WO2016133092A1

WO2016133092A1 - Mold release film

Info

Publication number: WO2016133092A1
Application number: PCT/JP2016/054453
Authority: WO
Inventors: 佐藤　慶一; 知巳深谷
Original assignee: リンテック株式会社
Priority date: 2015-02-18
Filing date: 2016-02-16
Publication date: 2016-08-25
Also published as: JP6678933B2; JPWO2016133092A1; SG11201706672UA; CN107249879A; TWI702145B; KR102675215B1; KR20170118730A; TW201634287A; PH12017501469A1

Abstract

According to the present invention, a mold release film 10A comprises a substrate 11, an antistatic layer 12 provided on one side 11A of the substrate 11 and a mold release layer 13 provided on the antistatic layer 12 or on the other side of the substrate 11, wherein the one side 11A of the substrate 11 has an arithmetical mean roughness R_a of at most 15 nm and a maximum peak height R_p of at most 150 nm and the antistatic layer 12 is formed by curing an aqueous thermosetting resin composition that comprises a polythiophene conductive polymer (A) so that the thickness of the antistatic layer 12 is from 12-250 nm.

Description

Release film

The present invention relates to a release film having an antistatic layer, and more particularly to a process film used in the production process of a multilayer ceramic capacitor.

In recent years, multilayer ceramic capacitors have been reduced in size and weight, and accordingly, the demand for thin ceramic green sheets has been increasing year by year, and green sheets having a thickness of less than 1 μm have been manufactured. Such a thin ceramic green sheet tends to generate pinholes, and even a slight unevenness tends to be a defective product, which tends to reduce the yield. The ceramic green sheet is generally manufactured by applying a ceramic slurry on a release film. However, in order to prevent the formation of the pin poles and irregularities, a release film with high surface smoothness is used. It is getting demanded.
On the other hand, a release film having a high surface smoothness is likely to have problems such as blocking when it is wound into a roll and charging being generated when the roll is unwound. In order to prevent such problems, it is known to add an antistatic agent or the like to the release film to impart an antistatic function.

In recent years, a conductive polymer such as PEDOT-PSS (a mixture of polyethylene dioxythiophene and polystyrene sulfonate) may be used as an antistatic agent used for a release film. For example, as disclosed in Patent Document 1, a release layer of a release film may be formed of a release agent composition composed of a curable silicone emulsion, a curing agent, and PEDOT-PSS.
In addition, the release film may be provided with an antistatic layer separately from the release layer. The antistatic layer is, for example, a resin composition in which a conductive polymer such as PEDOT-PSS is mixed with polyester resin, urethane resin, acrylic resin, or the like (see Patent Document 2), or PEDOT-PSS in a photo-curing coating agent It is known that it is formed of a resin composition (see Patent Document 3) in which a conductive polymer such as is mixed.

JP 2003-251756 A JP 2012-2224011 A JP 2010-6079 A

However, as disclosed in Patent Document 1, when PEDOT-PSS is blended in the release agent composition, the compatibility between the silicone emulsion as the release agent component and PEDOT-PSS is poor, and PEDOT-PSS aggregates to produce coarse protrusions. It is easy to become. Therefore, it becomes difficult to smooth the surface of the release film. Further, even with the resin composition described in Patent Document 3, PEDOT-PSS is likely to aggregate, making it difficult to ensure the surface smoothness of the antistatic layer and the release layer formed on the antistatic layer. Become.
On the other hand, since the resin composition described in Patent Document 2 is a non-crosslinked type, the film strength and the like are not sufficient, and the solvent resistance of the antistatic layer and the overcoat property of the antistatic layer, that is, Problems such as deterioration of the coating properties of the coating solution such as a release layer formed on the antistatic layer are likely to occur.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a release film excellent in antistatic performance, solvent resistance, and overcoatability while smoothing the surface.

As a result of intensive studies, the inventors of the present invention include a polythiophene-based conductive polymer such as PEDOT-PSS, and an aqueous and thermosetting resin composition having a predetermined thickness on a smooth substrate surface. It has been found that the above problems can be solved by forming an antistatic layer, and the following invention has been completed. That is, the present invention provides the following (1) to (9).
(1) A substrate, an antistatic layer provided on one surface of the substrate, and a release layer provided on the antistatic layer or on the other surface side of the substrate. ,
One surface of the substrate has an arithmetic average roughness Ra of 15 nm or less and a maximum protrusion height Rp of 150 nm or less,
A release film in which the antistatic layer is obtained by curing an aqueous thermosetting resin composition containing a polythiophene-based conductive polymer (A), and the antistatic layer has a thickness of 12 to 250 nm.
(2) The release film according to (1), wherein the release layer is provided on the antistatic layer.
(3) The release film according to (1) or (2), wherein the release layer has an arithmetic average roughness Ra of less than 10 nm and a maximum protrusion height Rp of less than 100 nm.
(4) The release film according to any one of (1) to (3), wherein the aqueous thermosetting resin composition further comprises a hydroxyl group-containing polyester resin (B) and a melamine compound (C).
(5) The aqueous thermosetting resin composition comprises 8 to 35 parts by mass of the melamine compound (C) with respect to 100 parts by mass in total of the polythiophene-based conductive polymer (A) and the hydroxyl group-containing polyester resin (B). The release film as described in (4) above.
(6) The above (4), wherein the aqueous thermosetting resin composition contains 0.5 to 50 parts by mass of the polythiophene conductive polymer (A) with respect to 100 parts by mass of the hydroxyl group-containing polyester resin (B). Or the release film as described in (5).
(7) The release film according to any one of (4) to (6), wherein the melamine compound (C) is methylol melamine.
(8) The release film according to any one of (1) to (7), wherein the polythiophene-based conductive polymer (A) is a mixture of polyethylene dioxythiophene and polystyrene sulfonate (PEDOT-PSS).
(9) The release film according to any one of (1) to (8), which is used for a production process of a ceramic green sheet.

In the present invention, it is possible to provide a release film excellent in antistatic performance, solvent resistance, and overcoatability while smoothing the surface.

It is typical sectional drawing which shows one Embodiment of the release film of this invention. It is typical sectional drawing which shows other embodiment of the release film of this invention.

Hereinafter, the present invention will be described in more detail using embodiments.
The release film of the present invention includes a base material, an antistatic layer provided on one surface of the base material, and a release layer provided on the antistatic layer or on the other surface side of the base material. Are provided.
More specifically, as the release film, as shown in FIG. 1, a base material 11, an antistatic layer 12 provided on one surface 11A of the base material 11, and an antistatic layer 12 A release film 10A provided with a release layer 13 provided on the substrate 11 is provided. As shown in FIG. 2, an antistatic layer 12 is provided on one surface 11A of the substrate 11, and the release layer 13 is provided. May be a release film 10 </ b> B provided on the other surface 11 </ b> B of the substrate 11.

The release film wound up in a roll shape causes blocking in some cases, and generates static electricity when the release film is unwound from the roll. The release film has an antistatic layer to prevent such pay-out charging and prevent blocking and lowering of winding property. In addition, when various articles such as a ceramic green sheet laminated on the release layer are peeled from the release film, poor peeling due to charging is less likely to occur. Furthermore, it is possible to prevent dust and the like from adhering to the release layer due to static electricity.
As the release film, as shown in FIG. 1, one in which a release layer 13 is provided on the antistatic layer 12 is preferable. In such a release film, charging on the release layer 13 is further easily prevented by the antistatic layer 12.

Next, each member of the release film will be described in detail.
[Base material]
In the base material, one surface (the surface 11A in FIGS. 1 and 2) on which the antistatic layer is formed has an arithmetic average roughness Ra of 15 nm or less and a maximum protrusion height Rp of 150 nm or less. In the present invention, when the arithmetic average roughness Ra or the maximum protrusion height Rp on one surface of the substrate exceeds these upper limit values, the aqueous thermosetting resin composition described later is a composition for forming an antistatic layer. However, it becomes difficult to smooth the surface of the antistatic layer. If the surface of the antistatic layer cannot be smoothed, for example, when a thin layer such as a release layer is provided on the antistatic layer, the surface of the release layer cannot be smoothed. Concavities and convexities and pinholes are likely to occur in the formed article such as a ceramic green sheet.
From the above viewpoints, the arithmetic average roughness Ra and the maximum protrusion height Rp are preferably 12 nm or less and 120 nm or less, respectively. In consideration of the ease of production of the substrate, the arithmetic average roughness Ra and the maximum protrusion height Rp are each preferably 1 nm or more and 5 nm or more.

The base material is not particularly limited as long as the arithmetic average roughness Ra and the maximum protrusion height Rp are in the above ranges, for example, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polypropylene and polymethylpentene, Examples thereof include films made of plastics such as polycarbonate and polyvinyl acetate, and these may be a single layer or a multilayer of two or more of the same or different types. Among these, a polyester film is preferable, and a polyethylene terephthalate film is particularly 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.
The thickness of the substrate is not particularly limited, and is usually about 10 to 300 μm, preferably about 15 to 200 μm.
In order to secure the arithmetic average roughness Ra and the maximum protrusion height Rp, the base material should not contain particles. However, as long as the arithmetic average roughness Ra and the maximum protrusion height Rp can be ensured, May be contained. In the case of containing particles, in order to reduce the arithmetic average roughness Ra and the maximum protrusion height Rp of the substrate, the particles (for example, fillers such as silica, calcium carbonate and titanium oxide for imparting slipperiness) What is necessary is just to make a particle size small or to reduce the compounding quantity of this particle | grain.

[Antistatic layer]
The antistatic layer is formed by curing an aqueous thermosetting resin composition containing the polythiophene-based conductive polymer (A) (hereinafter also simply referred to as the component (A)).
In the present invention, since the film strength of the antistatic layer is improved by making the resin composition forming the antistatic layer thermosetting, the solvent resistance of the antistatic layer is improved. Furthermore, when a thin layer such as a release layer is provided on the antistatic layer, the overcoat property of the thin layer is improved. That is, when forming a thin layer such as a release layer on the antistatic layer, it is possible to prevent coating unevenness, repelling, streaks, and the like.
Further, by making the composition aqueous, the polythiophene-based conductive polymer (A) can be easily dispersed or dissolved without agglomeration or the like in the composition, and the antistatic layer and the mold release formed thereon are formed. Layers and the like can be smoothed. Furthermore, unevenness and pinholes are prevented from being generated in the release layer formed on the antistatic layer.

The antistatic layer has a thickness of 12 to 250 nm. When the thickness of the antistatic layer is less than 12 nm, the thickness is too thin, the surface resistance value of the antistatic layer is not sufficiently lowered by the component (A), and it becomes difficult to impart antistatic performance. In addition, a sufficient film cannot be formed, and solvent resistance and overcoat properties are lowered. On the other hand, if it is larger than 250 nm, even if one surface of the substrate is a smooth surface, it becomes difficult to smooth the surface of the antistatic layer, and the surface smoothness of the release layer and the like formed on the antistatic layer is ensured. Difficult to do. From the above viewpoint, the thickness of the antistatic layer is preferably 15 to 200 nm. The thickness of the antistatic layer was measured using a spectroscopic ellipsometer.
The antistatic layer can be made to have a desired thickness by appropriately changing the solid content concentration in the aqueous thermosetting resin composition or changing the gap of the coating apparatus. The solid content concentration in the aqueous thermosetting resin composition is not particularly limited, but is preferably about 0.4 to 2.0% by mass, more preferably about 0.5 to 1.6% by mass. .

The antistatic layer is preferably composed of a cured film formed by crosslinking a polyester resin and a melamine compound. Specifically, in addition to the component (A), a hydroxyl group-containing polyester resin (B) (hereinafter simply referred to as a polyester). It is obtained by curing an aqueous thermosetting resin composition containing a resin (B) or (B) component) and a melamine compound (C) (hereinafter also simply referred to as (C) component). Is preferred.
The aqueous thermosetting resin composition may be water-dispersible or water-soluble so that each component is dispersed or dissolved in a diluent containing water.

Hereinafter, each component constituting the antistatic layer will be described in more detail.
<Polythiophene-based conductive polymer (A)>
Specific examples of the polythiophene-based conductive polymer (A) include, for example, polyalkylene dioxythiophenes such as polyethylene dioxythiophene, polypropylene dioxythiophene, poly (ethylene / propylene) dioxythiophene, and polystyrene sulfonate. Mixtures: Polythiophene compounds having a sulfonic acid group such as poly (3-thiophene-β-ethanesulfonic acid). Among these, a mixture of polyalkylene dioxythiophene and polystyrene sulfonate is preferable, and a mixture of polyethylene dioxythiophene and polystyrene sulfonate (PEDOT-PSS) is more preferable.
When the antistatic layer contains the polythiophene-based conductive polymer (A), even if it is a thin film, the surface resistance value is sufficiently low, and it becomes possible to effectively prevent charging. Further, the polythiophene-based conductive polymer (A) has water solubility or water dispersibility, and thus can be easily dissolved or dispersed in the aqueous thermosetting resin composition as described above.

The aqueous thermosetting resin composition for forming the antistatic layer may contain 0.5 to 50 parts by mass of the polythiophene-based conductive polymer (A) with respect to 100 parts by mass of the polyester resin (B). preferable. By containing the component (A) above the lower limit, it is possible to cause the release film to exhibit appropriate antistatic performance. Moreover, by setting it as the upper limit value or less, it is possible to prevent the component (A) from aggregating and the antistatic layer from being poorly cured.
From the above viewpoint, in the aqueous thermosetting resin composition, the component (A) is more preferably contained in an amount of 0.6 to 20 parts by mass with respect to 100 parts by mass of the component (B).

<Polyester resin (B)>
The polyester resin (B) can be obtained by reacting a polyvalent carboxylic acid component with a polyhydric alcohol component. The polyester resin (B) contains a hydroxyl group in the molecule, and the equivalent ratio of the OH group of the alcohol component to the COOH group of the polyvalent carboxylic acid component for constituting the polyester (OH group / COOH group) is Preferably it is greater than 1.0. The polyester resin (B) can be crosslinked with the melamine compound (C) by containing a hydroxyl group.

Here, the polyvalent carboxylic acid component is a compound having two or more carboxyl groups in one molecule. For example, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydroisophthalic acid, tetrahydroterephthalic acid, hexa Hydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, trimellitic acid, adipic acid, sebacic acid, succinic acid, azelaic acid, naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, het acid, fumaric acid, maleic acid Polybasic acids that can be generally used for the production of polyester resins such as itaconic acid and pyromellitic acid can be used. As the polyvalent carboxylic acid component, anhydrides of the above polyvalent carboxylic acid components can also be used. These polyvalent carboxylic acid components can be used alone or in combination of two or more.

The polyhydric alcohol component is a compound having two or more hydroxyl groups in one molecule, and specific examples thereof include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, Polypropylene glycol, neopentyl glycol, hexylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-butyl-2-ethyl-1,3 -Diols such as propanediol, methylpropanediol, cyclohexanedimethanol, 3,3-diethyl-1,5-pentanediol, glycerin, trimethylolethane, trimethylolpropane, erythritol, Pentaerythritol, etc. trihydric or higher alcohols such as dipentaerythritol, include those used in making the conventional polyester resin. These polyhydric alcohol components can be used alone or in combination of two or more.

The polyester resin (B) is preferably water-soluble or water-dispersible in order to be used as a component of the aqueous thermosetting resin composition. The polyester resin (B) is not particularly limited, but in order to impart water-solubility or water-dispersibility, those containing a structural unit containing a sulfonate group or a carboxylate group as a structural unit of the polyester are preferably used. .
The polyester resin (B) is a main component in the aqueous thermosetting resin composition, and is usually contained in an amount of 50% by mass or more based on the total solid content in the composition, preferably 65 to 92% by mass is contained. In addition, in this specification, solid content total amount means the quantity remove | excluding volatile components, such as a solvent volatilized in manufacturing processes, such as a hardening process, from the aqueous thermosetting resin composition.

<Melamine compound (C)>
Specific examples of the melamine compound (C) include methylol melamine and alkoxylated methylol melamine, and methylol melamine is more preferable from the viewpoint of high water solubility and high thermosetting speed. Examples of methylol melamine include those in which 1 to 6 methylol groups are bonded to the nitrogen atom of the amino group of melamine. Examples of the alkoxylated methylol melamine include those obtained by alkoxylating at least a part of the methylol group of methylol melamine with a lower alcohol. Specifically, the carbon number of the alkoxy group such as methoxylated methylol melamine and butoxylated methylol melamine Examples are 1 to 4.
The melamine compound (C) is preferably water-soluble melamine, and an aqueous solution of the above compound is used.
In the antistatic layer, since the polyester resin and the melamine compound are cross-linked by blending the component (C) in addition to the component (B), the above-described overcoat property, solvent resistance and the like are improved.

The aqueous thermosetting resin composition preferably contains 8 to 35 parts by mass of the melamine compound (C) with respect to 100 parts by mass in total of the components (A) and (B). When the component (C) is blended in an amount of 8 parts by mass or more in the antistatic layer, the above-described solvent resistance and overcoat properties are improved, and the surface of the antistatic layer is easily smoothed. Moreover, by setting it as 35 mass parts or less, the dispersion stability of a composition becomes favorable and it becomes difficult to generate | occur | produce an aggregate.
Further, the content of the melamine compound (C) is more preferably 10 to 32 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B).

Further, the surface resistance value of the antistatic layer is preferably less than 1 × 10 ¹¹ Ω / □, and more preferably less than 1 × 10 ¹⁰ Ω / □. By making the surface resistance value of the antistatic layer less than 1 × 10 ¹¹ Ω / □, it becomes possible to appropriately prevent the release film from being charged. It is easy to suppress various problems that occur when manufacturing the.

The aqueous thermosetting resin composition for forming the antistatic layer contains at least water as a diluent solvent, and further contains a polar solvent other than water, such as dimethyl sulfoxide, isopropyl alcohol (IPA), and ethanol, as a diluent solvent. Also good. In addition, as for a dilution solvent, it is more preferable to use the thing whose 30 mass% or more and 70 mass% or less in all the solvents are water. By making water 70 mass% or less, it becomes difficult to generate the repelling etc. which arise when apply | coating an aqueous thermosetting resin composition.
Moreover, by making water 30 mass% or more, it becomes possible to disperse | distribute or melt | dissolve (A) component in a diluent, and it becomes easy to prevent aggregation of (A) component. Furthermore, the water-soluble or water-dispersible component (B) and the water-soluble (C) component can be easily dispersed or dissolved in the composition. Therefore, it becomes possible to form an appropriate film with good coating properties of the thermosetting resin composition.

The antistatic layer is obtained by applying an aqueous thermosetting resin composition obtained by diluting at least the components (A) to (C) with a diluting solvent onto a base material, followed by drying by heating and thermosetting. is there.
Here, the application method of the aqueous thermosetting resin composition is not particularly limited, and examples thereof include a gravure coating method, a bar coating method, a spray coating method, a spin coating method, a knife coating method, a roll coating method, and a die coating method. Can be mentioned.
In addition to the components (A) to (C) and the diluting solvent, the aqueous thermosetting resin composition is not limited to the resin components other than the components (A) to (C), as long as the effects of the present invention are not impaired. It may contain additives. However, the aqueous thermosetting resin composition preferably does not contain a filler such as an inorganic filler in order to ensure the smoothness of the surface of the antistatic layer.

[Release layer]
The release layer is composed of a release agent. Specifically, a silicone resin release agent, an alkyd resin release agent, an olefin resin release agent, an acrylic resin release agent, rubber System release agents, melamine resin release agents, fluororesin release agents and the like can be used, but silicone resin release agents are preferred. Hereinafter, the case where a silicone resin type release agent is used as the release agent will be described in detail.

As the silicone resin release agent, an addition reaction type silicone resin composition is preferably used. The addition reaction type silicone resin composition includes a main component composed of an addition reaction type silicone resin and a crosslinking agent, a catalyst, and, if necessary, an addition reaction inhibitor, a release adjusting agent, an adhesion improver, a photosensitizer, and the like. Other additives are added.
There are no particular limitations on the addition reaction type silicone resin, and various types can be used. For example, polyorganosiloxane having an alkenyl group as a functional group in the molecule can be used, and more specifically, a vinyl group. And polydimethylsiloxane having a functional group such as a hexenyl group.
In addition, a linear polyorganosiloxane having an alkenyl group and having a mass average molecular weight (Mw) of 70000 or more, and a branched organosiloxane having an alkenyl group and a mass average molecular weight (Mw) of about 500 to 50000 What mixed with the oligomer etc. can also be used as an addition reaction type silicone resin. In addition, in this specification, a mass average molecular weight (Mw) means what was calculated | required as a polystyrene conversion value by gel permeation chromatography (GPC).

Examples of the crosslinking agent include polyorganosiloxane having hydrogen atoms bonded to at least two silicon atoms in one molecule, and specifically, polymethylhydrogensiloxane. The amount of the crosslinking agent used is preferably 0.1 to 100 parts by weight, more preferably 0.5 to 25 parts by weight with respect to 100 parts by weight of the addition reaction type silicone resin. As the catalyst, a platinum-based catalyst is used.

The release layer preferably has a smooth surface in order to prevent irregularities and pin poles from being generated on an article such as a ceramic green sheet laminated on the release layer. Specifically, the surface of the release layer preferably has an arithmetic average roughness Ra of less than 10 nm, a maximum protrusion height Rp of less than 100 nm, an arithmetic average roughness Ra of 8 nm or less, The maximum protrusion height Rp is more preferably 80 nm or less. In consideration of the ease of production of the release layer, the arithmetic average roughness Ra and the maximum protrusion height Rp are each preferably 1 nm or more and 10 nm or more.
In the present invention, as described above, the arithmetic average roughness Ra and the maximum protrusion height Rp of the base material are set to a predetermined value or less, and the structure of the antistatic layer is set to a predetermined value. As described above, it is possible to reduce the arithmetic average roughness Ra and the maximum protrusion height Rp of the release layer formed in the above.

As a release agent constituting the release layer, a non-solvent type or an aqueous type using water as a dilution solvent can be used, but a solvent type using an organic solvent as a dilution solvent is used. It is preferable to do. By using a solvent-type release agent, various release agents can be widely used, and various required performances such as release performance can be easily designed.
When the release agent is a solvent type, specific examples of the organic solvent used as the diluting solvent include toluene, IPA, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK) and the like. Since the antistatic layer has good solvent resistance as described above, even when a solvent-type release agent is used, the antistatic layer dissolves when the release layer is formed. Can be prevented.

For the release layer, the release agent composition is applied on the antistatic layer or on the other side of the substrate (that is, the side on which the antistatic layer is not provided), and then the coating film is dried by heating. It can be formed by curing the same. Moreover, the application | coating method of a mold release agent is not specifically limited, For example, the gravure coat method, the bar coat method, the spray coat method, the spin coat method, the knife coat method, the roll coat method, the die coat method etc. are mentioned.
The thickness of the release layer is not particularly limited, but is preferably adjusted so that the basis weight after drying is about 0.03 to 0.4 g / m ² .

[How to use the release film]
The release film is preferably used in the production process of the multilayer ceramic capacitor, and more preferably used for the production process of the ceramic green sheet. Specifically, the ceramic green sheet is produced by applying a ceramic slurry on a release layer of a release film and then drying it appropriately. In addition to the ceramic green sheet, the release film may be used when various materials are applied on the release layer and appropriately cured to produce a sheet-shaped article. It may be used for other purposes. In addition, the ceramic green sheet and other articles produced on the release film are peeled from the release film after the sheet is produced.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

The measurement method and evaluation method in the present invention are as follows.
[Measurement method of antistatic layer thickness]
J. et al. A. Measurement was performed using a spectroscopic ellipsometer “M-2000” manufactured by Woollam Japan.
[Evaluation of surface resistance]
The surface resistance value of the antistatic layer was measured by the following method.
Measuring device: “HIESTA UP” manufactured by Mitsubishi Chemical Analytech Co., Ltd.
Measurement conditions: applied voltage 100 V, measurement time 10 seconds later, measured value is an average of 5 measurements [evaluation of coating properties of antistatic layer]
The surface of the antistatic layer formed on the substrate was rubbed 10 times with a finger, and smear (cloudy) and rub-off (dropout) were judged visually under a fluorescent lamp according to the following evaluation criteria.
A: No change B: Either cloudy or fallen.
[Evaluation of solvent resistance]
An appropriate amount of solvent (MEK) is contained in Bencot (model number: AP-2) manufactured by Asahi Kasei Co., Ltd., and the surface of the antistatic layer formed on the substrate is 10 cm long with a load of about 100 g / cm ^2. 20 reciprocations were wiped at a speed of about 1 second reciprocation, and the presence or absence of the antistatic layer was visually confirmed under a fluorescent lamp according to the following evaluation criteria.
A: No change B: Dropout
[Evaluation of overcoat properties]
In each of Examples and Comparative Examples, the surface to which the release agent composition was applied was not formed or formed with defects (whitening, unevenness, or scratches) in the surface state due to the dilution solvent of the release agent composition. The surface state of the release layer was visually confirmed under a fluorescent lamp for defects (repellency or streaks). A case without the above-mentioned problem was determined as “A”, and when any one occurred, it was determined as “B”.
[Measurement of surface roughness]
The arithmetic average roughness Ra and the maximum protrusion height Rp were measured under the following conditions based on JIS B0601-1994.
Measuring device: Optical interference surface roughness meter “WYKO-1100” manufactured by Veeco
Measurement conditions: PSI mode, lens 50 magnification

[Example 1]
(Formation of antistatic layer)
8.4 parts by mass of a water-soluble hydroxyl group-containing polyester resin (component (B)) and 0.5 parts by mass of PEDOT-PSS (component (A)) are diluted with 15 parts by mass of dimethyl sulfoxide and 85 parts by mass of water. From 100 parts by mass of dilution liquid A (manufactured by Chukyo Yushi Co., Ltd., S-495: solid content 8.2% by mass), 70 parts by mass of water-soluble methylol melamine (component (C)) and 30 parts by mass of water 1.7 parts by mass of a melamine compound solution (manufactured by Chukyo Yushi Co., Ltd., P-795: solid content: 70.0% by mass) is further mixed with a mixed solvent of water and IPA (mass ratio of 1: 1). In addition, it was diluted so as to have a solid content of 0.6% by mass to obtain a thermosetting resin composition coating solution.
After drying the coating liquid of this thermosetting resin composition on a base material comprising a polyethylene terephthalate film (thickness 31 μm, arithmetic average roughness Ra 10 nm of the surface on which the coating liquid is applied, maximum protrusion height Rp 80 nm) The film was uniformly coated to a thickness of 15 nm and dried at 120 ° C. for 60 seconds to form an antistatic layer.

(Formation of release layer)
A mixture of both ends trivinyl-modified linear polyorganosiloxane, branched vinyl-modified organosiloxane oligomer, and polymethylhydrogensiloxane (mass average molecular weight: 287000) was diluted with MEK so as to have a solid content of 30% by mass. . Add 2 parts by mass of a platinum-based catalyst (PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) to 100 parts by mass of this diluted solution, and adjust the solid content concentration to 0.7% by mass with MEK. A coating liquid of a reactive silicone resin composition was obtained.
The obtained coating solution was uniformly applied on the antistatic layer by a bar coating method so that the film thickness after drying was 0.04 g / m ^2, and then dried at 130 ° C. for 1 minute. Thus, a release layer was formed, and a release film having a release layer laminated on the antistatic layer was obtained.

[Example 2]
The amount of the mixed solvent of water and IPA (mass ratio 1: 1) is adjusted so that the solid content concentration of the coating liquid of the thermosetting resin composition is 1.5% by mass, and the thickness of the antistatic layer is 200 nm. The same operation as in Example 1 was carried out except that

[Example 3]
It implemented similarly to Example 1 except having changed the compounding quantity of the melamine compound solution with respect to 100 mass parts of dilution liquid A into 3.5 mass parts.

[Example 4]
The amount of the mixed solvent of water and IPA (mass ratio 1: 1) is adjusted so that the solid content concentration of the coating liquid of the thermosetting resin composition is 1.5% by mass, and the thickness of the antistatic layer is 200 nm. Example 3 was carried out in the same manner as in Example 3 except that.

[Example 5]
It implemented similarly to Example 1 except having changed the compounding quantity of the melamine compound solution with respect to 100 mass parts of dilution liquid A into 1.45 mass parts.

[Example 6]
(Formation of antistatic layer)
8.4 parts by mass of a water-soluble hydroxyl group-containing polyester resin (component (B)) and 0.5 parts by mass of PEDOT-PSS (component (A)) are diluted with 15 parts by mass of dimethyl sulfoxide and 85 parts by mass of water. From 100 parts by mass of dilution liquid A (manufactured by Chukyo Yushi Co., Ltd., S-495: solid content 8.2% by mass), 70 parts by mass of water-soluble methylol melamine (component (C)) and 30 parts by mass of water 1.7 parts by mass of a melamine compound solution (manufactured by Chukyo Yushi Co., Ltd., P-795: solid content: 70.0% by mass) is further mixed with a mixed solvent of water and IPA (mass ratio of 1: 1). In addition, it was diluted so as to have a solid content of 0.6% by mass to obtain a thermosetting resin composition coating solution.
After drying the coating liquid of this thermosetting resin composition on a base material comprising a polyethylene terephthalate film (thickness 31 μm, arithmetic average roughness Ra 10 nm of the surface on which the coating liquid is applied, maximum protrusion height Rp 80 nm) The film was uniformly coated to a thickness of 15 nm and dried at 120 ° C. for 60 seconds to form an antistatic layer.

(Formation of release layer)
A mixture of both ends trivinyl-modified linear polyorganosiloxane, branched vinyl-modified organosiloxane oligomer, and polymethylhydrogensiloxane (mass average molecular weight: 287000) was diluted with MEK so as to have a solid content of 30% by mass. . Add 2 parts by mass of a platinum-based catalyst (PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) to 100 parts by mass of this diluted solution, and adjust the solid content concentration to 0.7% by mass with MEK. A coating liquid of a reactive silicone resin composition was obtained.
The obtained coating liquid was uniformly applied to a polyethylene terephthalate film opposite to the antistatic layer by a bar coating method so that the film thickness after drying was 0.04 g / m ^2, and then 130 A release layer was formed by drying at 0 ° C. for 1 minute to obtain a release film in which the antistatic layer and the release layer were laminated.

[Comparative Example 1]
The addition amount of a mixed solvent of water and IPA (mass ratio 1: 1) is adjusted so that the solid content concentration of the coating liquid of the thermosetting resin composition is 0.5 mass%, and the film thickness after drying is 10 nm. An antistatic layer was formed in the same manner as in Example 1 except that coating was performed so that Thereafter, in the same manner as in Example 1, a release layer was formed on the antistatic layer.

[Comparative Example 2]
The addition amount of a mixed solvent of water and IPA (mass ratio 1: 1) is adjusted so that the solid content concentration of the coating liquid of the thermosetting resin composition is 2.0 mass%, and the film thickness after drying is 300 nm. An antistatic layer was formed in the same manner as in Example 1 except that coating was performed so that Thereafter, in the same manner as in Example 1, a release layer was formed on the antistatic layer.

[Comparative Example 3]
A mixed solvent of water and IPA (mass ratio 1: 1) was added to the diluent A, and diluted to a solid content of 0.6% by mass to obtain a resin composition coating solution. This resin composition does not contain the melamine compound (C) and does not have thermosetting. The resin composition coating solution is uniformly applied to the same substrate as in Example 1 so that the film thickness after drying is 15 nm, and dried at 120 ° C. for 60 seconds to form an antistatic layer. did. Thereafter, in the same manner as in Example 1, a release layer was formed on the antistatic layer.

[Comparative Example 4]
75 parts by mass of an acrylic monomer mixture containing dipentaerythritol hexaacrylate, dipentaerythritol triacrylate and N-vinylpyrrolidone in a mass ratio of 45:20:10, 20 parts by mass of butyl acetate, and 30 parts by mass of IPA 15.5 parts by mass of an aqueous solution containing 1.3% by mass of PEDOT-PSS and 0.2 part by mass of α-hydroxycyclohexylphenylmethanone (photoinitiator) The mixture was further diluted with IPA so that the total amount of the acrylic monomer mixture and PEDOT-PSS was 2.5% by mass to obtain a coating solution of the photocurable resin composition.
The photocurable resin composition coating solution was applied uniformly to the same substrate as in Example 1 so that the film thickness after drying was 100 nm, dried at 70 ° C. for 60 seconds, and then irradiated with ultraviolet rays. Was irradiated with a light amount of 200 mJ / cm ² to form an antistatic layer. Thereafter, in the same manner as in Example 1, a release layer was formed on the antistatic layer.

[Comparative Example 5]
A partial hydrolyzate of tetraethoxysilane (manufactured by Colcoat, N-103X) was diluted with IPA to a solid content of 0.6% by mass to obtain a resin coating solution. This resin coating solution was applied uniformly on the same substrate as in Example 1 so that the film thickness after drying was 70 nm, and dried at 120 ° C. for 60 seconds to form an antistatic layer. did. Thereafter, in the same manner as in Example 1, a release layer was formed on the antistatic layer.

* In Table 1, the mass part of the component (A) (PEDOT-PSS) represents the mass part relative to 100 parts by mass of the component (B). (C) The mass part of a component (melamine compound) shows the mass part with respect to a total of 100 mass parts of (A) component and (B) component.

In Examples 1 to 5 described above, the antistatic performance of the release film is formed by forming an antistatic layer having a predetermined thickness on a smooth substrate with an aqueous thermosetting resin composition containing PEDOT-PSS. The coating properties, solvent resistance, and overcoat properties of the antistatic layer could be improved. In addition, since the smoothness of the surface of the antistatic layer has been secured, the arithmetic average roughness Ra of the release layer formed on the antistatic layer and the maximum protrusion height Rp are lowered, and the smoothness of the release layer is ensured. did it. Furthermore, in Example 6, the release layer was provided on the surface opposite to the surface provided with the antistatic layer of the base material, but various performances could be improved.
On the other hand, since the release film of Comparative Example 1 had a thin antistatic layer, the surface resistance value was high, the antistatic performance could not be sufficient, and the solvent resistance and overcoat properties were insufficient. . In Comparative Example 2, since the antistatic layer was too thick, smoothness of the surface of the antistatic layer could not be ensured, and the surface roughness of the release layer was increased.
Further, in Comparative Examples 3 and 4, since the resin composition was not aqueous thermosetting, the solvent resistance and overcoat properties were insufficient, and the (A) component was agglomerated and the smoothness was sufficient. Could not secure. In addition, the release film of Comparative Example 5 is one in which the antistatic layer does not contain the component (A), which is inferior in the solvent resistance and overcoat property of the antistatic layer, and the surface roughness of the release layer is increased. However, sufficient smoothness could not be secured.

10A, 10B Release film 11 Base material 11A One side 12 Antistatic layer 13 Release layer

Claims

A base material, an antistatic layer provided on one surface of the base material, and a release layer provided on the antistatic layer or on the other surface side of the base material,
One surface of the substrate has an arithmetic average roughness Ra of 15 nm or less and a maximum protrusion height Rp of 150 nm or less,
A release film in which the antistatic layer is obtained by curing an aqueous thermosetting resin composition containing a polythiophene-based conductive polymer (A), and the antistatic layer has a thickness of 12 to 250 nm.
The release film according to claim 1, wherein the release layer is provided on the antistatic layer.
3. The release film according to claim 1, wherein the release layer has an arithmetic average roughness Ra of less than 10 nm and a maximum protrusion height Rp of less than 100 nm.
The release film according to any one of claims 1 to 3, wherein the aqueous thermosetting resin composition further comprises a hydroxyl group-containing polyester resin (B) and a melamine compound (C).
The aqueous thermosetting resin composition contains 8 to 35 parts by mass of the melamine compound (C) with respect to a total of 100 parts by mass of the polythiophene conductive polymer (A) and the hydroxyl group-containing polyester resin (B). Item 5. The release film according to Item 4.
6. The aqueous thermosetting resin composition according to claim 4, wherein the polythiophene conductive polymer (A) is contained in an amount of 0.5 to 50 parts by mass with respect to 100 parts by mass of the hydroxyl group-containing polyester resin (B). Release film.
The release film according to any one of claims 4 to 6, wherein the melamine compound (C) is methylolmelamine.
The release film according to any one of claims 1 to 7, wherein the polythiophene-based conductive polymer (A) is a mixture of polyethylene dioxythiophene and polystyrene sulfonate.
The release film according to any one of claims 1 to 8, which is used for a production process of a ceramic green sheet.