TW201708393A - Release film for ceramic green sheet production process - Google Patents

Abstract

A release film 1A for a ceramic green sheet production process, comprising a base material 11 and a release agent layer 12 provided on one side of the base material 11. The release agent layer 12 comprises a release agent composition containing: a melamine resin having a total acid value of 0.030-0.154 mg KOH/g and a weight-average molecular weight of 1,000-10,000; and a polyorganosiloxane. The release film 1A for a ceramic green sheet production process displays good release properties and has reduced occurrence of curling.

Description

Release film for ceramic green sheet manufacturing process

The present invention relates to a release film used in the process of manufacturing a ceramic green sheet.

Conventionally, in the production of a laminated ceramic product such as a laminated ceramic capacitor or a multilayer ceramic substrate, a ceramic green sheet is molded, and a plurality of obtained ceramic green sheets are laminated and fired.

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

The release film is usually composed of a substrate and a release agent layer provided on one side of the substrate. As the release agent layer, an ultraviolet curable compound is used as a material. The release agent layer is formed by applying a release agent composition containing an ultraviolet curable compound to a substrate, and curing the composition by ultraviolet irradiation. However, in the ultraviolet curable compound, there is a type in which hardening is inhibited by oxygen. When such an ultraviolet curable compound is used, there is a hardening in the vicinity of the side opposite to the base material of the release agent layer (the surface in contact with the ceramic slurry or the ceramic green sheet; hereinafter, sometimes referred to as the "peeling surface"). Insufficient circumstances. If the hardening of the release agent layer is insufficient, the elasticity of the release agent layer is lowered. the result, The peeling force required when the release sheet is peeled off from the ceramic green sheet formed on the release surface becomes strong.

On the other hand, Patent Document 1 and Patent Document 2 disclose a release film in which a release agent layer is formed using a melamine resin which is one of thermosetting compounds. In the release film, a release agent composition containing a melamine resin is applied onto a substrate and heated to form a release agent layer containing a cured product of a melamine resin. In the release agent layer, when the ultraviolet curable compound is used, the above-mentioned specific problem is not caused.

Further, in general, "melamine resin" means a mixture of at least one of a plurality of melamine compounds and a polynuclear compound obtained by condensing one or more melamine compounds. In the present specification, the phrase "melamine resin" means a mixture of the above mixture or a melamine compound. Further, in the present specification, the melamine resin is cured and referred to as "melamine cured product".

[Previous Technical Literature]

[Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. Hei 11-300896

Patent Document 2: Japanese Laid-Open Patent Publication No. 2006-7568

However, in the release film described in Patent Document 1 and Patent Document 2, curling is likely to occur at the stage of forming the release agent layer from the melamine resin. In particular, when the release agent layer is produced under high temperature conditions, the generation of curl can be promoted. The peeling film which produces such a curl has poor handleability and is not suitable for the manufacture of ceramic green sheets.

The present invention has been completed in view of such actual circumstances, and its purpose is Provided is a release film for a ceramic green sheet manufacturing process which exhibits excellent peelability and which suppresses generation of curl.

In order to achieve the above object, the present invention provides a release film for a ceramic green sheet manufacturing process, comprising a substrate and a release agent layer disposed on one side of the substrate, wherein the release agent layer is a release agent. The composition is formed, and the release agent composition contains: a melamine resin having a total acid value of 0.030 to 0.154 mgKOH/g and a weight average molecular weight of 1,000 to 10,000; and a polyorganosiloxane (Invention 1).

According to the above invention (Invention 1), the release agent layer is formed of a release agent composition containing a melamine resin having a weight average molecular weight of 1,000 to 10,000, a total acid value of 0.030 to 0.154 mgKOH/g, and a polyorganoquinone. The oxane, thereby showing excellent peelability, and suppressing the generation of curl.

In the above invention (Invention 1), it is preferred that the melamine resin contains a compound represented by the following formula (a) or a polynuclear compound obtained by condensing two or more of the above compounds (Invention 2).

(wherein, X represents -H, -CH ₂ -OH or -CH ₂ -OR, and may be the same or different. R represents an alkyl group having 1 to 8 carbon atoms, and may be the same or different. At least one X is -CH ₂ -OH.)

In the above invention (Inventions 1 and 2), it is preferred that the polyorganosiloxane has at least one hydroxyl group in one molecule (Invention 3).

In the above invention (Inventions 1 to 3), it is preferred that the polyorganosiloxane has at least one organic group selected from the group consisting of a polyester group and a polyether group in one molecule (Invention 4).

In the above inventions (Inventions 1 to 4), it is preferred that the polyorganosiloxane has a weight average molecular weight of from 1,000 to 300,000 (Invention 5).

In the above invention (Inventions 1 to 5), it is preferred that the release agent composition further contains an acid catalyst (Invention 6).

In the above invention (Inventions 1 to 6), it is preferred that the release agent layer has a thickness of 0.1 to 3 μm (Invention 7).

In the above invention (Inventions 1 to 7), it is preferable to further include a resin layer between the substrate and the release agent layer (Invention 8).

In the above invention (Invention 8), the resin layer is formed of a composition containing melamine resin, a total acid value of 0.030 to 0.154 mgKOH/g, and a weight average molecular weight of preferably 1,000 to 10,000. 9).

The release film for a ceramic green sheet manufacturing process of the present invention exhibits excellent peelability and suppresses generation of curl.

1A, 1B‧‧‧Removal film for ceramic green sheet manufacturing process

11‧‧‧Substrate

12‧‧‧ Stripper layer

13‧‧‧ resin layer

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

Fig. 2 is a cross-sectional view showing a release film for a ceramic green sheet manufacturing process according to another embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described.

[Removal film for ceramic green sheet manufacturing process]

As shown in Fig. 1, the release film 1A for a ceramic green sheet manufacturing process according to the first embodiment (hereinafter sometimes referred to simply as "release film 1A") is composed of a substrate 11 and a laminate on one side of the substrate 11. The release agent layer 12 (the upper surface in Fig. 1) is configured.

In addition, as shown in FIG. 2, the release film 1B for ceramic green sheet manufacturing process of the second embodiment (hereinafter sometimes referred to simply as "release film 1B") is included in the substrate 11 including the substrate 11. The resin layer 13 of one surface (upper surface in FIG. 2) and the release agent layer 12 laminated on the surface (upper surface in FIG. 2) of the resin layer 13 on the opposite side to the substrate 11 are formed.

Stripper layer

The release agent layer 12 of the release film 1A and the release film 1B is formed of a release agent composition containing a melamine resin having a total acid value of 0.030 to 0.154 mgKOH/g and a weight average molecular weight of 1,000 to 10,000. And polyorganosiloxane.

In the release film 1A and the release film 1B, the release agent layer 12 is formed of a release agent composition containing polyorganosiloxane. Therefore, the surface free energy in the peeling surface is appropriately reduced. Further, the release agent layer 12 is formed of a release agent composition containing a melamine resin. Therefore, by the heating, the release agent composition can be sufficiently hardened, and the knot is As a result, the formed release agent layer 12 has sufficient elasticity. By this, when the peeling film 1A and the peeling film 1B are peeled off from the ceramic green sheet formed on the peeling surface of the peeling film 1A and the peeling film 1B, the peeling force is suitably reduced, and the outstanding peeling property is exhibited.

Further, when the melamine resin is subjected to a crosslinking reaction, an alcohol (R-OH), an ether (R-O-R) or water is usually removed depending on the kind of the functional group used in the reaction. These removed components are discharged from the release agent layer 12 when the release agent layer 12 is formed. In particular, when the crosslinking reaction is carried out under high temperature conditions, the discharge can be promoted. Due to such discharge, it is considered that volume shrinkage of the release agent layer 12 may occur, and along with this phenomenon, curl of the release film may occur.

On the other hand, in the release agent composition for forming the release agent layer 12 of the release film 1A and the release film 1B, the total acid value of the melamine resin is 0.030 to 0.154 mgKOH/g. This indicates that the amount of the methylol group (-CH2-OH) in the melamine resin is relatively large. When such a melamine resin is subjected to a condensation reaction, the ratio of water is increased as a component to be removed. Thereby, the release agent layer 12 formed of the melamine resin has a smaller volume shrinkage than the release agent layer formed of the melamine resin having a small content of the methylol group, and the release film 1A and the release film can be suppressed. Curl is produced in 1B.

Further, in the release agent composition for forming the release agent layer 12 of the release film 1A and the release film 1B, the melamine resin has a weight average molecular weight of 1,000 to 10,000. This means that the melamine resin contains a large number of polynuclear bodies of melamine compounds. The polynuclear body of the melamine compound has a chemical structure in which a certain degree of condensation reaction is carried out as compared with the mononuclear body. The composition of the release agent comprising the melamine resin containing a polynuclear compound containing a large amount of the melamine compound is hardened, and the volume shrinkage is reduced by an amount corresponding to the amount of the component to be removed. From this The point can also suppress the occurrence of curl in the release film 1A and the release film 1B.

Melamine resin

In the release agent composition for forming the release agent layer 12, the total acid value of the melamine resin is 0.030 to 0.154 mgKOH/g, preferably 0.032 to 0.100 mgKOH/g, and particularly preferably 0.035 to 0.070 mgKOH/g. The total acid value of the melamine resin means that the group can be reacted with potassium hydroxide contained in 1 g of the melamine resin in order to make the mass (mg) of potassium hydroxide required for the complete reaction of a group. In the present specification, the total acid value of the melamine resin is represented by an actual measured value, and is not represented by a theoretical value. Here, the group reactive with potassium hydroxide is hydroxymethyl (-CH2-OH). On the other hand, the imido group (-NH-) and the alkyl ether group (-CH2-OR) are not reacted with potassium hydroxide. Further, a specific measurement method of the total acid value of the melamine resin is shown in the test examples described later. When the total acid value is less than 0.030 mgKOH/g, the ratio of the imine group and the alkyl ether group in the melamine resin becomes relatively large, and when the condensation reaction is carried out, the ratio of the component having a large molecular volume is removed. Thereby, the degree of volume shrinkage by the condensation reaction becomes large, and curling occurs in the obtained release film. On the other hand, when the total acid value is more than 0.154 mgKOH/g, the acidic group which does not participate in the condensation reaction is excessively large, and it becomes difficult to control the crosslinking speed. As a result, the quality of the ceramic green sheets formed on the peeling surface is lowered.

The melamine resin has a weight average molecular weight of from 1,000 to 10,000, preferably from 1,000 to 5,000, more preferably from 1,000 to 4,000, in the release agent composition for forming the release agent layer 12. If the weight average molecular weight is less than 1,000, the melamine resin contains more mononuclear bodies, and the amount of components removed by the condensation reaction increases. Thereby, when the release agent composition is cured, volume shrinkage is likely to occur, and curling is likely to occur in the release film 1A and the release film 1B obtained. The other side When the weight average molecular weight is more than 10,000, the viscosity of the release agent composition becomes high, and the coatability when the release agent composition is applied onto the substrate 11 is deteriorated. In addition, the weight average molecular weight in this specification is a standard polystyrene conversion value measured by the gel permeation chromatography (GPC) method.

Specifically, the melamine resin preferably contains a melamine compound represented by the following formula (a) or a polynuclear compound obtained by condensing two or more of the melamine compounds.

In the formula (a), X represents -H, -CH ₂ -OH, or -CH ₂ -OR. These groups constitute a reactive group in the condensation reaction of the above melamine compounds with each other. Specifically, the -NH group formed by the fact that X is H can carry out a condensation reaction between the -N-CH ₂ -OH group and the -N-CH ₂ -R group. Further, the -N-CH ₂ -OH group formed by X being -CH ₂ -OH and the -N-CH ₂ -R group formed by X being -CH ₂ -R can be together in the -NH group A condensation reaction is carried out between the -N-CH ₂ -OH group and the -N-CH ₂ -R group. In the formula (a), at least one X system is -CH ₂ -OH. When a condensation reaction occurs in the -CH ₂ -OH group, the effect of suppressing volume shrinkage is increased, and curling in the release film 1A and the release film 1B can be further suppressed. When the melamine resin contains a polynuclear body obtained by condensation of the above melamine compound, the polynuclear body itself has at least one -CH ₂ -OH group. Further, when the polyorganosiloxane has a reactive group such as a hydroxyl group, a -CH ₂ -OH group and a -CH ₂ -OR group are chemically bonded to the reactive group.

In the above -CH ₂ -OR group, R represents a C 1-8 alkyl group. The number of carbon atoms is preferably from 1 to 6, and from 1 to 3 is particularly preferred. 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. The methyl group is particularly preferred.

The above X may be the same or different. Further, the above R may be the same or different.

Among the melamine compounds, there are generally the following types: all X is a full ether type of -CH ₂ -OR; at least one X is -CH ₂ -OH and at least one X is H an imido hydroxymethyl type; at least one X It is -CH ₂ -OH and there is no hydroxymethyl group of X which is H, and at least one imine type of X is H and -CH ₂ -OH which is H is absent. In the release film 1A and the release film 1B, the melamine resin contains an imidomethylol group or a hydroxymethyl group from the viewpoint of easy suppression of curl and easy realization of physical properties of a total acid value of 0.030 to 0.154 mgKOH/g. A melamine compound is preferred. In particular, (a) In the formula, X is more preferred to -CH ₂ -OH, specifically, -CH ₂ -OH by the number of X is at least one of preferred, at least three are particularly preferred .

Further, from the viewpoint of easily suppressing the curl in the release film 1A and the release film 1B, and from the viewpoint of easily achieving physical properties such as a weight average molecular weight of 1,000 to 10,000, the melamine resin is condensed by 2 to 10 and represented by the above formula (a). The polynuclear compound formed by the compound is preferable, and the multinuclear body formed by condensing 3 to 9 is particularly preferable, and the multinuclear body formed by condensing 4 to 7 is further preferable.

(2) Polyorganooxane

The polyorganosiloxane is not particularly limited. The release agent layer 12 of the release film 1A and the release film 1B is formed of a release agent composition containing polyorganosiloxane, whereby the release film 1A and the release film 1B can exhibit excellent peelability. As the polyorganosiloxane, a polymer containing a ruthenium compound represented by the following formula (b) can be used.

In the formula (b), m is an integer of 1 or more. Further, it is preferred that at least one of R1 to R8 is a hydroxyl group or an organic group having a hydroxyl group. That is, the polyorganosiloxane having the formula (b) preferably contains at least one hydroxyl group or an organic group having a hydroxyl group in one molecule. Further, the upper limit of the number of hydroxyl groups or the number of organic groups having a hydroxyl group in one molecule of the polyorganosiloxane is not particularly limited, and is, for example, 20 or more. The polyorganosiloxane comprises a hydroxyl group or an organic group having a hydroxyl group, whereby a condensation reaction occurs between the hydroxyl group and a -CH ₂ -OH group or a -CH ₂ -OR group of the melamine resin, and a polyorganosiloxane is formed. A structure in which an alkane is bonded to a melamine hardened material. Thereby, it is possible to suppress the transfer of the polyorganosiloxane from the release agent layer 12 to the ceramic green sheets formed on the release surface of the release film 1A and the release film 1B. In particular, it is preferred that at least one of R3 to R8 is a hydroxyl group or an organic group having a hydroxyl group. That is, it is preferred that at least one of the hydroxyl groups is present at the end of the polyorganosiloxane. A hydroxyl group is present at the terminal, whereby the polyorganosiloxane is easily subjected to a condensation reaction with the melamine resin, and the above transfer can be effectively suppressed.

In the formula (b), at least one of the groups other than the hydroxyl group in R1 to R8 is preferably an organic group. Here, when at least one of R1 to R8 in the formula (b) is a hydroxyl group, the other organic group contained in R1 to R8 may be an organic group having a hydroxyl group, or may be an organic group having no hydroxyl group. On the other hand, when any of R1 to R8 in the formula (b) is a non-hydroxy group, the other organic group contained in R1 to R8 is preferably an organic group having a hydroxyl group. In the present specification, the "organic group" is defined as a group which does not contain an alkyl group which will be described later. The polyorganosiloxane having the formula (b) preferably has at least one organic group having a hydroxyl group or an organic group having no hydroxyl group in one molecule, and is preferably 1 to 10, and has 1 to 5 It is further preferred. Here, the organic group is preferably one or more organic groups selected from the group consisting of a polyester group and a polyether group. Both a polyester group and a polyether group may be present in one molecule. When the polyester or polyether group contains a hydroxyl group, the hydroxyl group may be present at the end of the organic group or may be present in the side chain of the organic group. The polyorganosiloxane has the above organic group, whereby the polyorganosiloxane and the melamine resin are well mixed in the release agent composition, and the extreme phase separation can be suppressed at the time of hardening.

In the formula (b), a group other than the above group in R1 to R8 is preferably an alkyl group 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. The methyl group is particularly preferred.

R1~R8 can be the same or different. Moreover, when there are a plurality of R1 and R2, R1 and R2 may be the same or different.

The polyorganosiloxane has a weight average molecular weight of 1000~ 300000 is preferred, 3000~100000 is particularly preferred, and 4000~50000 is further preferred. When the weight average molecular weight of the polyorganosiloxane is 1000 or more, the surface free energy of the release surface of the release agent layer 12 is appropriately reduced, and the peeling film 1A and the release film 1B can be effectively reduced when peeled off from the ceramic green sheet. Peel force. The polyorganosiloxane has a weight average molecular weight of 300,000 or less, whereby the viscosity of the release agent composition is suppressed from becoming too high, and the release agent composition is easily applied to the substrate 11.

The content of the polyorganosiloxane in the release agent composition is preferably 0.05 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 8 parts by mass, based on 100 parts by mass of the melamine resin. When the content of the polyorganosiloxane in the release agent composition is 0.05 parts by mass or more, the surface free energy on the release surface of the release agent layer 12 is sufficiently reduced, and an appropriate peeling force can be achieved. On the other hand, the content of the polyorganosiloxane in the release agent composition is 15 parts by mass or less, whereby the content of the melamine resin can be secured. Thereby, the elasticity of the release agent layer 12 is improved, and an appropriate peeling force can be achieved.

(3) Other ingredients

The stripper composition further preferably contains an acid catalyst. As an example of the acid catalyst, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, p-toluenesulfonic acid or the like is preferred, and p-toluenesulfonic acid is particularly preferred. The stripper composition contains an acid catalyst, whereby the condensation reaction in the above melamine resin can be effectively carried out.

The content of the acid catalyst in the release agent composition is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and still more preferably 1 to 15 parts by mass, based on 100 parts by mass of the melamine resin.

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

(4) Thickness

The thickness of the release agent layer 12 is preferably 0.1 to 3 μm, particularly preferably 0.2 to 2 μm, and further preferably 0.3 to 1.5 μm. The thickness of the release agent layer 12 is 0.1 μm or more, whereby the function as the release agent layer 12 can be effectively exhibited. In particular, the thickness of the release agent layer 12 containing the melamine cured product is thicker than usual, whereby the elasticity of the release agent layer 12 is increased, and the peelability is improved. Further, when the thickness of the release agent layer 12 is 3 μm or less, when the release film 1A and the release film 1B are curled into a roll shape, clogging can be suppressed. The release agent layer 12 such as 0.1 to 3 μm is thicker than the usual release agent layer 12. Generally, the thicker the stripper layer 12 is, the more likely it is to cause curling. However, in the release film 1A and the release film 1B, the release agent layer 12 is formed of a release agent composition containing the melamine resin, whereby the occurrence of curl can be suppressed even when the thickness of the release agent layer 12 is thick. .

2. Substrate

The base material 11 of the release film 1A and the release film 1B is not particularly limited as long as the release agent layer 12 or the resin layer 13 can be laminated. Examples of the substrate 11 include polyesters such as polyethylene terephthalate and polyethylene naphthalate; polyolefins such as polypropylene and polymethylpentene; polycarbonate and polyvinyl acetate; A film composed of a plastic such as an ester. The films may be a single layer or may be 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 further preferable. The polyethylene terephthalate film is less likely to generate dust or the like during processing, use, and the like, and thus it is possible to effectively prevent coating defects such as coating of ceramics due to dust or the like. Moreover, by antistatic treatment of the polyethylene terephthalate film, it is possible to improve the ceramic slurry which prevents the use of the organic solvent by coating. The effect of ignition caused by static electricity or prevention of coating failure during material feeding.

In order to improve the adhesion to the release agent layer 12 or the resin layer 13 provided on the surface of the substrate 11, it is possible to perform surface treatment by an oxidation method or a roughening method on one or both surfaces as needed. Or primer treatment. Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromium oxidation treatment (wet), flame treatment, hot air treatment, ozone, and ultraviolet irradiation treatment. Further, examples of the unevenness forming method include a sand blasting method and a thermal spraying method. These surface treatment methods are appropriately selected depending on the type of the base film, but in view of effects and workability, a corona discharge treatment method is generally preferably used.

The thickness of the substrate 11 is usually 10 to 300 μm, preferably 15 to 200 μm, and particularly preferably 20 to 125 μm.

3. Resin layer

The resin layer 13 provided on the release film 1B is located between the substrate 11 and the release agent layer 12 as shown in Fig. 2 . By providing the resin layer 13 between the substrate 11 and the release agent layer 12, it is possible to absorb the unevenness on the side of the release agent layer 12 of the substrate 11, and to reduce the roughness of the release surface of the release film 1B.

The resin forming the resin layer 13 is not particularly limited, and examples thereof include melamine resin, epoxy resin, phenol resin, urea resin, polyester resin, urethane resin, acrylic resin, polyimine resin, and benzene. And oxazine resin and the like. Among them, it is particularly preferable to form the resin layer 13 from a melamine resin. The resin layer 13 is formed of a melamine resin, whereby the adhesion between the resin layer 13 and the substrate 11 and between the resin layer 13 and the release agent layer 12 is improved. Further, the elasticity of the release surface side of the release film 1B is improved, and the peeling force when the release film 1B is peeled off from the ceramic green sheet is appropriately reduced.

There is no particular limitation on the melamine resin used to form the resin layer 13. set. However, from the viewpoint of suppressing shrinkage of the resin layer 13 itself, as the melamine resin for forming the resin layer 13, the above-mentioned melamine resin used for forming the release agent layer 12 is preferably used. That is, it is preferred to form the resin layer 13 using a composition containing the aforementioned melamine resin.

Further, the resin layer 13 may contain components other than the melamine resin and the melamine resin, and may contain, for example, an epoxy resin, a phenol resin, a urea resin, a polyester resin, a polyurethane resin, an acrylic resin, a polyimide resin, a benzo Resin such as oxazine resin. When the resin layer 13 contains the resins, the content thereof is preferably from 1 to 200 parts by mass, more preferably from 10 to 150 parts by mass, even more preferably from 30 to 100 parts by mass, per 100 parts by mass of the melamine resin. Further, the resin layer 13 may contain a crosslinking agent, a reaction inhibitor, an adhesion promoter, and the like.

The thickness of the resin layer 13 is usually 0.1 to 3 μm, preferably 0.2 to 2 μm, and particularly preferably 0.3 to 1.5 μm.

4. Physical properties of the release film for the ceramic green sheet manufacturing process

The peeling force required to peel off the release film 1A and the release film 1B from the ceramic green sheets formed on the release surface of the release film 1A and the release film 1B can be appropriately set, but 2.5 to 50 mN/20 mm is preferable, and 5 to 25 mN is preferable. /20mm is especially good. The release agent layer in the release film 1A and the release film 1B is formed of a release agent composition containing the above melamine resin and polyorganosiloxane. Therefore, the peeling force of 2.5 to 50 mN / 20 mm can be suitably set.

5. Method for producing release film for ceramic green sheet manufacturing process

When the release film 1A is produced, the release agent composition and the coating liquid containing an organic solvent as necessary are applied to one surface of the substrate 11, and then dried and heated to cure the release agent composition to form the release agent layer 12. . With this, you can get stripped From the film 1A. As the coating method, 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.

When the release film 1B is produced, for example, a coating liquid containing a melamine resin which is a raw material of the melamine resin is applied onto one surface of the substrate 11, and then dried and heated to form the resin layer 13. Further, after applying the release agent composition and the coating liquid containing an organic solvent as necessary on the surface of the resin layer 13 opposite to the substrate 11, drying and heating are performed to cure the release agent composition to form a release agent. Layer 12. Thereby, the peeling film 1B can be obtained. As such a coating method, the same as the above coating method can be used.

The organic solvent is not particularly limited, and various solvents can be used. For example, isopropanol, isobutanol, acetone, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and the like may be used, including a hydrocarbon compound such as toluene, hexane or heptane. In particular, a mixture of methyl ethyl ketone and isopropyl alcohol is preferred.

It is preferred that the release agent composition after coating as described above is thermally cured. In this case, the heating temperature is preferably from 90 to 140 ° C, and 110 to 130 ° C is particularly preferred. Moreover, the heating time is preferably about 10 to 120 seconds, and about 50 to 70 seconds is particularly good.

In the release film 1A and the release film 1B, the release agent layer 12 is formed of a release agent composition containing the melamine resin and the polyorganosiloxane, whereby excellent peelability can be exhibited and curl generation can be suppressed. In particular, in the case where the release agent layer 12 is formed under high temperature conditions, the occurrence of curl can be effectively suppressed.

6. Method for using peeling film for ceramic green sheet manufacturing process

The release film 1A and the release film 1B can be used for producing a ceramic green sheet. Specifically, after a ceramic slurry containing a ceramic material such as barium titanate or titania is applied to the release surface of the release agent layer 12, the ceramic slurry is dried to obtain a ceramic. Raw film. The coating can be performed, for example, by a slit die coating method, a doctor blade method, or the like.

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

As described above, the release film 1A and the release film 1B exhibit excellent peelability, and the occurrence of curl is suppressed. When the release film 1A and the release film 1B are used to form the ceramic green sheet, when the release film 1A and the release film 1B are peeled off from the ceramic green sheet, peeling can be performed with an appropriate peeling force. Further, a flat ceramic green sheet which is not bent can be obtained.

The embodiments described above are described in order to facilitate the understanding of the present invention, and are not intended to limit the present invention. Therefore, the respective elements disclosed in the above embodiments are intended to encompass all design changes and equivalents of the technical scope of the invention.

For example, between the substrate 11 on the side opposite to the release agent layer 12, the substrate 11 in the release film 1A and the release agent layer 12, or between the substrate 11 and the resin layer 13 in the release film 1B or Another layer such as an antistatic layer may be provided between the resin layer 13 and the release agent layer 12.

[Examples]

Hereinafter, the present invention will be specifically described by way of Examples and the like, but the scope of the present invention is not limited to the Examples and the like.

[Example 1]

100 parts by mass of the imine-based methylated melamine resin (a1) (manufactured by NIPPON CARBIDE INDUSTRIES CO., INC., trade name: MX-730, weight average molecular weight 1508) (the amount converted as a solid component, the same applies hereinafter ), Polydimethyl methoxide (b1) containing a polyether-modified hydroxyl group (manufactured by BYK Japan KK, trade name: BYK-377) 1.0 part by mass, and p-toluenesulfonic acid as an acid catalyst (Hitachi Chemical Co., Ltd.) Manufactured, product name: dryer 900) 4.0 parts by mass, mixed in a mixed solvent of methyl ethyl ketone, isopropyl alcohol and isobutanol to obtain a coating liquid of a release agent composition having a solid content of 20% by mass .

The maximum protrusion height Rp of the obtained coating liquid uniformly applied to the biaxially-oriented polyethylene terephthalate film (thickness: 25 μm) as a substrate was 452 nm by Meyer Bar #6. On the face. Subsequently, the release agent composition was cured by heating and drying at 120 ° C for 1 minute to obtain a release film having a release layer having a thickness of 1.2 μm laminated on the substrate.

Further, the thickness of the substrate and the release agent layer was measured using a reflective film thickness meter (manufactured by Filmetrics, Inc., product name: F20).

[Example 2 to Example 4]

Polydimethyl methoxy oxane (b1) containing a polyether-modified hydroxyl group (manufactured by BYK Japan KK, trade name: BYK-377) was changed to polydimethyl methoxy oxane (b2) containing a polyester-modified hydroxyl group. A release film was obtained in the same manner as in Example 1 except that the mass fraction of b2 was changed as shown in Table 1 (manufactured by BYK Japan KK, trade name: BYK-370).

[Example 5]

A release film was obtained in the same manner as in Example 2 except that the parts by mass of the acid catalyst were changed as shown in Table 1.

[Example 6]

Imino-type methylated melamine resin (a1) (manufactured by NIPPON CARBIDE INDUSTRIES CO., INC., trade name: MX-730, weight average molecular weight 1508) changed to imine hydroxymethyl type methylated melamine resin (a2) (manufactured by NIPPON CARBIDE INDUSTRIES CO., INC., trade name: MS-001, weight average molecular weight 3987, molecular weight distribution (Mw/Mn) 1.51 A release film was obtained in the same manner as in Example 2 except for the above.

[Examples 7, 8]

A release film was obtained in the same manner as in Example 2 except that the thickness of the release agent layer was changed as shown in Table 1.

[Example 9]

Polydimethyl methoxide (b1) containing polyether modified hydroxyl group (manufactured by BYK Japan KK, trade name: BYK-377) was changed to polyether modified polymethylalkyl decane (b3) (BYK) A release film was obtained in the same manner as in Example 1 except that the product was manufactured by Japan KK, trade name: BYK-325.

[Example 10]

Polydimethyl methoxy oxane (b1) containing polyether modified hydroxyl group (manufactured by BYK Japan KK, trade name: BYK-377) was changed to polydimethyl methacrylate containing polyether modified acrylic group (b4) A release film was obtained in the same manner as in Example 1 except that (manufactured by BYK Japan KK, trade name: BYK-UV3500).

[Comparative Example 1]

The imine-type methylated melamine resin (a1) (manufactured by NIPPON CARBIDE INDUSTRIES CO., INC., trade name: MX-730, weight average molecular weight 1508) was changed to a perether methylated melamine resin (a3) ( A release film was obtained in the same manner as in Example 2 except that the product name: MW-30, weight average molecular weight: 608, molecular weight distribution (Mw/Mn): 1.01, manufactured by NIPPON CARBIDE INDUSTRIES CO., INC., was used.

[Comparative Example 2]

The imine-type methylated melamine resin (a1) (manufactured by NIPPON CARBIDE INDUSTRIES CO., INC., trade name: MX-730, weight average molecular weight 1508) was changed to a perether methylated melamine resin (a4) ( A release film was obtained in the same manner as in Example 2 except that the product name: L-105-60, weight average molecular weight 684, molecular weight distribution (Mw/Mn) 1.52, manufactured by DIC Corporation.

[Test Example 1] (Measurement of total acid value)

The melamine resin used in the examples and the comparative examples was diluted with isopropyl alcohol so that the solid content concentration became 50% by mass. 10 g of this dilution was collected in a 200 mL beaker. On the other hand, 125 mL of a solution of toluene, pure water, and 2-propanol was mixed at a mass ratio of 500:5:495 to obtain a measurement sample. In addition, when each of the melamine resins used in the examples and the comparative examples is a solvent other than isopropyl alcohol as a solvent, the solvent is removed to remove the solvent, and then diluted with isopropyl alcohol to set the solid content concentration. 50% by mass.

The measurement sample was subjected to titration based on a potassium hydroxide standard 2-propanol solution using a potentiometric auto-titration device (manufactured by KYOTO ELECTRONICS MANUFACTURING CO., LTD., product name: AT-610 EBU-610-20B), and was measured. The amount of potassium hydroxide standard 2-propanol solution required for the time. The measurement was performed 3 times, and the average value was calculated. From the average value, the amount (mg) of potassium hydroxide required for neutralizing 1 g of the melamine resin was calculated as the total acid value (mgKOH/g). The results are shown in Table 1.

[Test Example 2] (Measurement of curl amount)

The release film produced by the examples and the comparative examples was cut into a 10 cm angle to obtain a measurement sample. The measurement sample was allowed to stand in a thermostat at 70 ° C for two hours. Thereafter, the measurement sample was placed on a flat glass. If the measurement sample is in a curved state, it is placed such that the convex surface faces the glass. The heights of the glass were measured for the four apexes of the measurement sample, and the total amount was measured as the measured value (mm) of the curl amount. The results are shown in Table 1.

[Test Example 3] (Measurement of peeling force)

100 parts by mass of barium titanate (BaTiO3; manufactured by SAKAI CHEMICAL INDUSTRY CO., LTD., trade name: BT-03), polyvinyl butyral (manufactured by SEKISUI CHEMICAL CO., LTD., trade name: S- LEC B.KBM-2) 10 parts by mass and dioctyl phthalate (manufactured by KANTO CHEMICAL CO., INC., trade name: dioctyl phthalate deer 1), 69 mass added The toluene and 46 parts by mass of ethanol were mixed and dispersed in a ball mill to prepare a ceramic slurry.

In the release film which was stored at room temperature for 48 hours after the production of the examples and the comparative examples, the ceramic slurry was uniformly applied to the release surface of the release agent layer using a coater. Thereafter, it was dried at 80 ° C for 1 minute by a dryer. Thereby, 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.

The release film with the ceramic green sheets was allowed to stand in an atmosphere of 23 ° C and a humidity of 50% for 24 hours. Next, an acrylic adhesive tape (manufactured by NITTO DENKO CORPORATION, trade name: 31B tape) was attached to the side opposite to the release film in the ceramic green sheet, and in this state, a width of 20 mm was cut. This was taken as a measurement sample.

The adhesive tape side of the measurement sample was fixed to a flat plate, and was peeled off from the ceramic green sheet by 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. Stripping the film, The force required for peeling (peeling force; mN/20 mm) was measured. The results are shown in Table 1.

In addition, the ellipsis and the like described in Table 1 are specifically as follows.

[melamine resin]

A1: imine-based methylated melamine resin (manufactured by NIPPON CARBIDE INDUSTRIES CO., INC., trade name: MX-730, weight average molecular weight 1508, molecular weight distribution (Mw/Mn) 1.18)

A2: imine hydroxymethyl type methylated melamine resin (manufactured by NIPPON CARBIDE INDUSTRIES CO., INC., trade name: MS-001, weight average molecular weight 3987, molecular weight distribution (Mw/Mn) 1.51)

A3: perether type methylated melamine resin (manufactured by NIPPON CARBIDE INDUSTRIES CO., INC., trade name: MW-30, weight average molecular weight 608, molecular weight distribution (Mw/Mn) 1.01)

A4: a fully ether type methylated melamine resin (manufactured by DIC CORPORATION, trade name: L-105-60, weight average molecular weight 684, molecular weight distribution (Mw/Mn) 1.52)

[polyorganosiloxane]

B1: Polydimethyl methoxide containing polyether modified hydroxyl group (BYK Japan KK, trade name: BYK-377)

B2: Polydimethyl oxirane containing polyester modified hydroxyl group (BYK Japan KK, trade name: BYK-370)

B3: polyether modified polymethylalkyl decane (BYK Japan KK, trade name: BYK-325)

B4: polyether modified acrylic based polydimethyl siloxane (BYK Japan KK, trade name: BYK-UV3500)

As is clear from Table 1, the occurrence of curl in the release film obtained by the examples was suppressed. Further, when peeling off from the ceramic green sheet, peeling can be performed with an appropriate peeling force. Further, in the release sheet obtained in the examples, it was confirmed that the maximum projection height Rp of the release surface was relatively low, and the smoothness was also excellent.

On the other hand, in the release film obtained by the comparative example, a large curl was generated.

[Industrial availability]

The release film for a ceramic green sheet manufacturing process of the present invention is suitable for forming a ceramic green sheet.

1A‧‧‧Removal film for ceramic green sheet manufacturing process

11‧‧‧Substrate

12‧‧‧ Stripper layer

Claims (9)

A release film for a ceramic green sheet manufacturing process, comprising: a substrate; and a release agent layer disposed on one side of the substrate, wherein the release agent layer is formed of a release agent composition, and the release agent composition comprises: The melamine resin has a total acid value of 0.030 to 0.154 mgKOH/g and a weight average molecular weight of 1000 to 10,000; and a polyorganosiloxane. The release film for a ceramic green sheet manufacturing process according to claim 1, wherein the melamine resin contains a compound represented by the following formula (a) or a multinuclear compound obtained by condensing two or more of the above compounds. body: In the formula, X represents -H, -CH ₂ -OH or -CH ₂ -OR, which may be the same or different, and R represents an alkyl group having 1 to 8 carbon atoms, which may be the same or different, at least An X-system -CH ₂ -OH. The release film for a ceramic green sheet manufacturing process according to claim 1, wherein the polyorganosiloxane has at least one hydroxyl group in one molecule. The release film for a ceramic green sheet manufacturing process according to claim 1, wherein the polyorganosiloxane has at least one organic group selected from the group consisting of a polyester group and a polyether group in one molecule. . The release film for a ceramic green sheet manufacturing process according to claim 1, wherein the polyorganosiloxane has a weight average molecular weight of 1,000 to 300,000. The release film for a ceramic green sheet manufacturing process according to claim 1, wherein the release agent composition further contains an acid catalyst. The release film for a ceramic green sheet manufacturing process according to claim 1, wherein the release agent layer has a thickness of 0.1 to 3 μm. The release film for a ceramic green sheet manufacturing process according to claim 1, further comprising a resin layer between the substrate and the release agent layer. The release film for a ceramic green sheet manufacturing process according to claim 8, wherein the resin layer is formed of a composition containing melamine resin and having a total acid value of 0.030 to 0.154 mgKOH/g. And the weight average molecular weight is 1000~10000.