JP6619200B2 - Release film for ceramic green sheet manufacturing process - Google Patents

Description

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

  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 molded, 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. As the release film, a film substrate having a silicone compound such as polysiloxane released is used (Patent Documents 1 to 9). The peelable film is required to have a peelability capable of peeling a thin ceramic green sheet molded on the peelable film without breaking the peelable film.

  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.

JP 2002-011710 A JP 2004-182836 A JP 2004-216613 A JP 2008-254207 A JP 2008-150515 A JP 2009-034947 A JP 2009-215428 A JP 2009-227976 A JP 2009-227777 A

  When the thickness of the ceramic green sheet is reduced to 3 μm or less after drying, when the ceramic slurry is applied and dried, both ends of the coated surface of the ceramic slurry shrink toward the center in the width direction. Edge shrinkage that increases the thickness of both ends of the work surface is likely to occur. In addition, when the molded ceramic green sheet is peeled from the release film, problems such as breakage due to a decrease in strength of the ceramic green sheet are likely to occur, and the yield of the multilayer ceramic capacitor is reduced.

  In addition, electronic materials using ceramic green sheets differ in materials such as inorganic substances, binder resins, dispersants, organic solvents, etc., depending on the intended use, and the coating properties of the ceramic slurry on the release film depend on the type of ceramic slurry. Change. Therefore, it has been difficult for the release film to achieve both the coating performance of the ceramic slurry and the release performance of the ceramic green sheet.

  The present invention has been made in view of such a situation, and can suppress the occurrence of edge shrinkage in the ceramic green sheet, that is, it is excellent in the coating property of the ceramic slurry and the peelability of the ceramic green sheet. It is an object of the present invention to provide a release film for a ceramic green sheet manufacturing process excellent in the above.

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, wherein The adhesion energy of the surface of the release agent layer when measuring the sliding angle using 0 μl droplets is 4.4 to 8.0 mJ / m ² , and the storage elastic modulus at 23 ° C. of the release agent layer is 1. Provided is a release film for a ceramic green sheet manufacturing process characterized by being 6 GPa or more (Invention 1).

  According to the said invention (invention 1), when ceramic slurry is applied to the surface of the release agent layer and dried, the shrinkage of the coating width decreases, and the edge shrinkage increases in the thickness of both ends of the coated surface. Is suppressed. Accordingly, the coating property of the ceramic slurry is excellent, and the step due to the increase in the thickness of the end portion is small, so that the wound ceramic green sheet is not deformed or broken. In addition, the ceramic green sheet has excellent peelability, and therefore, when the ceramic green sheet is peeled off, the ceramic green sheet can be peeled off from the release agent layer with low peeling force without causing defects such as cracks and breakage. In addition, the yield in manufacturing the ceramic green sheet is improved.

  In the above invention (Invention 1), the release agent layer has a polyorganosiloxane (A) having at least two alkenyl groups in one molecule and at least one alkenyl group in a side chain, and one molecule. The polyorganosiloxane (B) having an alkenyl group or a hydroxyl group only at both ends therein, and the polyorganosiloxane (A) and the polyorganosiloxane (B) in a total of 100 parts by mass, It is preferable that the organosiloxane (B) is formed from a release agent composition having a solid content ratio of 1.2 to 19 parts by mass (Invention 2).

  In the said invention (invention 2), it is preferable that the weight average molecular weights of the said polyorganosiloxane (A) are 50,000-1,000,000 (invention 3).

  In the said invention (invention 2 and 3), it is preferable that the weight average molecular weights of the said polyorganosiloxane (B) are 100,000-1200,000 (invention 4).

  In the above inventions (Inventions 2 to 4), the release agent composition further contains a crosslinking agent (C) having a hydrosilyl group, and the content of the crosslinking agent (C) in the release agent composition is In such an amount that the number of hydrosilyl groups in the cross-linking agent (C) is 1.1 to 5.0 in terms of molar ratio relative to the number of alkenyl groups in the organosiloxane (A) and the polyorganosiloxane (B). It is preferable (Invention 5).

  In the said invention (invention 2-5), it is preferable that the said peeling agent composition further contains a platinum group metal type compound as a catalyst (D) (invention 6).

  According to the release film for a ceramic green sheet manufacturing process according to the present invention, the occurrence of edge shrinkage in the ceramic green sheet can be suppressed, and thus the coating property of the ceramic slurry is excellent. Moreover, the release film for a ceramic green sheet manufacturing process according to the present invention is also excellent in the peelability of the ceramic green sheet.

It is sectional drawing of the peeling film for ceramic green sheet manufacturing processes which concerns on one Embodiment of this invention. It is a figure explaining how to obtain the adhesion energy.

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 a ceramic green sheet manufacturing process according to the present embodiment (hereinafter sometimes simply referred to as “release film 1”) includes a base 11 and one surface of the base 11 ( The release agent layer 12 is laminated on the upper surface in FIG.

1. Physical properties The release film 1 according to the present embodiment has a surface of the release agent layer 12 (surface opposite to the surface on the substrate 11 side) when the sliding angle is measured using 7.0 μl of water droplets. Is an adhesive energy of 4.4 to 8.0 mJ / m ² , and the release elastic layer 12 has a storage elastic modulus at 23 ° C. of 1.6 GPa or more. The method for measuring the storage elastic modulus is as shown in the test examples described later.

Here, with reference to FIG. 2, how to obtain the adhesion energy will be described.
The release film 1 is fixed on the flat glass substrate 2, the inclination of the glass substrate 2 is set to 0 degree, and 7.0 μl of the water droplet 3 is dropped on the surface of the release agent layer 12 of the release film 1. 3 seconds after the droplet 3 is stationary, the glass substrate 2 is tilted at a speed of 0.5 degrees / second, and when the droplet 3 leaves the stationary position, the sliding angle α and the landing radius of the droplet 3 are as follows. From r, the droplet mass m and the gravitational acceleration g, the adhesion energy E (mJ / m ² ) is obtained by the following equation.
Adhesion energy: E = mg sin α / 2πr
α: Sliding angle (°)
r: Liquid landing radius (m)
m: Droplet mass (kg)
g: Gravity acceleration (m / s ² )

  According to the release film 1 satisfying the above physical properties, when the ceramic slurry is applied to the surface of the release agent layer 12 and dried, the shrinkage rate of the coating width is reduced, and the thickness of both ends of the coated surface is increased. Generation | occurrence | production of edge part shrinkage | contraction is suppressed. Accordingly, the coating property of the ceramic slurry is excellent, and the step due to the increase in the thickness of the end portion is small, so that the wound ceramic green sheet is not deformed or broken. In addition, the ceramic green sheet is excellent in releasability, and therefore, the ceramic green sheet can be peeled off from the release agent layer 12 with a low peeling force without causing defects such as cracks and breakage when the ceramic green sheet is peeled off. And the yield in the production of ceramic green sheets is improved.

  The excellent coating property of the ceramic slurry is mainly attributed to the adhesion energy, and the excellent peelability of the ceramic green sheet is considered to be attributable to the storage elastic modulus and the adhesion energy. The elastic modulus is also considered to have an influence on the coating properties of the ceramic slurry. That is, it is considered that the above two excellent effects are exhibited by the interaction of both physical properties.

The adhesion energy of the release film 1 according to this embodiment is 4.4 to 8.0 mJ / m ^{2 as} described above, and preferably 5.0 to 7.8 mJ / m ² . When the adhesion energy is less than 4.4 mJ / m ² , the contraction rate of the coating width is large, and the end shrinkage of the ceramic green sheet occurs. On the other hand, when the adhesion energy exceeds 8.0 mJ / m ² , the peelability of the ceramic green sheet is deteriorated.

  Moreover, the storage elastic modulus in 23 degreeC of the releasing agent layer 12 in the peeling film 1 which concerns on this embodiment is 1.6 GPa or more as mentioned above, Preferably it is 1.75-7 GPa. When the storage elastic modulus is less than 1.6 GPa, the release agent layer 12 becomes too soft and the peelability of the ceramic green sheet is deteriorated. On the other hand, if the storage elastic modulus is 7 GPa or less, the coating property when the release agent layer 12 is applied to the substrate 11 is improved, and the release film 1 can be handled roll-to-roll. It is possible to suppress the release agent layer 12 from being cracked.

2. Base Material The base material 11 of the release film 1 according to the present embodiment 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 side 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 according to the type of the base film, but generally, the corona discharge treatment method is preferably used from the viewpoints of effects and operability.

  The thickness of the base material 11 should just be 10-300 micrometers normally, Preferably it is 15-200 micrometers, Especially preferably, it is 20-125 micrometers.

3. Release Agent Layer The material constituting the release agent layer 12 of the release film 1 according to this embodiment may be any material having the above-described physical properties, but the release agent composition shown below (hereinafter referred to as “release agent composition”). According to R), the release agent layer 12 that satisfies the above-described physical properties can be formed. Therefore, the release agent layer 12 in this embodiment is preferably formed from the release agent composition R.

  The release agent composition R is preferably a polyorganosiloxane (A) having at least two alkenyl groups in one molecule and having at least one alkenyl group in the side chain, and both ends in one molecule. Only the polyorganosiloxane (B) having an alkenyl group or a hydroxyl group, and the polyorganosiloxane (B) is solid with respect to a total of 100 parts by mass of the polyorganosiloxane (A) and the polyorganosiloxane (B). The fraction is 1.2 to 19 parts by mass.

  The polyorganosiloxane (A) has at least two alkenyl groups in one molecule and has at least one alkenyl group in the side chain, so that it has a high curing speed and a crosslinked structure having a high crosslinking density. Form. On the other hand, polyorganosiloxane (B) forms a crosslinked structure having a low crosslinking density by having an alkenyl group or a hydroxyl group only at both ends in one molecule.

In the release agent composition R, the polyorganosiloxane (A) contains more alkenyl groups having higher polarity than the polyorganosiloxane (B). When the release agent composition R is applied to the substrate 11, the highly polar polyorganosiloxane (A) is segregated in the vicinity of the substrate 11, and the less polar polyorganosiloxane (B) is far from the substrate 11 ( Segregates on the surface of the coating solution. As described above, since the polyorganosiloxane (B) forms a crosslinked structure having a low crosslinking density, the surface of the release agent layer 12 to be formed is formed from a crosslinked structure having a low crosslinking density. The energy is 4.4 to 8.0 mJ / m ² . On the other hand, since the part other than the surface layer of the release agent layer 12 to be formed is formed from a crosslinked structure having a high crosslinking density, the release agent layer 12 as a whole has a certain degree of hardness. The elastic modulus is 1.6 GPa or more.

The polyorganosiloxane (A) is a polymer of a silicon-containing compound represented by the following general formula (a).

In formula (a), m and n are each an integer of 1 or more. R ¹ and R ² are each an alkyl group having 1 to 12 carbon atoms and must not be an alkenyl group. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and an octyl group.

R ³ is an alkenyl group, and R ⁴ is an alkyl group or alkenyl group having 1 to 12 carbon atoms. Examples of the alkenyl group include vinyl group, allyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group and the like.

R ¹ , R ² and R ⁴ may be the same or different. R ¹ , R ² and R ⁴ are preferably methyl groups.

When n in the formula (a) is 1, at least one of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ is an alkenyl group, and the rest are each an alkyl group having 1 to 12 carbon atoms. Or it is preferable that it is a hydroxyl group. When n in the formula (a) is 2 or more, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may each be an alkyl group, alkenyl group or hydroxyl group having 1 to 12 carbon atoms. preferable. From the viewpoint that segregation is likely to occur, it is preferable that the polyorganosiloxane (A) has two or more alkenyl groups only in the side chain and does not have an alkenyl group at the terminal. That is, it is preferable that n is 2 or more, and R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each an alkyl group having 1 to 12 carbon atoms or a hydroxyl group. In addition, since the hydroxyl group has relatively low reactivity with the alkenyl group present in the side chain, it is considered that the influence exerted on the above-mentioned segregation and the crosslinking reaction by the crosslinking agent described later is very small. Usually, the number of hydroxyl groups in R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ is 2 or less, and in the case of 2 there is one hydroxyl group at each end. Preferably it is present.

  The polyorganosiloxane (A) preferably contains 0.05 to 1.0 mmol of alkenyl groups in 1 g of the polyorganosiloxane (A), particularly preferably 0.075 to 0.75 mmol, and more preferably 0 It is preferable to contain 1-0.5 mmol. When the number of alkenyl groups is 2 or more per molecule and 1 or more in the side chain, and the amount of alkenyl groups is in the above range, the polyorganosiloxane (B) is removed from the release agent layer 12. It is easy to segregate on the surface layer and a crosslinked structure having a high crosslinking density can be formed. In particular, when the amount of alkenyl group contained in 1 g of polyorganosiloxane (A) is 0.05 mmol or more, after curing, the crosslink density in the vicinity of the substrate 11 of the release agent layer 12 is increased, and the storage elastic modulus is increased. Is sufficiently high, the peeling force when peeling the ceramic green sheet is further reduced. Further, since the amount of alkenyl group contained in 1 g of polyorganosiloxane (A) is 1.0 mmol or less, the release agent composition R is subjected to a crosslinking reaction before the release agent composition R is applied to the substrate 11. Thus, gelation is sufficiently prevented.

  The weight average molecular weight of the polyorganosiloxane (A) is preferably 50,000 to 1,000,000, particularly preferably 100,000 to 800,000, and more preferably 150,000 to 600,000. Preferably there is. 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.

  When the weight average molecular weight of the polyorganosiloxane (A) is in the above range, a crosslinked structure having a high crosslinking density is formed in the release agent layer, and the storage elastic modulus on the surface of the release agent layer is increased. can do. Further, when the weight average molecular weight of the polyorganosiloxane (A) is 50,000 or more, it is possible to prevent the coating viscosity of the release agent composition R from becoming too low, suppress the occurrence of repellency, and achieve a uniform surface state. The release agent layer 12 can be obtained. When the weight average molecular weight of the polyorganosiloxane (A) is 1,000,000 or less, an increase in coating viscosity of the release agent composition R can be suppressed, and solubility in a diluting solvent can be ensured.

On the other hand, the polyorganosiloxane (B) is a polymer of a silicon-containing compound represented by the following general formula (b).

In formula (b), p is an integer of 1 or more. R ¹¹ and R ¹² are alkyl groups having 1 to 12 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, and the like, and must not be an alkenyl group. . R ¹¹ and R ¹² may be the same or different. R ¹¹ and R ¹² are preferably a methyl group.

In the formula (b), at least one of R ¹³ , R ¹⁴ and R ¹⁵ is an alkenyl group or a hydroxyl group, and at least one of R ¹⁶ , R ¹⁷ and R ¹⁸ is an alkenyl group or a hydroxyl group. That is, polyorganosiloxane (B) has an alkenyl group or a hydroxyl group at both ends. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, and an octenyl group. Among them, a vinyl group is particularly preferable. The functional group other than the alkenyl group in R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ is an alkyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group. , A pentyl group, a hexyl group, an octyl group, and the like, preferably a methyl group. The alkyl groups in R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ may be the same or different.

  The release agent composition R may contain different types of polyorganosiloxane (B) at the same time, for example, polyorganosiloxane (B) having alkenyl groups at both ends and polyorganosiloxane having hydroxyl groups at both ends. (B) may be contained at the same time.

  The polyorganosiloxane (B) preferably contains 0.00005 to 0.05 mmol of alkenyl group or hydroxyl group in 1 g of polyorganosiloxane (B), particularly preferably 0.00008 to 0.03 mmol. Is preferably contained in an amount of 0.0001 to 0.01 mmol. The polyorganosiloxane (B) segregates on the surface layer of the release agent layer 12 because the alkenyl group or hydroxyl group exists only at both ends in one molecule and the amount of the alkenyl group or hydroxyl group is in the above range. It is easy to form a crosslinked structure having a low crosslinking density only near the surface layer. In particular, when the amount of alkenyl group or hydroxyl group contained in 1 g of polyorganosiloxane (B) is 0.00005 mmol or more, the reactivity of polyorganosiloxane (B) increases, and polyorganosiloxane (B) is ceramic. Transfer to the green sheet can be effectively prevented. Further, when the amount of alkenyl group or hydroxyl group contained in 1 g of polyorganosiloxane (B) is 0.05 mmol or less, the polarity of polyorganosiloxane (B) is lowered, and polyorganosiloxane (B) is peeled off. The surface layer of the agent layer 12 is easily segregated.

  The weight average molecular weight of the polyorganosiloxane (B) is preferably 100,000 to 1,200,000, particularly preferably 150,000 to 900,000, and more preferably 200,000 to 600,000. Preferably there is.

  When the weight average molecular weight of the polyorganosiloxane (B) is in the above range, a crosslinked structure having a low crosslinking density is formed in the release agent layer. Further, when the weight average molecular weight of the polyorganosiloxane (B) is 100,000 or more, the crosslink density of the polyorganosiloxane (B) is decreased, and the adhesion energy can be increased. When the weight average molecular weight of the polyorganosiloxane (B) is 1,200,000 or less, the curability of the release agent composition R can be maintained well, and the amount of silicone transferred to the ceramic green sheet can be reduced.

In the release agent composition R, the polyorganosiloxane (B) has a solid content ratio of 1.2 to 19 parts by mass with respect to a total of 100 parts by mass of the polyorganosiloxane (A) and the polyorganosiloxane (B). It is preferable that it is 3.0-17 mass parts, and it is especially preferable that it is 5-15 mass parts. When the solid component ratio of the polyorganosiloxane (B) that forms a crosslinked structure having a low crosslinking density is 19 parts by mass or less, the release agent layer 12 has a certain degree of hardness as a whole. The storage elastic modulus is 1.6 GPa or more. Moreover, when the solid component ratio of the polyorganosiloxane (B) is 1.2 parts by mass or more, the content of the polyorganosiloxane (B) on the surface of the release agent layer 12 can be secured, and the above adhesion The energy is 4.4 to 8.0 mJ / m ² .

  It is preferable that the release agent composition R further contains a crosslinking agent (C). The cross-linking agent (C) is not particularly limited as long as it has a cross-linkable functional group capable of cross-linking the polyorganosiloxane (A) and the polyorganosiloxane (B). The crosslinking agent (C) having a hydrogen atom (hydrosilyl group) bonded to a silicon atom as a crosslinkable functional group is preferred. Since the release agent composition R contains the crosslinking agent (C), the polyorganosiloxane (A) and the polyorganosiloxane (B) are crosslinked, and more stable release property is imparted to the resulting release agent layer 12. The

  The crosslinking agent (C) having a hydrosilyl group is preferably a polyorganosiloxane having at least two hydrosilyl groups in one molecule other than the polyorganosiloxane (A) and the polyorganosiloxane (B). Examples of the polyorganosiloxane include dimethylhydrogensiloxy group end-capped dimethylsiloxane-methylhydrogensiloxane copolymer, trimethylsiloxy group end-capped dimethylsiloxane-methylhydrogensiloxane copolymer, trimethylsiloxy group end-capped methylhydrol. Examples include polyorganohydrogensiloxanes such as genpolysiloxane and poly (hydrogensilsesquioxane). Among them, a trimethylsiloxy group end-capped dimethylsiloxane-methylhydrogensiloxane copolymer having excellent effects is preferable.

  Between the hydrosilyl group of the crosslinking agent (C) and the alkenyl group of the polyorganosiloxane (A) and the polyorganosiloxane (B), the carbon-carbon double bond of the alkenyl group is opened, and one of the carbon atoms is bonded to the hydrosilyl group. A reaction occurs in which the silicon atom of the group is covalently bonded. On the other hand, between the hydrosilyl group of the crosslinking agent (C) and the hydroxyl group of the polyorganosiloxane (B), hydrogens of these groups are dehydrogenated, and the silicon atom of the hydrosilyl group and the oxygen atom of the hydroxyl group are shared. The reaction of binding occurs. By the above reaction, crosslinking occurs between the polyorganosiloxane (A) and the polyorganosiloxane (B), between the polyorganosiloxane (A) and between the polyorganosiloxane (B).

  The weight average molecular weight of the polyorganosiloxane as the crosslinking agent (C) is preferably 100 to 10,000, and particularly preferably 500 to 5,000.

  The content of the crosslinking agent (C) in the release agent composition R according to this embodiment is such that the crosslinking agent (C) is the number of alkenyl groups of the polyorganosiloxane (A) and the polyorganosiloxane (B). The number of crosslinkable functional groups such as hydrosilyl groups possessed by is preferably an amount that is 1.1 to 5.0 in terms of molar ratio, and is particularly preferably an amount that is 1.75 to 4.5, Furthermore, it is preferable that it is the quantity used as 2.0-4.0.

  The release agent composition R preferably further contains a catalyst (D) and the like. The catalyst (D) is not particularly limited as long as it can cure the release agent composition R, and among them, a platinum group metal compound is preferable. Examples of the platinum group metal compounds include fine platinum, fine platinum adsorbed on a carbon powder carrier, chloroplatinic acid, alcohol-modified chloroplatinic acid, olefin complexes of chloroplatinic acid, palladium, rhodium and the like. . When the release agent composition R contains such a catalyst (D), the curing reaction of the release agent composition R can proceed more efficiently.

  The content of the catalyst (D) in the release agent composition R according to this embodiment is preferably about 1 to 1000 ppm with respect to the total amount of components other than the catalyst (D).

  The release agent composition R according to this embodiment may contain a reaction inhibitor, an adhesion improver, and the like in addition to the above components.

  The thickness of the release agent layer 12 is preferably 0.01 to 3 μm, and particularly preferably 0.03 to 1 μm. When the thickness of the release agent layer 12 is 0.01 μm or more, the function as a release agent layer can be exhibited, and a structure in which the cured polyorganosiloxane (B) is segregated on the surface layer can be formed. it can. On the other hand, if the thickness of the release agent layer 12 is 3 μm or less, blocking can be prevented from occurring when the release film 1 is rolled up.

4. Manufacturing method of release film for ceramic green sheet manufacturing process The release film 1 according to this embodiment is applied to one surface of a substrate 11 with a release agent composition R and a coating solution containing an organic solvent as required. After being worked, it is obtained by drying and curing to form the release agent layer 12. As the coating method, for example, gravure coating method, bar coating method, spray coating method, spin coating method, knife coating method, roll coating method, die coating method and the like can be used.

  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, acetone, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and mixtures thereof are used.

  The release agent composition R applied as described above is preferably thermoset. In this case, the heating temperature is preferably 90 to 140 ° C., and the heating time is preferably about 10 to 120 seconds. Moreover, you may accelerate | stimulate hardening of release agent composition R by irradiating an ultraviolet-ray as needed.

  In order to use the release film 1 described above, a ceramic green sheet is formed by applying a ceramic slurry to the surface of the release agent layer 12 and drying using a slot die coating method, a doctor blade method, or the like. To do. At this time, in the release film 1 according to this embodiment, the coating width of the ceramic slurry is contracted, and the occurrence of end contraction in which the thickness of both ends of the coating surface is increased is suppressed.

  Specifically, the dimension with which the coating width shrinks is preferably less than 5 mm, and particularly preferably 2 mm or less.

  On the other hand, even when a thin ceramic green sheet with low strength is molded into the release agent layer, it does not cause defects such as cracks and breakage, and has a low peel force, specifically a peel force of 15.5 mN / 50 mm or less. The ceramic green sheet can be peeled from the release agent layer 12. Thus, according to the peeling film 1 which concerns on this embodiment, while being excellent in the coating property of a ceramic slurry, it is excellent also in the peeling property of a ceramic green sheet, and the yield in ceramic green sheet manufacture improves.

  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]
The polyorganosiloxane (A) is a polyorganosiloxane (weight average molecular weight: 390,000, 1 g of polyorganosiloxane) that has two or more hexenyl groups only in the side chain and the portion that does not have a hexenyl group is a methyl group. And polyorganosiloxane (B) having one vinyl group only at both ends and the other functional groups being methyl groups. Organosiloxane (weight average molecular weight: 350,000, alkenyl group amount in 1 g of polyorganosiloxane: 0.0003 mmol; hereinafter referred to as “material B1”), and trimethylsiloxy group end-capped dimethylsiloxane-methyl as a crosslinking agent (C) Mixed with hydrogen siloxane copolymer (weight average molecular weight: 1,000). To obtain an addition reaction type polyorganosiloxane solution. At this time, the blending ratio (mass basis) of the material A1 and the material B1 was 83.3: 16.7. Moreover, content of a crosslinking agent (C) contains a crosslinking agent (C) with respect to the total number of the hexenyl group which a polyorganosiloxane (A) contains, and the vinyl group which a polyorganosiloxane (B) contains. The amount of hydrosilyl groups was 2.5 so that the molar ratio was 2.5.

  In this addition reaction type polyorganosiloxane solution, the solid content ratio of the material B1 to the total of 100 parts by mass of the material A1 and the material B1 was 16.7 parts by mass.

  Next, a platinum-based catalyst (manufactured by Dow Corning Toray, SRX-212) was added to and mixed with the addition reaction type polyorganosiloxane solution to obtain a solution (coating solution) of a release agent composition. The content of the platinum-based catalyst was 10 parts by mass with respect to 100 parts by mass of the addition reaction type polyorganosiloxane solution.

  A coating solution of the obtained release agent composition was used as a biaxially stretched polyethylene terephthalate film (thickness: 31 μm, width: 300 mm, arithmetic mean surface roughness Ra: 15 nm on both sides, maximum projection height Rp on both sides) : 84 nm) was uniformly applied by a bar coater. Subsequently, it heat-dried at 135 degreeC for 60 second, the release agent composition was hardened, and the laminated body by which the 0.07 micrometer-thick release agent layer was laminated | stacked on the base material was obtained. Thereafter, in order to eliminate the influence of the remaining functional group of the polyorganohydrogensiloxane, which is a crosslinking agent for the silicone release agent, the laminate was stored for 24 hours under 50 ° C./dry condition to obtain a release film. .

[Example 2]
A release film in the same manner as in Example 1 except that the addition reaction type polyorganosiloxane solution was mixed so that the blending ratio (mass basis) of the material A1 and the material B1 was 96.7: 3.3. Was made.

  In this addition reaction type polyorganosiloxane solution, the solid content ratio of the material B1 to the total of 100 parts by mass of the material A1 and the material B1 was 3.3 parts by mass.

Example 3
A release film in the same manner as in Example 1 except that the addition reaction type polyorganosiloxane solution was mixed so that the blending ratio (mass basis) of the material A1 and the material B1 was 98.3: 1.7. Was made.

  In the addition reaction type polyorganosiloxane solution, the solid content ratio of the material B1 to the total of 100 parts by mass of the material A1 and the material B1 was 1.7 parts by mass.

Example 4
Polyorganosiloxane (A) as material A1 and polyorganosiloxane (B) as polyorganosiloxane (B) having no alkenyl groups, one hydroxyl group only at both ends, and other functional groups being methyl groups Siloxane (weight average molecular weight: 400,000, hydroxyl group content in 1 g of polyorganosiloxane: 0.0002 mmol; hereinafter referred to as “material B2”), and trimethylsiloxy group end-capped dimethylsiloxane-methylhydrogen as a crosslinking agent (C) A siloxane copolymer (weight average molecular weight: 1,000) was mixed to obtain a polyorganosiloxane solution. At this time, the blending ratio (mass basis) of the material A1 and the material B2 was 83.3: 16.7. Moreover, content of a crosslinking agent (C) contains a crosslinking agent (C) with respect to the total number of the hexenyl group which a polyorganosiloxane (A) contains, and the vinyl group which a polyorganosiloxane (B) contains. The amount of hydrosilyl groups was 2.5 so that the molar ratio was 2.5.

  In this polyorganosiloxane solution, the solid content ratio of the material B2 to 100 parts by mass in total of the parts by mass of the material A1 and the material B2 was 16.7 parts by mass.

  Next, a platinum-based catalyst (manufactured by Dow Corning Toray, SRX-212) was added to and mixed with the polyorganosiloxane solution to obtain a release agent composition solution (coating solution). The content of the platinum-based catalyst was 10 parts by mass with respect to 100 parts by mass of the polyorganosiloxane solution.

  A release film was produced in the same manner as in Example 1 except that the coating solution of the release agent composition thus obtained was used.

Example 5
A release film was produced in the same manner as in Example 4 except that a polyorganosiloxane solution was used so that the mixing ratio (mass basis) of the material A1 and the material B2 was 96.7: 3.3. .

  In this polyorganosiloxane solution, the solid content ratio of the material B2 to the total of 100 parts by mass of the material A1 and the material B2 was 3.3 parts by mass.

Example 6
A release film was prepared in the same manner as in Example 4 except that a polyorganosiloxane solution was used so that the blending ratio (mass basis) of the material A1 and the material B2 was 98.3: 1.7. .

  In this polyorganosiloxane solution, the solid content ratio of the material B2 to the total of 100 parts by mass of the parts by mass of the material A1 and the material B2 was 1.7 parts by mass.

[Comparative Example 1]
A release film was prepared in the same manner as in Example 1 except that the addition reaction type polyorganosiloxane was mixed so that the blending ratio (mass basis) of the material A1 and the material B1 was 80.0: 20.0. Produced.

  In this addition reaction type polyorganosiloxane solution, the solid content ratio of the material B to the total of 100 parts by mass of the parts by mass of the material A1 and the material B1 was 20.0 parts by mass.

[Comparative Example 2]
A release film was prepared in the same manner as in Example 1 except that the addition reaction type polyorganosiloxane was mixed so that the blending ratio (mass basis) of the material A1 and the material B1 was 99.2: 0.8. Produced.

  In this addition reaction type polyorganosiloxane solution, the solid content ratio of the material B to the total of 100 parts by mass of the parts by mass of the material A1 and the material B1 was 0.8 part by mass.

[Comparative Example 3]
A release film was produced in the same manner as in Example 1 except that only the material A1 was used as the addition reaction type polyorganosiloxane.

[Comparative Example 4]
A release film was prepared in the same manner as in Example 4 except that the addition reaction type polyorganosiloxane was mixed so that the blending ratio (mass basis) of the material A1 and the material B2 was 80.0: 20.0. Produced.

  In this addition reaction type polyorganosiloxane solution, the solid content ratio of the material B2 to the total of 100 parts by mass of the material A1 and the material B2 was 20.0 parts by mass.

[Comparative Example 5]
A release film was prepared in the same manner as in Example 4 except that the addition reaction type polyorganosiloxane was mixed so that the blending ratio (mass basis) of the material A1 and the material B2 was 99.2: 0.8. Produced.

  In this addition reaction type polyorganosiloxane solution, the solid content ratio of the material B2 to the total of 100 parts by mass of the material A1 and the material B2 was 0.8 part by mass.

[Test Example 1] (Measurement of adhesion energy)
The adhesion energy on the surface of the release agent layer in the release films obtained in Examples and Comparative Examples was measured using a fully automatic contact angle meter DM-701 manufactured by Kyowa Interface Science Co., Ltd. Specifically, in an environment of a temperature of 23 degrees and a humidity of 50%, the release film is stopped on a flat glass substrate, and the tilt of the glass substrate is set to 0 degree, and 7.0 μl of water droplets are applied to the release film. 3 seconds after the droplet dropped on the surface of the release agent layer and the droplet stopped, the glass substrate was tilted at a speed of 0.5 degrees / second, and the droplet end point was separated from the rest position. The adhesion energy (mJ / m ² ) was determined from the sliding angle, landing radius, droplet mass and gravitational acceleration. The results are shown in Table 1.

[Test Example 2] (Storage elastic modulus measurement)
The release films obtained in Examples and Comparative Examples were cut to a size of 10 mm × 10 mm, and then the substrate back surface of the cut release film was coated with a two-component epoxy adhesive on a glass plate adhered to an aluminum base. Fixed. Then, using a micro hardness evaluation apparatus (manufactured by MTS, Nano Indenter SA2), a nanoindentation test was performed at a maximum indentation depth of 200 nm, a strain rate of 0.05 sec ⁻¹ , a displacement amplitude of 2 nm, and a vibration frequency of 45 Hz The storage elastic modulus (GPa) of the release agent layer of the release film was measured. The results are shown in Table 1.

[Test Example 3] (Slurry coating property evaluation (end part shrinkage evaluation))
100 parts by mass of barium titanate (BaTiO ₃ ; manufactured by Sakai Chemical Industry Co., Ltd., BT-03), 8 parts by mass of polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd., ESREC B · KBM-2) and dioctyl phthalate (manufactured by Kanto Chemical Co., Inc.) , Dioctyl phthalate, deer grade 1) To 135 parts by mass of a mixed solution of toluene and ethanol (mass ratio 6: 4) was added to 4 parts by mass, and the mixture was mixed and dispersed in a ball mill to prepare a ceramic slurry.

  A die coater (width) is formed on the surface of the release agent layer of a release film (width: 300 mm) that has been manufactured in Examples and Comparative Examples and stored at room temperature for 48 hours so that the film thickness after drying the ceramic slurry becomes 3 μm. : 250 mm), and then dried at 80 ° C. for 1 minute in a dryer. In this way, a 300 m release film roll with a ceramic green sheet was produced.

In the obtained release film with a ceramic green sheet, the edge shrinkage width was calculated using the following formula, and the slurry coatability (edge shrinkability) was evaluated based on the calculated edge shrinkage width. The results are shown in Table 1.
Edge shrinkage width = (Ceramic slurry coating width = 250 mm) − (Width of formed ceramic green sheet)
○: End shrinkage width is less than 2 mm (slurry coating property is good)
Δ: End shrinkage width is 2 mm or more and less than 5 mm (can be used)
X: Edge shrinkage width is 5 mm or more (slurry coating property is poor)

[Test Example 4] (Peeling force measurement)
A release film with a ceramic green sheet obtained in the same manner as in Test Example 3 was allowed to stand for 24 hours in an atmosphere having a room temperature of 23 degrees and a humidity of 50%, and then cut into a size of 100 mm in the flow direction and 50 mm in the width direction. And it was set as the sample for peeling force measurement. An acrylic adhesive tape (manufactured by Nitto Denko Corporation, 31B tape) having a width of 5 mm was attached to one end of the short side of the sample on the ceramic green sheet surface side. The release film surface side of this sample was fixed to a flat plate with a double-sided tape, and the flat plate was horizontally placed on a peel tester (manufactured by Shimadzu Corporation, AG-IS 500N) so that the sample became the upper surface. And the edge part of the ceramic green sheet of the side which stuck the acrylic adhesive tape was peeled off from the peeling film, and the said edge part was attached to the jig | tool of a peeling tester. In this state, the ceramic green sheet was pulled vertically upward (90 ° peeling) at a peeling speed of 200 mm / min, and the peeling force (mN / 50 mm) between the peeling film and the ceramic green sheet was measured. Based on the measurement result of the peeling force, the peelability of the release film was evaluated according to the following criteria. The results are shown in Table 1.
○: Peeling force is 15.5 mN / 50 mm or less (good peelability)
X: Peeling force exceeds 15.5 mN / 50 mm (poor peelability)

  As is apparent from Table 1, the release films obtained in the examples had a small edge shrinkage width of the coated ceramic slurry, and were excellent in the coating property of the ceramic slurry. Moreover, the ceramic green sheet could be peeled with a low peel force, and the peelability of the ceramic green sheet was excellent.

DESCRIPTION OF SYMBOLS 1 ... Release film for ceramic green sheet manufacturing process 11 ... Base material 12 ... Release agent layer 2 ... Glass substrate 3 ... Droplet

Claims (5)

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,
When the sliding angle is measured using a droplet of 7.0 μl of water, the adhesion energy of the surface of the release agent layer is 4.4 to 8.0 mJ / m ² ,
Ri der storage modulus than 1.6GPa at 23 ° C. of the release agent layer,
The release agent layer is
A polyorganosiloxane (A) having at least two alkenyl groups in one molecule and having at least one alkenyl group in the side chain;
A polyorganosiloxane (B) having an alkenyl group or a hydroxyl group only at both ends in one molecule;
Containing
Release agent composition in which the polyorganosiloxane (B) is 1.2 to 19 parts by mass in terms of solid content with respect to 100 parts by mass in total of the parts by mass of the polyorganosiloxane (A) and the polyorganosiloxane (B). A release film for a ceramic green sheet manufacturing process, wherein the release film is formed from a product . The release film for a ceramic green sheet production process according to claim 1 , wherein the polyorganosiloxane (A) has a weight average molecular weight of 50,000 to 1,000,000. The release film for manufacturing a ceramic green sheet according to claim 1 or 2 , wherein the polyorganosiloxane (B) has a weight average molecular weight of 100,000 to 1,200,000. The release agent composition further contains a crosslinking agent (C) having a hydrosilyl group,
The content of the crosslinking agent (C) in the release agent composition is such that the crosslinking agent (C) has hydrosilyl with respect to the number of alkenyl groups that the polyorganosiloxane (A) and the polyorganosiloxane (B) have. The release film for a ceramic green sheet production process according to any one of claims 1 to 3 , wherein the number of groups is an amount of 1.1 to 5.0 in terms of molar ratio. The release agent composition, a release film for producing a ceramic green sheet process according to any one of claims 1 to 4, characterized in that it further contains a platinum-group metal compound as a catalyst (D).

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