JP6586376B2 - Peeling film for ceramic green sheet manufacturing process and manufacturing method thereof - Google Patents

Description

  The present invention relates to a release film used in a process for producing a ceramic green sheet and a production method thereof.

  Conventionally, in order to manufacture 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 obtained ceramic green sheets are stacked and fired.

  The ceramic green sheet is formed by applying a ceramic slurry containing a ceramic material such as barium titanate or titanium oxide on a release film. The release film is required to have releasability that allows the release film to be peeled off from the thin ceramic green sheet formed on the release film with an appropriate peeling force without causing cracks or breakage.

  In recent years, along with miniaturization and high performance of electronic devices, the miniaturization and multilayering of multilayer ceramic capacitors and multilayer ceramic substrates have progressed, and thinning of ceramic green sheets has progressed. When the thickness of the ceramic green sheet is reduced to 3 μm or less, for example, when the ceramic slurry is applied and dried, the ceramic green sheet is caused by the surface state of the release agent layer in the release film. Defects such as pinholes and uneven thickness are likely to occur. Therefore, the release agent layer of the release film is required to have high smoothness on the surface in contact with the ceramic slurry / ceramic green sheet (hereinafter sometimes referred to as “release surface”).

  Patent Documents 1 and 2 describe a layer formed by curing a thermosetting resin between a base material and a release agent layer for the purpose of preventing the occurrence of defects such as pinholes and uneven thickness in a ceramic green sheet. A release film provided with is disclosed. In these release films, the thermosetting resin is cured for the purpose of reducing the influence of the roughness of the substrate surface on the smoothness of the release surface of the release agent layer, thereby improving the smoothness of the release surface. A layer is provided. In these release films, by providing the layer, the influence of the roughness of the substrate surface on the release surface is reduced, and the smoothness of the release surface is being improved.

JP 2007-69360 A JP 2014-177093 A

  By the way, the present inventors have proposed a release agent composition containing a thermosetting resin and a polyorganosiloxane, and an active energy ray curable for the purpose of improving the smoothness, productivity, stability over time of the release surface. Development of a release film comprising a release agent layer formed using a release agent composition containing a component, a polyorganosiloxane, and a photopolymerization initiator is in progress. Examples of thermosetting resins include a combination of an amino resin and an acid catalyst.

  Moreover, in the said peeling film, when the thing containing a thermosetting resin and an active energy ray hardening component is used as a release agent composition, one of the above-mentioned thermosetting resin and an active energy ray hardening component is used. Compared to the case of using the release agent composition contained, since the release agent composition can be cured while suppressing the application of heat and active energy rays, it is expected to improve the productivity of the release 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. Thus, after forming the coating layer, the coating layer is heated to cause a condensation reaction between the amino resins, thereby forming a three-dimensional structure of the amino resins. Subsequently, the application layer is irradiated with active energy rays to cause a polymerization reaction between the active energy ray-curable components, thereby reinforcing the three-dimensional structure.

  At this time, the polyorganosiloxane is taken into the structure formed by the amino resin and the active energy ray-curable component, and is dispersed or unevenly distributed in the resulting release agent layer. 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, when each component mentioned above is mixed in the organic solvent in order to prepare the coating liquid of the said release agent composition, the component which does not melt | dissolve in an organic solvent will generate | occur | produce, and a coating liquid may become cloudy. Since the white turbid coating solution contains a lump of components that do not dissolve in the organic solvent, it cannot be applied to a uniform thickness. Moreover, since the unevenness | corrugation resulting from the said lump arises in the peeling surface of the release agent layer formed using the said coating liquid, the smoothness of the said peeling surface becomes very bad.

  The present invention has been made in view of such a situation, and is formed using a release agent composition that does not cause white turbidity, and has a release surface for a ceramic green sheet manufacturing process excellent in smoothness of a release surface, and its manufacture It aims to provide a method.

  In order to achieve the above object, first, the present invention is a release film for a ceramic green sheet manufacturing process, comprising a base material and a release agent layer provided on one side of the base material, the release agent The layer is formed from 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. The amount of the photopolymerization initiator in the agent composition is 1 part by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the acid catalyst. Provided (Invention 1)

  In the said invention (invention 1), a cloudiness does not arise in the coating liquid of a peeling agent composition by containing the photoinitiator which has a nitrogen atom in the peeling agent composition mentioned above in the compounding quantity mentioned above. And when a release agent layer is formed from the coating liquid of such a release agent composition, the peeling surface of a release agent layer shows high smoothness.

  In the said invention (invention 1), the compounding quantity of the said photoinitiator in the said release agent composition is 0.5 mass part or more and 25 mass parts or less with respect to 100 mass parts of said active energy ray hardening components. (Invention 2)

  In the said invention (invention 1 and 2), it is preferable that the said amino resin is a melamine resin (invention 3).

  In the said invention (invention 1-3), the compounding quantity of the said active energy ray hardening component in the said release agent composition is 10 mass parts or more and 1000 mass parts or less with respect to 100 mass parts of said amino resins. (Invention 4)

  In the said invention (invention 1-4), the compounding quantity of the said polyorganosiloxane in the said release agent composition shall be 0.1 mass part or more and 10 mass parts or less with respect to 100 mass parts of said amino resins. Is preferred (Invention 5).

  In the said invention (invention 1-5), the compounding quantity of the said acid catalyst in the said release agent composition is 0.5 mass part or more and 20 mass parts or less with respect to 100 mass parts of said amino resins. Preferred (Invention 6).

  In the said invention (invention 1-6), it is preferable that the said active energy ray hardening component has at least 1 hydroxy group in 1 molecule (invention 7).

  In the said invention (invention 1-7), it is preferable that the said polyorganosiloxane has at least 1 hydroxy group in 1 molecule (invention 8).

  2ndly, this invention is a manufacturing method of the release film for ceramic green sheet manufacturing processes provided with the base material and the release agent layer provided in the one side of the said base material, Comprising: Amino resin and active energy ray hardening Applying a release agent composition containing an organic component, a polyorganosiloxane, an acid catalyst, and a photopolymerization initiator having a nitrogen atom to one side of the substrate to form a coating layer; and The step of heating the coating layer and further irradiating the coating layer with active energy rays to form the release agent layer, the blending amount of the photopolymerization initiator in the release agent composition, Provided is a method for producing a release film for a ceramic green sheet production process, which is 1 part by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the acid catalyst (Invention 9).

  The release film for a ceramic green sheet production process according to the present invention is formed using a release agent composition that does not cause white turbidity, and is excellent in the smoothness of the release surface.

It is sectional drawing of the peeling film for ceramic green sheet manufacturing processes which concerns on one Embodiment of this invention.

Hereinafter, embodiments of the present invention will be described.
[Peeling film for ceramic green sheet manufacturing process]
As shown in FIG. 1, a release film 1 for manufacturing a ceramic green sheet according to the present embodiment (hereinafter sometimes simply referred to as “release film 1”) includes a base material 11 and one surface of the base material 11. The release agent layer 12 is laminated on the upper surface (the upper surface in FIG. 1).

1. Release agent layer The release agent layer 12 of the release film 1 contains an amino resin, an active energy ray-curable component, a polyorganosiloxane, an acid catalyst, and a photopolymerization initiator having a nitrogen atom. It is formed from. Here, 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 with respect to 100 parts by mass of the acid catalyst.

  As a result of intensive studies by the present inventors, the phenomenon in which the coating solution of the release agent composition becomes cloudy is that when a compound containing a nitrogen atom is used as a photopolymerization initiator in a predetermined amount, the photopolymerization initiator and It was presumed that this was caused by the formation of a salt that was hardly soluble or insoluble in the organic solvent with the acid catalyst. On the other hand, in the release film 1 according to this embodiment, the photopolymerization initiator and the acid catalyst are prepared when the coating liquid of the release agent composition is prepared by using the photopolymerization initiator having a nitrogen atom in the amount described above. The formation of sparingly soluble or insoluble salts from the above is suppressed, and the coating solution does not become cloudy. And since the release agent layer 12 is formed using the said coating liquid, the unevenness | corrugation resulting from the hardly soluble or insoluble salt does not arise in the peeling surface, but the said peeling surface is very high. Shows smoothness.

(1) Amino resin In the release film 1 according to this embodiment, the release agent composition contains an amino resin. When the release agent layer 12 is formed from the release agent composition, since the amino resin undergoes a condensation reaction in the presence of an 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 by heating, for example. Since the release agent layer 12 includes the above-described three-dimensional structure, the release agent layer 12 exhibits sufficient elasticity, and thus the release film 1 according to the present embodiment can exhibit excellent peelability. In the present specification, the phrase “amino resin” refers to a component capable of causing a condensation reaction, and is not necessarily a polymer compound. Here, the component may be one that has not undergone a condensation reaction at all or may have undergone a partial condensation reaction.

  As said amino resin, a known thing can be used, for example, a melamine resin, a urea resin, a guanamine resin, or an aniline resin can be used. Among these, it is preferable to use a melamine resin having a very fast condensation reaction. In the present specification, the phrase “melamine resin” means an aggregate of one type of melamine compound, or a mixture containing a plurality of types of melamine compounds and / or polynuclear products formed by condensation of the melamine compounds. To do.

Specifically, the melamine resin preferably contains a melamine compound represented by the following general formula (a) or a polynuclear product formed by condensation of two or more melamine compounds.

In formula (a), X preferably represents —H, —CH ₂ —OH, or —CH ₂ —O—R. These groups constitute reactive groups in the condensation reaction between the melamine compounds. Specifically, the —NH group formed when X becomes H can undergo a condensation reaction between the —N—CH ₂ —OH group and the —N—CH ₂ —R group. In addition, both —N—CH ₂ —OH group formed by X becoming —CH ₂ —OH and —N—CH ₂ —R group formed by X becoming —CH ₂ —R are both , —NH group, —N—CH ₂ —OH group and —N—CH ₂ —R group can be subjected to a condensation reaction.

In the —CH ₂ —O—R group, R preferably represents an alkyl group having 1 to 8 carbon atoms. The number of carbon atoms is preferably 1 to 6, and particularly 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, and a methyl group is particularly preferable.

  Said X may be the same respectively, and may differ. Moreover, said R may be the same respectively, and may differ.

Melamine compounds generally include a full ether form in which all X is —CH ₂ —O—R, an imino methylol in which at least one X is —CH ₂ —OH and at least one X is H. A methylol type in which at least one X is —CH ₂ —OH and H is not present X, and an imino in which at least one X is H and —CH ₂ —OH is absent There are types such as types. 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, particularly preferably 500 or more, and more preferably 700 or more. The weight average molecular weight is preferably 10,000 or less, particularly preferably 5000 or less, and more preferably 4000 or less. When the weight average molecular weight is 350 or more, the crosslinking rate is stabilized and a smoother 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 it becomes easy to apply the application liquid of the release agent composition on the substrate 11. In addition, the weight average molecular weight in this specification is the value of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method.

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

  The active energy ray-curable component preferably has at least one reactive functional group selected from the group consisting of a (meth) acryloyl group, an alkenyl group, and a maleimide group. In addition, as said alkenyl group, a C2-C10 thing, such as a vinyl group and an allyl group, is illustrated. In particular, it is preferable to have two or more such reactive functional groups in one molecule, and more preferable to have three or more in one molecule. Thereby, the release agent layer 12 becomes 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 (meth) acrylate, di Examples thereof include polyfunctional (meth) acrylates such as pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate. Among these, it is preferable to use at least one polyfunctional acrylate of dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate. .

  The active energy ray-curable component preferably has at least one hydroxy group in one molecule. Furthermore, the active energy ray-curable component preferably has 3 or less hydroxy groups in one molecule, and particularly preferably has 2 or less hydroxy groups in one molecule. When the active energy ray-curable component has at least one hydroxy group in one molecule, and the amino resin has a group capable of reacting with the hydroxy group, the active energy ray-curable component and the amino resin are: It becomes possible to couple | bond through these groups, and it becomes possible to further reinforce the three-dimensional structure mentioned above.

  In the release film 1 according to this embodiment, the compounding amount of the active energy ray-curable component in the release agent composition is preferably 10 parts by mass or more, particularly 15 parts by mass with respect to 100 parts by mass of the amino resin. It is preferable that it is above, and more preferably 75 parts by mass or more. Moreover, the compounding 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, based on 100 parts by mass of the amino resin. Is preferably 500 parts by mass or less. When the amino resin and the active energy ray-curable component are blended so that the blending amount of the active energy ray-curable component is in the above range, the release film 1 according to the present embodiment has the peelability and productivity. In addition, the stability over time is excellent.

(3) Polyorganosiloxane In the release film 1 according to the present embodiment, the release agent composition contains polyorganosiloxane. Thereby, in the release agent layer 12 formed using the said release agent composition, the surface free energy in a peeling surface falls moderately. Therefore, the peeling force at the time of peeling the release film 1 from the ceramic green sheet formed on the release surface of the release film 1 is moderately reduced, and good peelability is exhibited.

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

In the formula (b), m is an integer of 1 or more. In addition, at least one of R ^{1 to} R ⁸ is preferably a hydroxy group or an organic group having a hydroxy group. That is, the polyorganosiloxane represented by the formula (b) preferably contains at least one hydroxy group or an organic group having a hydroxy group in one molecule. The upper limit of the number of hydroxy groups or organic groups having a hydroxy group in one molecule of the polyorganosiloxane is, for example, 20 although it is not particularly limited. The ceramic green sheet formed on the release surface of the release film 1 as a result of the polyorganosiloxane containing a hydroxy group or an organic group having a hydroxy group being fixed to an amino resin having a group capable of reacting with the hydroxy group On the other hand, the migration of the polyorganosiloxane from the release agent layer 12 is effectively suppressed. In particular, at least one of R ^{3 to} R ⁸ is preferably a hydroxy group or an organic group having a hydroxy group. That is, at least one of the hydroxy groups is preferably present at the end of the polyorganosiloxane. The presence of a hydroxy group at the terminal makes it easier for the polyorganosiloxane to react with an amino resin or active energy ray-curable component having a group capable of reacting with the hydroxy group, and the above migration is more effective. It is suppressed.

In formula (b), it is preferable that at least one group other than the hydroxy group among R ^{1 to} R ⁸ is an organic group. Here, when at least one of R ^{1 to} R ⁸ in the formula (b) is a hydroxy group, the organic group contained in the other R ^{1 to} R ⁸ may be an organic group having a hydroxy group. Or an organic group having no hydroxy group. On the other hand, when any of R ^{1 to} R ⁸ in the formula (b) is not a hydroxy group, the organic groups contained in other R ^{1 to} R ⁸ are preferably organic groups having a hydroxy group. In the present specification, the “organic group” does not include an alkyl group described later. The polyorganosiloxane represented by the formula (b) preferably has at least one organic group having a hydroxy group or an organic group not having a hydroxy group in one molecule, particularly preferably 1 to 10, Furthermore, it is preferable to have 1-5. Here, the organic group is preferably one or more organic groups selected from a polyester group and a polyether group. Both polyester groups and polyether groups may be present in one molecule. When the polyester group or the polyether group includes a hydroxy group, the hydroxy group may be present at the end of these organic groups, or may be present in the side chain of these organic groups. When the polyorganosiloxane has the above organic group, the polyorganosiloxane and the melamine resin are well mixed in the release agent composition, and the phase separation of these during the curing is suppressed.

In formula (b), among R ^{1 to} R ⁸ , 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, and a methyl group is particularly preferable.

R ^{1 to} R ⁸ may be the same or different. When a plurality of R ¹ and R ² are present, R ¹ and R ² may be the same or different from each other.

  The polyorganosiloxane preferably has a weight average molecular weight of 1000 or more, particularly preferably 3000 or more, and more preferably 4000 or more. The weight average molecular weight is preferably 300,000 or less, particularly preferably 100,000 or less, and more preferably 50000 or less. When the weight average molecular weight of the polyorganosiloxane is 1000 or more, the surface free energy on the release surface of the release agent layer 12 is appropriately reduced, and the release force when the release film 1 is released from the ceramic green sheet is effectively reduced. Can be reduced. When the weight average molecular weight of the polyorganosiloxane is 300000 or less, the viscosity of the release agent composition is suppressed from being excessively high, and the application liquid of the release agent composition is easily applied to the substrate 11.

  The compounding amount of the polyorganosiloxane in the release agent composition is preferably 0.1 parts by mass or more, particularly preferably 0.5 parts by mass or more, with respect to 100 parts by mass of the amino resin. It is preferable that it is 1.0 mass part or more. Further, 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 with respect to 100 parts by mass of the amino resin. Part or less. When the content of the polyorganosiloxane in the release agent composition is in the above range, the surface free energy of the release surface of the release agent layer 12 is appropriately reduced, and an excellent release force can be achieved.

(4) Acid catalyst In the release film 1 according to this 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, phosphorous acid and the like. When a full ether type melamine resin is mainly used as the amino resin, it is preferable to use p-toluenesulfonic acid as the acid catalyst from the viewpoint of allowing the condensation reaction to proceed efficiently. Further, when an imino / methylol type melamine resin is mainly used as the amino resin, it is preferable to use phosphoric acid as an 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 part by mass or more, and more preferably 2 parts per 100 parts by mass of the amino resin. It is preferably 0.0 part by mass or more. The 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, and more preferably 10 parts by mass with respect to 100 parts by mass of the amino resin. The following is preferable. The condensation reaction of an amino resin can be efficiently advanced because the compounding quantity of an acid catalyst is 0.5 mass part or more. Moreover, a low molecular weight component is hold | maintained in a three-dimensional structure because the compounding quantity of an acid catalyst is 20 mass parts or less, and precipitation from a releasing agent layer can be prevented effectively.

(5) Photopolymerization initiator having nitrogen atoms In the release film 1 according to this embodiment, the release agent composition contains a photopolymerization initiator having nitrogen atoms. Here, 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 with respect to 100 parts by mass of the acid catalyst. Thereby, the clouding of the coating liquid of a release agent composition does not arise, and the polymerization reaction of an active energy ray-curable component can be advanced efficiently. Moreover, generally, the photoinitiator which has a nitrogen atom can advance the polymerization reaction of an active energy ray hardening component more efficiently compared with the photoinitiator which does not have a nitrogen atom. Therefore, in the release film 1 according to the present embodiment, the release agent composition contains a photopolymerization initiator having nitrogen atoms in a relatively small amount range as described above. The three-dimensional structure by amino resin is reinforced more firmly.

  In the release film 1 according to this embodiment, the blending amount of the photopolymerization initiator having a nitrogen atom in the release agent composition is 1 part by mass or more and 10 parts by mass or more with respect to 100 parts by mass of the acid catalyst. It is preferable that it is particularly 50 parts by mass or more. Moreover, the compounding quantity of the said photoinitiator is 300 mass parts or less with respect to 100 mass parts of acid catalysts, It is preferable that it is 270 mass parts or less, It is especially preferable that it is 250 mass parts or less. When the amount of the photopolymerization initiator is less than 1 part by mass, the effect of advancing the polymerization reaction with the photopolymerization initiator cannot be sufficiently obtained, and the resulting release agent layer has a three-dimensional structure with an amino resin. The reinforcement will be insufficient. Moreover, when the compounding quantity of the said photoinitiator exceeds 300 mass parts, the cloudiness arises in the coating liquid of a peeling agent composition, and in the peeling agent layer formed using the said coating liquid, the smoothness of a peeling surface Is low.

  The blending amount of the photopolymerization initiator in the release agent composition is preferably 0.5 parts by mass or more, particularly 1.0 part by mass or more with respect to 100 parts by mass of the active energy ray-curable component. It is preferable that it is 2.0 mass parts or more. Further, 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, with respect to 100 parts by mass of the active energy ray-curable component. Furthermore, it is preferably 15 parts by mass or less. When the blending amount of the photopolymerization initiator is 0.5 parts by mass or more, the polymerization reaction of the active energy ray-curable component can be efficiently advanced. Moreover, the bad influence by the reaction residue can be reduced effectively because the compounding quantity of a photoinitiator is 25 mass parts or less.

  The photopolymerization initiator is not particularly limited as long as it has a nitrogen atom, and examples thereof include an α-aminoalkylphenone compound.

  Examples of α-aminoalkylphenone compounds include 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butanone-1, 2-dimethylamino-2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone and the like. Among these, it is particularly preferable to use 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one. These can be used individually by 1 type or in combination of 2 or more types.

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

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

2. Base Material 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 films made of polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polypropylene and polymethylpentene, plastics such as polycarbonate and polyvinyl acetate, and may be a single layer. However, it may be a multilayer of two or more layers of the same type or different types. Among these, a polyester film is preferable, a polyethylene terephthalate film is particularly preferable, and a biaxially stretched polyethylene terephthalate film is more preferable. Since the polyethylene terephthalate film hardly generates dust or the like during processing or use, for example, it is possible to effectively prevent a ceramic slurry coating failure due to dust or the like. Furthermore, by performing an antistatic treatment on the polyethylene terephthalate film, it is possible to increase the effect of preventing ignition due to static electricity when coating a ceramic slurry using an organic solvent or preventing defective coating.

  Moreover, in this base material 11, for the purpose of improving the adhesiveness with the release agent layer 12 provided on the surface, a surface treatment by an oxidation method or a concavo-convex method or a primer treatment is performed on one or both sides as desired. Can be applied. Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromium oxidation treatment (wet), flame treatment, hot air treatment, ozone, ultraviolet irradiation treatment, and the like. Examples include a thermal spraying method. These surface treatment methods are appropriately selected depending on the type of the base film, but generally, a corona discharge treatment method is preferably used from the viewpoints of effects and operability.

  The thickness of the substrate 11 is preferably 10 μm or more, particularly preferably 15 μm or more, and more preferably 20 μm or more. The thickness is preferably 300 μm or less, particularly preferably 200 μm or less, and more preferably 125 μm or less.

3. Properties of Release Film for Ceramic Green Sheet Manufacturing Process, etc. In the release film 1 according to this embodiment, the arithmetic average surface roughness (Ra) on the release surface of the release agent layer 12 is preferably 20 nm or less, particularly It is preferably 15 nm or less, and more preferably 10 nm or less. In the release film 1 according to the present embodiment, the release agent layer 12 is formed using the above-described release agent composition, whereby high smoothness in the above range can be achieved. In addition, arithmetic mean surface roughness (Ra) in this specification is calculated | required from the roughness curve measured using a contact-type roughness meter (for example, SV3000S4 by Mitutoyo Corporation) based on JIS B0601: 2013. Shall be.

  In addition, when the coating liquid of a release agent composition becomes cloudy, the insoluble component which causes white turbidity adheres to the surface of a release agent layer, and a processus | protrusion is produced. The protrusion generally has a size of several tens of μm to several hundreds of μm, and is a size that can be visually confirmed.

  The peeling force required to peel the release film 1 from the ceramic green sheet formed on the release surface of the release film 1 can be set as appropriate, but is preferably 5 mN / 20 mm or more, particularly 10 mN. / 20 mm or more is preferable. Further, the peeling force is preferably 100 mN / 20 mm or less, and particularly preferably 50 mN / 20 mm or less. In addition, the measuring method of the said peeling force is as showing to the test example mentioned later.

  The thickness of the release film 1 is preferably 10 μm or more, particularly preferably 15 μm or more, and more preferably 20 μm or more. The thickness is preferably 305 μm or less, particularly preferably 200 μm or less, and more preferably 125 μm or less.

4. Manufacturing method of release film for ceramic green sheet manufacturing process Release film 1 according to the embodiment can be manufactured by a normal method. For example, a coating solution is prepared by diluting the above-described release agent composition with an organic solvent, the coating solution is applied to one side of the substrate 11 to form a coating layer, and then the coating layer is heated. . Prior to this heating, the coating layer may be dried. This heating causes the condensation reaction of the amino resin to form a three-dimensional structure. After the heating, the coating layer is irradiated with active energy rays. By irradiation with active energy rays, a 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.

  There is no restriction | limiting in particular as said organic solvent, A various thing can be used. For example, hydrocarbon compounds such as toluene, hexane, heptane, isopropyl alcohol, isobutyl alcohol, acetone, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and mixtures thereof are used. In particular, it is preferable to use a mixed liquid of methyl ethyl ketone and isopropyl alcohol.

  As a coating method of the coating solution, for example, a gravure coating method, a bar coating method, a spray coating method, a spin coating method, a knife coating method, a roll coating method, a die coating method, or the like can be used.

  The heating temperature for the heating is preferably 90 ° C. or higher, and particularly preferably 110 ° C. or higher. In addition, the heating temperature is preferably 140 ° C. or lower, and particularly preferably 130 ° C. or lower. Furthermore, the heating time for the heating is preferably 10 seconds or longer, and more preferably 20 seconds or longer. In addition, the heating temperature is preferably 120 seconds or less, and 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. Although the irradiation amount of an active energy ray changes with kinds of energy ray, for example, in the case of ultraviolet rays, the amount of light is preferably 50 mJ / cm ² or more, particularly preferably 100 mJ / cm ² or more. Further, the irradiation amount of ultraviolet rays is preferably 1000 mJ / cm ² in terms of light quantity, and particularly preferably 500 mJ / cm ² . In the case of an electron beam, 0.1 kGy or more is preferable, and 50 kGy or less is preferable.

  In the release film 1 according to this embodiment, the release agent layer 12 is formed using the above-described release agent composition coating solution. In the coating solution of the release agent composition, a hardly soluble or insoluble salt due to the photopolymerization initiator and the acid catalyst is not formed, and the coating solution does not become cloudy. For this reason, the release surface of the release agent layer 12 does not have irregularities due to poorly soluble or insoluble salts, and the release surface exhibits very high smoothness.

5. Method of using release film for ceramic green sheet production process The release film 1 can be used for producing a ceramic green sheet. Specifically, after applying a ceramic slurry containing a ceramic material such as barium titanate or titanium oxide to the release surface of the release agent layer 12, a ceramic green sheet is obtained by drying the ceramic slurry. Can do. The coating can be performed using, for example, a slot die coating method or a doctor blade method.

  Examples of the binder component contained in the ceramic slurry include butyral resins and acrylic resins. Examples of the solvent contained in the ceramic slurry include organic solvents and aqueous solvents.

  As described above, the release film 1 according to the present embodiment has excellent quality with no defects such as pinholes and uneven thickness by using the release film 1 because the release surface exhibits high smoothness as described above. Ceramic green sheets can be formed.

  The embodiment described above is described for facilitating understanding of the present invention, and is not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.

  For example, another layer such as an antistatic layer may be provided between the surface of the substrate 11 opposite to the release agent layer 12 or between the substrate 11 and the release agent layer 12.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples etc.

[Example 1]
100 parts by mass (converted as solid content) of full ether type methylated melamine resin as amino resin (manufactured by Nippon Carbide, product name “MW-30”, weight average molecular weight 608, molecular weight distribution (Mw / Mn) 1.005) Amount, the same applies hereinafter), 100 parts by mass of pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name “A-TMM-3L”) as an active energy ray-curable component, and polyether-modified hydroxyl group as polyorganosiloxane 3. 2.0 parts by mass of polydimethylsiloxane (produced by BYK Japan, product name “BYK-377”) and p-toluenesulfonic acid as an acid catalyst (product name “Dryer 900”, manufactured by Hitachi Chemical Co., Ltd.) 0 part by mass and 2-methyl-1- (4-methylthiophenyl) -2-morpholinop as a photopolymerization initiator Pan-1-one (manufactured by Ciba, product name “Irgacure 907”) is mixed with 5.0 parts by mass of a mixed solvent of methyl ethyl ketone and isopropyl alcohol, and a coating solution of a release agent composition having a solid content of 18% by mass is prepared. Obtained.

The obtained coating solution was uniformly applied to one side of a biaxially stretched polyethylene terephthalate film (thickness: 25 μm) as a base material with a Mayer bar # 5 to obtain a coating layer. Next, the coating layer was heated at 120 ° C. for 30 seconds, and then the release agent composition was cured by irradiating 50 mJ / cm ² of ultraviolet light from the coating layer side with a high-pressure mercury lamp in a nitrogen atmosphere. A release film was obtained in which a release agent layer having a thickness of 1.2 μm was laminated.

  In addition, the thickness of the base material and the release agent layer was measured using a reflective film thickness meter (manufactured by Filmetrics, product name “F20”).

[Examples 2 to 4]
A release film was obtained in the same manner as in Example 1 except that the blending amounts of the active energy ray-curable component, the acid catalyst, and the photopolymerization initiator were changed as shown in Table 1.

Example 5
Except for using 125 parts by mass of an imino methylated melamine resin (manufactured by Nippon Carbide, product name “MX-730”, weight average molecular weight 1508, molecular weight distribution (Mw / Mn) 1.18) as an amino resin, A release film was obtained in the same manner as in Example 1.

[Comparative Example 1]
A release film was obtained in the same manner as in Example 1 except that the amounts of the active energy ray-curable component and the photopolymerization initiator were changed as shown in Table 1.

[Test Example 1] (Evaluation of cloudiness)
About the coating liquid of the release agent composition prepared in the Example and the comparative example, the presence or absence of cloudiness was confirmed visually. An example in which the coating solution was not cloudy was evaluated as ◯, and an example in which the coating solution was clouded was evaluated as x. The results are shown in Table 1.

[Test Example 2] (Evaluation of smoothness)
About the release film manufactured in the Example and the comparative example, the smoothness of the peeling surface of a release agent layer was evaluated visually. The example in which unevenness was not generated on the peeled surface was evaluated as “◯”, and the example in which unevenness was generated on the peeled surface was evaluated as “x”. The results are shown in Table 1.

[Test Example 3] (Measurement of peel force)
100 parts by mass of barium titanate (BaTiO ₃ ; manufactured by Sakai Chemical Industry Co., Ltd., product name “BT-03”), 10 parts by mass of polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd., product name “ESREC B / KBM-2”), and 69 parts by mass of toluene and 46 parts by mass of ethanol were added to 5 parts by mass of dioctyl phthalate (manufactured by Kanto Chemical Co., Ltd., product name “dioctyl phthalate first grade”), and mixed and dispersed in a ball mill to prepare a ceramic slurry. .

  In the release films that were produced in the examples and comparative examples and stored at room temperature for 48 hours, the ceramic slurry was uniformly applied to the release surface of the release agent layer using an applicator, and then 80% in a dryer. Dry at 1 ° C. for 1 minute. As a result, a ceramic green sheet having a thickness of 3 μm was obtained on the release film. In this way, a release film with a ceramic green sheet was produced.

  This release film with a ceramic green sheet was allowed to stand for 24 hours in an atmosphere at room temperature of 23 degrees and humidity of 50%. Next, an acrylic adhesive tape (manufactured by Nitto Denko Corporation, product name “31B tape”) was applied to the surface of the ceramic green sheet opposite to the release film, and cut into a width of 20 mm in that state. This was used as a measurement sample.

  From the ceramic green sheet, the pressure-sensitive adhesive tape side of the measurement sample is fixed to a flat plate, using a tensile tester (manufactured by Shimadzu Corporation, product name “AG-IS500N”) at a peeling angle of 180 ° and a peeling speed of 100 mm / min The release film was peeled off, and the force required to peel off (peeling force; mN / 20 mm) was measured. The results are shown in Table 1.

Details of the abbreviations and the like described in Table 1 are as follows.
[Amino resin]
MW-30: full ether type methylated melamine resin (manufactured by Nippon Carbide, product name “MW-30”, weight average molecular weight 608, molecular weight distribution (Mw / Mn) 1.005)
MX-730: imino methylated melamine resin (manufactured by Nippon Carbide, product name “MX-730”, weight average molecular weight 1508, molecular weight distribution (Mw / Mn) 1.18)

  As is clear from Table 1, the coating solutions prepared in the examples were not cloudy and the release surface of the release agent layer showed high smoothness. Furthermore, in the peeling film obtained in the Example, it was possible to peel with an appropriate peeling force when peeling from the ceramic green sheet.

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

DESCRIPTION OF SYMBOLS 1 ... Release film for ceramic green sheet manufacturing process 11 ... Base material 12 ... Release agent layer

Claims (9)

A release film for a ceramic green sheet manufacturing process comprising a substrate and a release agent layer provided on one side of the substrate,
The release agent layer is formed from 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. ,
The amount of the photopolymerization initiator in the release agent composition is 1 part by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the acid catalyst. the film.   The amount of the photopolymerization initiator in the release agent composition is 0.5 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the active energy ray-curable component. Item 2. A release film for a ceramic green sheet production process according to item 1.   The release film for a ceramic green sheet manufacturing process according to claim 1, wherein the amino resin is a melamine resin.   The compounding 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 with respect to 100 parts by mass of the amino resin. The peeling film for ceramic green sheet manufacturing processes as described in any one of these.   The blending amount of the polyorganosiloxane in the release agent composition is 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the amino resin. The peeling film for ceramic green sheet manufacturing processes as described in any one.   The amount of the acid catalyst in the release 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. A release film for a ceramic green sheet manufacturing process according to claim 1.   The said active energy ray hardening component has at least 1 hydroxy group in 1 molecule, The release film for ceramic green sheet manufacturing processes as described in any one of Claims 1-6 characterized by the above-mentioned.   The said polyorganosiloxane has at least 1 hydroxy group in 1 molecule, The release film for ceramic green sheet manufacturing processes as described in any one of Claims 1-7 characterized by the above-mentioned. A method for producing a release film for a ceramic green sheet production process comprising a substrate and a release agent layer provided on one side of the substrate,
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 is applied to one side of the substrate, and then applied. Forming a layer, and heating the coating layer, and further irradiating the coating layer with active energy rays to form the release agent layer,
The amount of the photopolymerization initiator in the release agent composition is 1 part by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the acid catalyst. A method for producing a film.

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