heating. The release agent layer 12 exhibits sufficient elasticity because it contains the above-described three-dimensional structure, and thus the release film 1 according to the present embodiment can exhibit excellent releasability. In the present specification, the phrase " amino resin " refers to a component capable of causing a condensation reaction, and may not necessarily be a polymer compound. Here, the component may be one which does not cause a condensation reaction at all, or may be a product in which a condensation reaction occurs partially.

As the amino resin, known ones can be used. For example, a melamine resin, a urea resin, a guanamine resin or an aniline resin can be used. Of these, it is preferable to use a melamine resin having a very high rate of condensation reaction. In the present specification, the phrase " melamine resin " means a mixture of one kind of melamine compound or a mixture containing a plurality of melamine compounds and / or a polynuclear substance in which the melamine compound is condensed.

Specifically, the melamine resin preferably contains a melamine compound represented by the following general formula (a), or a polynuclear substance in which two or more of the melamine compounds are condensed.

[Chemical Formula 1]

In the formula (a), X preferably represents -H, -CH ₂ -OH, or -CH ₂ -OR. These groups constitute a reactor in the condensation reaction of the melamine compounds. Specifically, the -NH group formed by X becoming H can undergo a condensation reaction between an -N-CH ₂ -OH group and an -N-CH ₂ -R group. The -N-CH ₂ -R group formed by the formation of the -N-CH ₂ -OH group and the X group -CH ₂ -R formed by forming X as -CH ₂ -OH may be all -NH groups, -N- A condensation reaction can be carried out between the CH ₂ -OH group and the -N-CH ₂ -R group.

In the -CH ₂ -OR group, R preferably represents an alkyl group having 1 to 8 carbon atoms. The number of carbon atoms is preferably 1 to 6, more preferably 1 to 3. Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and an octyl group.

Each X may be the same or different. Each R may be the same or different.

In the melamine compound, typically every X is -CH ₂ -OR a full ether-type, and that at least one X -CH ₂ -OH Additionally, at least one X is an H-imino-methyl olhyeong, at least one X - CH ₂ -OH, and X is absent in H, and imino forms in which at least one X is H and X is absent, -CH ₂ -OH. In the release film 1 according to the present embodiment, any of these types of melamine compounds may be used.

In the release agent composition for forming the release agent layer 12, the weight average molecular weight of the melamine resin is preferably 350 or more, more preferably 500 or more, and further preferably 700 or more. The weight average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and further preferably 4,000 or less. By setting the weight average molecular weight to 350 or more, the crosslinking rate is stabilized and a smooth release surface can be formed. On the other hand, when the weight average molecular weight is 10,000 or less, the viscosity of the release agent composition becomes moderately low, and the application liquid of the release agent composition becomes easy to coat on the substrate 11. The weight average molecular weight in the present specification is a value in terms of standard polystyrene measured by Gel Permeation Chromatography (GPC).

(2) Active energy ray-curable component

In the release film (1) according to the present embodiment, the release agent composition contains an active energy ray curable component. In the release film 1 according to the present embodiment, when the release agent layer 12 is formed, following the formation of the three-dimensional structure by the amino resin described above, the active energy ray is applied to the release layer of the release agent composition, The polymerization reaction of the energy ray-curable component proceeds to form a structure in which the component reinforces the three-dimensional structure. By further reinforcing the three-dimensional structure described above, the elasticity of the release agent layer 12 is further improved, whereby the release film 1 according to the present embodiment can exhibit excellent releasability.

The active energy ray curable component preferably has at least one reactive functional group selected from the group consisting of (meth) acryloyl groups, alkenyl groups and maleimide groups. Examples of the alkenyl group include a vinyl group and an allyl group having 2 to 10 carbon atoms. Particularly, it is preferable that two or more such reactive functional groups are contained in one molecule, more preferably three or more in one molecule. As a result, the release agent layer 12 is more excellent in curability, solvent resistance, and peelability.

Specific examples of the active energy ray-curable component include trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra Acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa Meth) acrylate. Among these, at least one of dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate It is preferable to use one kind of polyfunctional acrylate.

It is preferable that the active energy ray-curable component has at least one hydroxy group in one molecule. The active energy ray-curable component preferably has 3 or less hydroxy groups in one molecule, more preferably 2 or less in one molecule. When the amino resin has a group capable of reacting with the hydroxy group by having the active energy ray-curable component having at least one hydroxy group in one molecule, the active energy ray-curable component and the amino resin can bond through these groups So that it becomes possible to further reinforce the above-described three-dimensional structure.

In the release film (1) according to the present embodiment, the blending amount of the active energy ray-curable component in the release agent composition is preferably 10 parts by mass or more, particularly preferably 15 parts by mass or more based on 100 parts by mass of the amino resin More preferably not less than 75 parts by mass. The blending amount of the active energy ray-curable component in the release agent composition is preferably 1000 parts by mass or less, particularly preferably 750 parts by mass or less, more preferably 500 parts by mass or less, based on 100 parts by mass of the amino resin . The amino resin and the active energy ray-curable component are blended so that the compounding amount of the active energy ray-curable component is in the range described above, so that the release film (1) according to the present embodiment is excellent in peelability, productivity and time- It will be excellent.

(3) Polyorganosiloxane

In the release film (1) according to the present embodiment, the release agent composition contains a polyorganosiloxane. As a result, the surface free energy on the release surface is appropriately lowered in the release agent layer 12 formed using the release agent composition. Therefore, the peeling force when the peeling film 1 is peeled off from the ceramic green sheet formed on the peeling surface of the peeling film 1 is suitably lowered, and the good peeling property is exhibited.

The polyorganosiloxane used in the release film 1 according to the present embodiment is not particularly limited, and for example, a polymer of the silicon-containing compound represented by the following general formula (b) can be used.

(2)

In the formula (b), m is an integer of 1 or more. It is preferable that at least one of R ¹ to R ⁸ is an organic group having a hydroxyl group or a hydroxy group. That is, the polyorganosiloxane represented by the formula (b) preferably contains an organic group having at least one hydroxyl group or a hydroxy group in one molecule. The upper limit of the number of organic groups having a hydroxyl group or a hydroxy group in one molecule of the polyorganosiloxane is not particularly limited, but is, for example, 20. As a result that the polyorganosiloxane contains an organic group having a hydroxyl group or a hydroxy group, it is fixed to an amino resin having a group capable of reacting with the hydroxy group. As a result, the ceramic green sheet formed on the release surface of the release film , The migration of the polyorganosiloxane from the release agent layer 12 is effectively suppressed. In particular, it is preferable that at least one of R ³ to R ⁸ is an organic group having a hydroxyl group or a hydroxy group. That is, at least one of the hydroxyl groups is preferably present at the end of the polyorganosiloxane. Since the hydroxy group is present at the terminal, the polyorganosiloxane is easily reacted with the amino resin or the active energy ray-curable component having a group capable of reacting with the hydroxy group, and the migration is more effectively suppressed.

In formula (b), at least one of the groups other than the hydroxyl group of R ¹ to R ⁸ is preferably an organic group. Here, when at least one of R ¹ to R ⁸ in the formula (b) is a hydroxy group, the other organic groups contained in R ¹ to R ⁸ may be an organic group having a hydroxy group or an organic group having no hydroxy group do. On the other hand, when all of R ¹ to R ⁸ in the formula (b) are not a hydroxy group, the other organic groups contained in R ¹ to R ⁸ are preferably organic groups having a hydroxy group. In the present specification, " organic group " does not include an alkyl group which will be described later. The polyorganosiloxane represented by the formula (b) preferably has at least one organic group having a hydroxy group or an organic group having no hydroxy group in one molecule, particularly preferably 1 to 10, more preferably 1 To 5 is preferable. Here, the organic group is preferably at least one organic group selected from a polyester group and a polyether group. Both of a polyester group and a polyether group may be present in one molecule. When a hydroxy group is contained in a polyester group or a polyether group, the hydroxy group may be present at the terminal of these organic groups, or may exist in the side chain of these organic groups. By having the polyorganosiloxane having the organic group, the polyorganosiloxane and the melamine resin are mixed well in the exfoliant composition, and they are prevented from being extremely phase-separated at the time of curing.

Among the groups represented by R ¹ to R ⁸ in the formula (b), the groups other than the groups described above are preferably alkyl groups having 1 to 12 carbon atoms. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and an octyl group.

R ¹ to R ⁸ may be the same or different. The may be the same or different and each R ¹ and R ^2, if there is a plurality, R ¹ and R ^2.

The weight average molecular weight of the polyorganosiloxane is preferably 1,000 or more, more preferably 3,000 or more, and further preferably 4,000 or more. The weight average molecular weight is preferably 300000 or less, more preferably 100000 or less, and further preferably 50000 or less. When the weight average molecular weight of the polyorganosiloxane is 1000 or more, the surface free energy at the peeling surface of the peeling agent layer 12 is appropriately lowered, and the peeling force at the time of peeling the peeling film 1 from the ceramic green sheet is effectively . When the weight average molecular weight of the polyorganosiloxane is 300000 or less, the viscosity of the exfoliant composition is prevented from becoming excessively high, and the application liquid of the exfoliant composition is easily applied to the substrate 11. [

The blending amount of the polyorganosiloxane in the release agent composition is preferably 0.1 part by mass or more, particularly preferably 0.5 part by mass or more, and more preferably 1.0 part by mass or more, based on 100 parts by mass of the amino resin. The blending amount of the polyorganosiloxane in the release agent composition is preferably 10 parts by mass or less, particularly preferably 5 parts by mass or less, more preferably 4 parts by mass or less, based on 100 parts by mass of the amino resin. When the content of the polyorganosiloxane in the release agent composition is in the range described above, the surface free energy of the release surface of the release agent layer 12 is appropriately lowered, and excellent peeling force can be achieved.

(4) An acid catalyst

In the release film (1) according to the present embodiment, the release agent composition contains an acid catalyst. When the release agent composition contains an acid catalyst, the condensation reaction of the amino resin proceeds efficiently, and the release agent layer 12 exhibiting sufficient elasticity is formed.

Examples of the acid catalyst include p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid. When a full ether type melamine resin is mainly used as the amino resin, it is preferable to use p-toluenesulfonic acid as an acid catalyst from the viewpoint that the condensation reaction can proceed effectively. When an imino-methylol-type melamine resin is mainly used as the amino resin, it is preferable to use phosphoric acid as the acid catalyst from the same viewpoint.

The blending amount of the acid catalyst in the release agent composition is preferably 0.5 parts by mass or more, particularly preferably 1.0 parts by mass or more, and more preferably 2.0 parts by mass or more based on 100 parts by mass of the amino resin. The blending amount of the acid catalyst in the release agent composition is preferably 20 parts by mass or less, particularly preferably 15 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the amino resin. The mixing amount of the acid catalyst is 0.5 part by mass or more, so that the condensation reaction of the amino resin can be promoted efficiently. Further, when the compounding amount of the acid catalyst is 20 parts by mass or less, the low molecular weight component is retained in the three-dimensional structure, and precipitation from the release agent layer can be effectively prevented.

(5) A photopolymerization initiator having a nitrogen atom

In the release film (1) according to the present embodiment, the release agent composition contains a photopolymerization initiator having a nitrogen atom. Here, the blending amount of the photopolymerization initiator in the exfoliant composition is 1 part by mass or more and 300 parts by mass or less based on 100 parts by mass of the acid catalyst. As a result, the coating solution of the releasing agent composition is not clouded, and the polymerization reaction of the active energy ray-curable component can be promoted efficiently. In addition, in general, the photopolymerization initiator having a nitrogen atom can promote the polymerization reaction of the active energy ray-curable component more efficiently than the photopolymerization initiator having no nitrogen atom. Therefore, in the release film (1) according to the present embodiment, the release agent composition contains a photopolymerization initiator having a nitrogen atom in a relatively small amount range as described above, The three-dimensional structure is strengthened more strongly.

In the release film (1) according to the present embodiment, the amount of the photopolymerization initiator having a nitrogen atom in the release agent composition is preferably 1 part by mass or more and 10 parts by mass or more based on 100 parts by mass of the acid catalyst , Particularly preferably 50 parts by mass or more. The blending amount of the photopolymerization initiator is preferably 300 parts by mass or less, more preferably 270 parts by mass or less, particularly preferably 250 parts by mass or less based on 100 parts by mass of the acid catalyst. When the blending amount of the photopolymerization initiator is less than 1 part by mass, the effect of advancing the polymerization reaction by the photopolymerization initiator can not be sufficiently obtained. In the resulting releasing agent layer, the three-dimensional structure reinforcement by the amino resin becomes insufficient. When the blending amount of the photopolymerization initiator is more than 300 parts by mass, the coating liquid of the exfoliating composition becomes cloudy, and the exfoliant layer formed by using the coating liquid becomes low in smoothness of the exfoliating surface.

The blending amount of the photopolymerization initiator in the release agent composition is preferably 0.5 parts by mass or more, particularly preferably 1.0 parts by mass or more, and more preferably 2.0 parts by mass or more based on 100 parts by mass of the active energy ray curable component. The blending amount of the photopolymerization initiator in the release agent composition is preferably 25 parts by mass or less, particularly preferably 20 parts by mass or less, more preferably 15 parts by mass or less, based on 100 parts by mass of the active energy ray- Do. The blending amount of the photopolymerization initiator is 0.5 parts by mass or more, whereby the polymerization reaction of the active energy ray-curable component can proceed efficiently. Further, when the blending amount of the photopolymerization initiator is 25 parts by mass or less, adverse effects due to the reaction residues can be effectively reduced.

The photopolymerization initiator is not particularly limited as long as it has a nitrogen atom, and for example, an? -Aminoalkylphenone-based compound can be given.

Examples of the? -aminoalkylphenone-based compound include 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane- - (4-morpholinophenyl) -butanone-1, 2-dimethylamino-2 - [(4- methylphenyl) methyl] And the like. Among them, it is particularly preferable to use 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1-one. These may be used singly or in combination of two or more.

(6) Other components

The release agent composition may contain, in addition to the above components, a crosslinking agent, a reaction inhibitor, a sensitizer, an antistatic agent, a curing agent and the like.

(7) Thickness

The thickness of the release agent layer 12 is preferably 0.1 占 퐉 or more, more preferably 0.5 占 퐉 or more, and further preferably 0.75 占 퐉 or more. The thickness is preferably 5 占 퐉 or less, more preferably 4 占 퐉 or less, further preferably 3 占 퐉 or less. When the thickness is 0.1 占 퐉 or more, the function as the release agent layer 12 can be effectively exerted. On the other hand, when the thickness is 5 占 퐉 or less, the occurrence of blocking when the release film 1 is rolled up can be effectively suppressed.

2. Equipment

The base material 11 of the release film 1 is not particularly limited as long as the release agent layer 12 can be laminated. Examples of the substrate 11 include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polypropylene and polymethylpentene, films made of polycarbonate and polyvinyl acetate and the like, Or may be a multilayer of two or more layers of the same type or different types. Among these, a polyester film is preferable, and a polyethylene terephthalate film is particularly preferable, and further, a biaxially stretched polyethylene terephthalate film is preferable. Since the polyethylene terephthalate film is free from dust or the like during processing, use, and the like, it is possible to effectively prevent defective coating of ceramic slurry by dust or the like. In addition, by applying antistatic treatment to the polyethylene terephthalate film, it is possible to prevent ignition by static electricity when coating a ceramic slurry using an organic solvent, and to improve the effect of preventing coating failure or the like.

In order to improve the adhesion of the base material 11 to the release agent layer 12 formed on the surface of the base material 11, a surface treatment or an primer treatment may be applied to one surface or both surfaces of the base material 11 by oxidation, . Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromium oxidation treatment (wet type), flame treatment, hot air treatment, ozone, ultraviolet ray irradiation treatment and the like. Blast method, spray treatment method, and the like. These surface treatment methods are appropriately selected depending on the kind of the base film, and corona discharge treatment methods are generally used preferably from the viewpoints of effectiveness and operability.

The thickness of the substrate 11 is preferably 10 占 퐉 or more, more preferably 15 占 퐉 or more, and further preferably 20 占 퐉 or more. The thickness is preferably 300 탆 or less, more preferably 200 탆 or less, and further preferably 125 탆 or less.

3. Physical Properties of Peel Film for Ceramic Green Sheet Manufacturing Process

In the release film 1 according to the present embodiment, the arithmetic average surface roughness (Ra) of the release surface of the release agent layer 12 is preferably 20 nm or less, more preferably 15 nm or less, and further preferably 10 nm or less. In the release film 1 according to the present embodiment, since the release agent layer 12 is formed by using the release agent composition described above, high smoothness in the above-mentioned range can be achieved. The arithmetic average surface roughness (Ra) in the present specification is calculated from a roughness curve measured using a contact type roughness meter (for example, SV3000S4 manufactured by Mitsutoyo Corporation) according to JIS B0601: 2013 .

In addition, when the coating liquid of the release agent composition is clouded, insoluble components which cause clouding appear on the surface of the release agent layer to generate protrusions. The projections generally have a size of several tens of micrometers to several hundreds of micrometers, and can be visually confirmed.

The peeling force required when peeling the peeling film 1 from the ceramic green sheet formed on the peeling film 1 of the peeling film 1 can be appropriately set, but it is preferably 5 mN / 20 mm or more, particularly 10 mN / 20 mm or more. The peel force is preferably 100 mN / 20 mm or less, particularly preferably 50 mN / 20 mm or less. The method of measuring the peeling force is as shown in the following test example.

The thickness of the release film 1 is preferably 10 占 퐉 or more, more preferably 15 占 퐉 or more, and further preferably 20 占 퐉 or more. The thickness is preferably not more than 305 占 퐉, more preferably not more than 200 占 퐉, further preferably not more than 125 占 퐉.

4. Method for manufacturing a release film for a ceramic green sheet manufacturing process

The release film (1) related to the embodiment can be produced by a conventional method. For example, a coating liquid is prepared by diluting the above-described release agent composition with an organic solvent, and the coating liquid is applied to one side of the substrate 11 to form a coating layer, followed by heating the coating layer. The coating layer may be dried before this heating. By this heating, a condensation reaction of the amino resin occurs and a three-dimensional structure is formed. After heating, the coated layer is irradiated with an active energy ray. By the irradiation of the active energy ray, the polymerization reaction of the active energy ray-curable resin occurs and the three-dimensional structure is reinforced. Thus, the release agent layer 12 is formed.

The organic solvent is not particularly limited and various solvents can be used. Isopropyl alcohol, isobutyl alcohol, acetone, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and a mixture thereof, as well as hydrocarbon compounds such as toluene, hexane and heptane. In particular, it is preferable to use a mixture of methyl ethyl ketone and isopropyl alcohol.

Examples of the application method of the coating liquid include a gravure coating method, a bar coating method, a spray coating method, a spin coating method, a knife coating method, a roll coating method and a die coating method.

The heating temperature for the heating is preferably 90 占 폚 or higher, and more preferably 110 占 폚 or higher. The heating temperature is preferably 140 占 폚 or lower, more preferably 130 占 폚 or lower. The heating time of the heating is preferably 10 seconds or more, and particularly preferably 20 seconds or more. The heating time is preferably 120 seconds or less, particularly preferably 70 seconds or less.

As the active energy ray, ultraviolet rays, electron beams and the like are usually used, and ultraviolet rays are particularly preferable. The irradiation amount of the active energy ray differs depending on the kind of the energy ray. For example, in the case of ultraviolet ray, the amount of the active energy ray is preferably 50 mJ / cm2 or more, and more preferably 100 mJ / cm2 or more. The irradiation amount of the ultraviolet ray is preferably 1000 mJ / cm2, more preferably 500 mJ / cm2 in terms of light quantity. In the case of electron beam, 0.1 kGy or more is preferable, and 50 kGy or less is preferable.

The release film (1) according to the present embodiment is formed by using the release agent layer (12) using the application liquid of the release agent composition described above. In the coating liquid of the exfoliant composition, an insoluble or insoluble salt by the photopolymerization initiator and the acid catalyst is not formed, and the coating liquid is not cloudy. Therefore, unevenness caused by the poorly soluble or insoluble salt does not occur on the release surface of the release agent layer 12, and the release surface exhibits very high smoothness.

5. How to use the release film for ceramic green sheet manufacturing process

The release film 1 can be used for producing a ceramic green sheet. Specifically, a ceramic slurry containing a ceramic material such as barium titanate or titanium oxide is coated on the release surface of the release agent layer 12, and then the ceramic slurry is dried to obtain a ceramic green sheet. The coating can be carried out using, for example, a slot die coating method or a doctor blade method.

Examples of the binder component contained in the ceramic slurry include a butyral resin and an acrylic resin. Examples of the solvent contained in the ceramic slurry include an organic solvent and an aqueous solvent.

As described above, the release film 1 according to the present embodiment exhibits a high level of smoothness, and therefore, by using the release film 1, it is possible to obtain excellent quality without defects such as pinholes and unevenness in thickness Can be formed.

The embodiments described above are provided for the purpose of facilitating understanding of the present invention and are not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design modifications and equivalents falling within the technical scope of the present invention.

For example, another layer such as an antistatic layer may be formed on the opposite side of the release agent layer 12 in the base material 11 or between the base material 11 and the release agent layer 12.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the scope of the present invention is not limited to these Examples and the like.

[Example 1]

100 parts by mass (in terms of solid content, hereinafter the same) of a full ether type methylated melamine resin (product name "MW-30", product of Nippon Carbide Corp., weight average molecular weight 608, molecular weight distribution (Mw / Mn) , 100 parts by mass of pentaerythritol triacrylate (Shin-Nakamura Chemical Co., Ltd., product name "A-TMM-3L") as an active energy ray curable component, and 100 parts by mass of a polyether-modified hydroxyl group-containing polydimethylsiloxane as a polyorganosiloxane 4.0 parts by mass of p-toluenesulfonic acid (manufactured by Hitachi Chemical Co., Ltd., trade name " Dryer 900 ") as a photocatalytic polymerization initiator, 2 parts by mass of 2- (4-methylthiophenyl) -2-morpholinopropane-1-one (trade name: Irgacure 907, manufactured by Ciba) were mixed with a mixed solvent of methyl ethyl ketone and isopropyl alcohol to obtain a solid content of 18 mass% foil To obtain a coating liquid of the lyase composition.

The obtained coating liquid was uniformly coated on one side of a biaxially oriented polyethylene terephthalate film (thickness: 25 mu m) as a base with Meyer bar # 5 to obtain a coated layer. Subsequently, the coated layer was heated at 120 DEG C for 30 seconds and irradiated with ultraviolet rays of 50 mJ / cm < 2 > from the coating layer side with a high-pressure mercury lamp in a nitrogen atmosphere to cure the exfoliating composition to form a 1.2 mu m- Whereby a laminated release film was obtained.

The thickness of the base material and the peeling agent layer was measured using a reflective film thickness meter (product name: "F20", manufactured by Philmetrix).

[Examples 2 to 4]

A release film was obtained in the same manner as in Example 1 except that the blending amount of the active energy ray-curable component, the acid catalyst, and the photopolymerization initiator was changed as shown in Table 1.

[Example 5]

Except that 125 parts by mass of an imino-type methylated melamine resin (trade name: MX-730, manufactured by Nippon Carbide Co., Ltd., weight average molecular weight: 1508, molecular weight distribution (Mw / Mn): 1.18) A release film was obtained.

[Comparative Example 1]

A release film was obtained in the same manner as in Example 1, except that the blending amount of the active energy ray-curable component and the photo polymerization initiator was changed as shown in Table 1.

[Test Example 1] (Evaluation of turbidity)

With respect to the coating solution of the release agent composition prepared in Examples and Comparative Examples, the presence or absence of turbidity was visually confirmed. The results are shown in Table 1. The results are shown in Table 1. The results are shown in Table 1. The results are shown in Table 1. The results are shown in Table 1. The results are shown in Table 1.

[Test Example 2] (Evaluation of smoothness)

With respect to the release films produced in Examples and Comparative Examples, the smoothness of the release surface of the release agent layer was visually evaluated. The results are shown in Table 1. The results are shown in Table 1. The results are shown in Table 1. The results are shown in Table 1. The results are shown in Table 1. The results are shown in Table 1.

[Test Example 3] (Measurement of peel force)

, 100 parts by mass of barium titanate (BaTiO ₃ ; product name: "BT-03", manufactured by Sakai Chemical Industry Co., Ltd.), 10 parts by mass of polyvinyl butyral (trade name: "Sureck B / KBM-2" manufactured by Sekisui Chemical Co., 69 parts by mass of toluene and 46 parts by mass of ethanol were added to 5 parts by mass of dioctyl (manufactured by Kanto Chemical Co., Ltd., product name "dioctyl phthalate Cica grade 1") and mixed and dispersed in a ball mill to prepare a ceramic slurry.

The ceramic slurry was uniformly coated on the release surface of the release agent layer by using an applicator in the release film prepared in Examples and Comparative Examples and then stored at room temperature for 48 hours and then dried in a drier at 80 DEG C for 1 minute . Thus, a ceramic green sheet having a thickness of 3 占 퐉 was obtained on the release film. Thus, a release film with a ceramic green sheet was produced.

The release film with a ceramic green sheet was allowed to stand for 24 hours under an atmosphere of a room temperature of 23 degrees and a humidity of 50%. Next, an acrylic adhesive tape (product name "31B tape", manufactured by Nitto Denki Kogyo Co., Ltd.) was stuck to the side opposite to the release film in the ceramic green sheet, and cut in a state of 20 mm width in this state. This was used as a measurement sample.

The adhesive tape side of the measurement sample was fixed on a flat plate and peeled off from the ceramic green sheet at a peeling angle of 180 DEG and a peeling rate of 100 mm / min using a tensile tester (product name: " AG-IS500N " The film was peeled off and the force (peeling force; mN / 20 mm) required for peeling was measured. The results are shown in Table 1.

Details of the abbreviations and the like listed in Table 1 are as follows.

[Amino resin]

(MW-30, weight average molecular weight 608, molecular weight distribution (Mw / Mn) 1.005, manufactured by Nippon Carbide Co., Ltd.)

MX-730: imino-type methylated melamine resin (trade name: MX-730, manufactured by Nippon Carbide Co., Ltd., weight average molecular weight: 1508, molecular weight distribution (Mw / Mn): 1.18)

As is apparent from Table 1, the coating liquid prepared in Example was not opaque, and the release surface of the release agent layer exhibited high smoothness. Further, in the release film obtained in the examples, it was possible to peel off with a suitable peeling force when peeling off from the ceramic green sheet.

The release film for the ceramic green sheet manufacturing process of the present invention is preferable for forming a ceramic green sheet having a high surface smoothness.

One… Release film for ceramic green sheet manufacturing process
11 ... materials
12 ... Release agent layer

Claims (9)

A release film for a ceramic green sheet manufacturing process comprising a substrate and a release agent layer formed on one side of the substrate,
Wherein the release agent layer is formed of a release agent composition containing an amino resin, an active energy ray-curable component, a polyorganosiloxane, an acid catalyst and a photopolymerization initiator having a nitrogen atom,
Wherein the blending amount of the photopolymerization initiator in the exfoliant composition is 1 part by mass or more and 300 parts by mass or less based on 100 parts by mass of the acid catalyst. The method according to claim 1,
Wherein the blending amount of the photopolymerization initiator in the exfoliant composition is 0.5 parts by mass or more and 25 parts by mass or less based on 100 parts by mass of the active energy ray curable component. The method according to claim 1,
The release film for a ceramic green sheet manufacturing process according to claim 1, wherein the amino resin is a melamine resin. The method according to claim 1,
Wherein the amount of the active energy ray-curable component in the release agent composition is 10 parts by mass or more and 1000 parts by mass or less based on 100 parts by mass of the amino resin. The method according to claim 1,
Wherein the blending amount of the polyorganosiloxane in the releasing agent composition is 0.1 parts by mass or more and 10 parts by mass or less based on 100 parts by mass of the amino resin. The method according to claim 1,
Wherein the amount of the acid catalyst to be incorporated in the releasing agent composition is 0.5 parts by mass or more and 20 parts by mass or less based on 100 parts by mass of the amino resin. The method according to claim 1,
Wherein the active energy ray-curable component has at least one hydroxy group in one molecule. The method according to claim 1,
Wherein the polyorganosiloxane has at least one hydroxy group in one molecule. 1. A method for producing a release film for a ceramic green sheet manufacturing process comprising a substrate and a release agent layer formed on one side of the substrate,
A step of applying a release agent composition containing an amino resin, an active energy ray-curable component, a polyorganosiloxane, an acid catalyst and a photopolymerization initiator having a nitrogen atom to one surface side of the substrate to form a coating layer, and
And heating the coating layer and further irradiating the coating layer with an active energy ray to form the releasing agent layer,
Wherein the blending amount of the photopolymerization initiator in the exfoliant composition is 1 part by mass or more and 300 parts by mass or less based on 100 parts by mass of the acid catalyst.

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