KR20230141468A - Release film, method of producing release film and laminate - Google Patents

Abstract

Provided are a release film having excellent peelability and solvent resistance and the application thereof, and provided are the release film comprising a polyester base material and a release layer, wherein the release layer is formed by crosslinking a composition containing a silicone compound and an oxazoline compound, and the application thereof.

Description

Release film, method for producing release film, and laminate {RELEASE FILM, METHOD OF PRODUCING RELEASE FILM AND LAMINATE}

This disclosure relates to a release film, a method of producing the release film, and a laminate.

As the performance and miniaturization of electronic devices increase, the electronic components used in electronic devices are also required to have higher performance and miniaturization. Among electronic components, for example, the number of multilayer ceramic capacitors mounted on a substrate is increasing, and there is a strong demand for miniaturization.

In the production of a multilayer ceramic capacitor, a process of applying a ceramic slurry on a release film with a release layer and drying it to form a ceramic green sheet is generally included.

For example, in Patent Document 1, at least one side of a polyester film has an application layer formed from a coating liquid containing a crosslinking agent and a mold release agent and containing 30% by weight or less of polymers other than these as a proportion of non-volatile components. A laminated polyester film characterized by this is described. Patent Document 2 describes a laminated film having a resin layer on at least one side of a polyester film, wherein the resin layer is on at least one surface layer, the water contact angle of the resin layer is 85° or more and 100° or less, and the haze of the laminated film is When H1 (%) and H2 (%) are the haze after subjecting the laminated film to a solvent immersion and abrasion test, a laminated film with |H2-H1|≤1.0 (%) is described.

Patent Document 1: Japanese Patent Publication No. 2016-30378 Patent Document 2: International Publication No. 2020/017289

However, in release films, there are cases where improvement in peelability and solvent resistance is required. In particular, when the release film is a release film for producing ceramic green sheets, there is room for improvement in terms of peelability from the ceramic green sheet and improvement in solvent resistance when a ceramic slurry is applied to the release film.

The present disclosure has been made in consideration of the above circumstances, and the problem to be solved by one embodiment of the present invention is to provide a release film with excellent peelability and solvent resistance, and a method for manufacturing the release film, in particular, a ceramic green sheet. The object is to provide a release film that is excellent in peelability from and solvent resistance when a ceramic slurry is applied, and a method for producing the release film.

In addition, the problem to be solved by another embodiment of the present invention is to provide a laminate including a release film excellent in peelability and solvent resistance, particularly in peelability from a ceramic green sheet and when applying a ceramic slurry. The object is to provide a laminate containing a release film excellent in solvent resistance.

The present disclosure includes the following aspects.

<1> A release film comprising a polyester base material and a release layer, wherein the release layer is formed by crosslinking a composition containing a silicone compound and an oxazoline compound.

<2> The release film according to <1>, wherein the composition contains an acid-generating compound.

<3> The release film according to <2>, wherein the acid-generating compound is ammonium phosphate.

<4> The release film according to any one of <1> to <3>, in which the polyester base material does not substantially contain particles.

<5> The release film according to any one of <1> to <4>, wherein the composition satisfies at least one of the following conditions 1 and 2.

Condition 1: The silicone compound contains an acid group.

Condition 2: The composition further contains an acid group-containing non-silicone resin.

<6> The peeling according to <5>, wherein the composition further contains an acid group-containing non-silicone resin, and the acid group-containing non-silicone resin is at least one member selected from the group consisting of an acid group-containing urethane resin and an acid group-containing olefin resin. film.

<7> In <5> or <6>, the composition further contains an acidic radical-containing non-silicone resin, and the mass ratio of the content of the acidic radical-containing non-silicone resin to the content of the silicone compound in the composition is 1 to 30. Release film described.

<8> The release film according to any one of <1> to <7>, wherein the mass ratio of the content of the silicone compound to the content of the oxazoline compound in the composition is 0.1 to 10.

<9> The peeling film according to any one of <1> to <8>, wherein the peeling layer has a thickness of 0.001 μm to 0.2 μm.

<10> The release film according to any one of <1> to <9>, further comprising a particle-containing layer, and comprising a release layer, a polyester substrate, and a particle-containing layer in this order.

<11> The release film according to <10>, wherein the particle-containing layer contains a non-polyester resin.

<12> The release film according to <11>, wherein the non-polyester resin is at least one type of resin selected from the group consisting of an acrylic resin, a urethane resin, and an olefin resin.

<13> The release film according to any one of <1> to <12>, which is for producing a ceramic green sheet.

<14> A method for producing a release film comprising a polyester substrate and a release layer, comprising the step of forming the release layer using a composition for forming a release layer containing a silicone compound and an oxazoline compound. Manufacturing method.

<15> Peeling according to <14>, wherein the step of forming the release layer is a step of forming a release layer by applying a release layer forming composition to one side of an unstretched polyester film or a uniaxially stretched polyester film. Method of manufacturing the film.

<16> A laminate comprising the release film according to any one of <1> to <13> and a layer containing ceramic.

According to one embodiment of the present invention, a release film having excellent peelability and solvent resistance, and a method for producing the release film, particularly, a peeling film having excellent peelability from a ceramic green sheet and excellent solvent resistance when applying a ceramic slurry. A film and a method of producing a release film are provided.

Furthermore, according to another embodiment of the present invention, a laminate comprising a release film excellent in peelability and solvent resistance, particularly peelability from a ceramic green sheet and excellent solvent resistance when a ceramic slurry is applied, is provided. A laminate including a film is provided.

Hereinafter, the release film, the production method of the release film, and the laminate of the present disclosure will be described in detail.

In this specification, the numerical range indicated using "~" means a range that includes the numerical values written before and after "~" as the minimum and maximum values, respectively.

In the numerical range described stepwise in this specification, the upper limit or lower limit value described as a predetermined numerical range may be replaced with the upper limit or lower limit value of another numerical range described stepwise. In addition, in the numerical range described in this specification, the upper limit or lower limit described in the predetermined numerical range may be replaced with the value shown in the examples.

In this specification, the amount of each component in the composition means the total amount of the multiple substances present in the composition, unless otherwise specified, when multiple substances corresponding to each component exist in the composition.

In this specification, a combination of two or more preferred aspects is a more preferred aspect.

In this specification, the word "process" is included in this term not only as an independent process, but also in cases where the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes.

In this specification, the “longitudinal direction” means the elongated direction of the release film during production of the release film, and has the same meaning as the “conveyance direction” and “machine direction.”

In this specification, “width direction” means a direction perpendicular to the longitudinal direction. In this specification, “orthogonal” is not limited to strict orthogonal but includes approximately orthogonal. “Approximately perpendicular” means intersecting within the range of 90°±5°, preferably intersecting within the range of 90°±3°, and more preferably intersecting within the range of 90°±1°. do.

In addition, in this specification, "film width" means the distance between both ends in the width direction of a peeling film.

[Release film]

The release film of the present disclosure includes a polyester base material and a release layer, and the release layer is formed by crosslinking a composition containing a silicone compound and an oxazoline compound.

According to the release film of the present disclosure, it is excellent in peelability and solvent resistance. The reason for this is not clear, but is guessed as follows.

In the release film of the present disclosure, the release layer is formed by crosslinking a composition containing a silicone compound and an oxazoline compound. The peeling layer is obtained by crosslinking the oxazoline compound with the components contained in the composition. The component crosslinked with the oxazoline compound may be a silicone compound, or may be a component other than the silicone compound. Since the release layer contains a silicone compound and a crosslinked product with a structure derived from the silicone compound, the release property is excellent. Additionally, since the release layer contains a crosslinked product based on an oxazoline compound, it has excellent solvent resistance.

In contrast, Patent Document 1 does not contain any description focusing on silicone compounds. In Patent Document 2, there is no description regarding the combined use of a silicone compound and an oxazoline compound.

<Polyester base material>

A polyester substrate is a film-like object containing polyester resin as the main polymer component. Here, the “main polymer component” means the polymer with the highest content (mass) among all polymers contained in the film-like object.

The polyester base material may contain one type of individual polyester resin, or may contain two or more types of polyester resin.

[polyester resin]

Polyester resin is a polymer that has an ester bond in its main chain. Polyester resin is usually formed by polycondensing a dicarboxylic acid compound and a diol compound, which will be described later.

In the present disclosure, “main chain” refers to the relatively longest bond chain among the molecules of the polymer compound constituting the resin.

The polyester resin is not particularly limited, and known polyester resins can be used. Polyester resins include, for example, polyethylene terephthalate (PET), polyethylene-2,6-naphthalate (PEN), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT), and copolymers thereof. Among them, at least one selected from the group consisting of PET, PEN, and copolymers thereof is preferable, and PET is more preferable.

The intrinsic viscosity of the polyester resin is preferably 0.50 dl/g or more and less than 0.80 dl/g, and more preferably 0.55 dl/g or more and less than 0.70 dl/g.

The melting point (Tm) of the polyester resin is preferably 220°C to 270°C, and more preferably 245°C to 265°C.

The glass transition temperature (Tg) of the polyester resin is preferably 65°C to 90°C, and more preferably 70°C to 85°C.

The manufacturing method of the polyester resin is not particularly limited, and known methods can be used. For example, a polyester resin can be produced by polycondensing at least one dicarboxylic acid compound and at least one diol compound in the presence of a catalyst.

Hereinafter, the materials used for manufacturing polyester and manufacturing conditions will be described.

(Dicarboxylic acid compound)

Examples of dicarboxylic acid compounds include dicarboxylic acids such as aliphatic dicarboxylic acid compounds, alicyclic dicarboxylic acid compounds, and aromatic dicarboxylic acid compounds, and dicarboxylic acid esters such as methyl ester compounds and ethyl ester compounds of these dicarboxylic acids. I can hear it. Among them, aromatic dicarboxylic acid or methyl aromatic dicarboxylate is preferable.

Examples of aliphatic dicarboxylic acid compounds include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, dimer acid, eicosanedioic acid, pimelic acid, azelaic acid, Examples include methylmalonic acid and ethylmalonic acid.

Examples of alicyclic dicarboxylic acid compounds include adamantane dicarboxylic acid, norbornenedicarboxylic acid, cyclohexanedicarboxylic acid, and decalindadicarboxylic acid.

As aromatic dicarboxylic acid compounds, for example, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 4 , 4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 5-sodium sulfoisophthalic acid, phenylindicarboxylic acid, anthracenedicarboxylic acid, phenanthrenedicarboxylic acid, and 9,9'-bis. (4-carboxyphenyl)fluorenic acid and their methyl ester forms.

Among them, terephthalic acid or 2,6-naphthalenedicarboxylic acid is preferable, and terephthalic acid is more preferable.

Only one type of dicarboxylic acid compound may be used, or two or more types may be used in combination. When using terephthalic acid as a dicarboxylic acid compound, terephthalic acid may be used alone, or may be copolymerized with other aromatic dicarboxylic acids such as isophthalic acid, or aliphatic dicarboxylic acids.

(diol compound)

Examples of diol compounds include aliphatic diol compounds, alicyclic diol compounds, and aromatic diol compounds, with aliphatic diol compounds being preferred.

Examples of aliphatic diol compounds include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, and 1,2-butanediol. , 1,3-butanediol, and neopentyl glycol, with ethylene glycol being preferred.

Examples of alicyclic diol compounds include cyclohexanedimethanol, spiroglycol, and isosorbide.

Examples of aromatic diol compounds include bisphenol A, 1,3-benzenedimethanol, 1,4-benzenedimethanol, and 9,9'-bis(4-hydroxyphenyl)fluorene. .

As for the diol compound, only one type may be used, or two or more types may be used together.

(catalyst)

The catalyst used in the production of polyester resin is not particularly limited, and known catalysts that can be used in the synthesis of polyester resin can be used.

Catalysts include, for example, alkali metal compounds (e.g., potassium compounds, sodium compounds), alkaline earth metal compounds (e.g., calcium compounds, magnesium compounds), zinc compounds, lead compounds, manganese compounds, and cobalt compounds. , aluminum compounds, antimony compounds, titanium compounds, germanium compounds, and phosphorus compounds. Among them, titanium compounds are preferable from the viewpoint of catalytic activity and cost.

Only one type of catalyst may be used, or two or more types may be used together. At least one metal catalyst selected from potassium compounds, sodium compounds, calcium compounds, magnesium compounds, zinc compounds, lead compounds, manganese compounds, cobalt compounds, aluminum compounds, antimony compounds, titanium compounds, and germanium compounds; , it is preferable to use a phosphorus compound together, and it is more preferable to use a titanium compound and a phosphorus compound together.

As the titanium compound, an organic chelate titanium complex is preferable. The organic chelate titanium complex is a titanium compound that has an organic acid as a ligand.

Examples of organic acids include citric acid, lactic acid, trimellitic acid, and malic acid.

As the titanium compound, the titanium compounds described in [0049] to [0053] of Japanese Patent Publication No. 5575671 can also be used, and the contents of the above publication are incorporated herein by reference.

(End sealant)

In the production of polyester resin, an end capping agent may be used as needed. By using an end cap agent, a structure derived from the end cap agent is introduced into the ends of the polyester resin.

The end capping agent is not limited and any known end capping agent can be used. Examples of end capping agents include oxazoline-based compounds, carbodiimide-based compounds, and epoxy-based compounds.

As an end capping agent, the contents described in [0055] to [0064] of Japanese Patent Application Laid-Open No. 2014-189002 can also be referred to, and the contents of the above publication are incorporated herein by reference.

(manufacturing conditions)

The reaction temperature when producing the polyester resin is not limited and can be set appropriately depending on the raw materials. The reaction temperature is preferably 260°C to 300°C, and more preferably 275°C to 285°C.

The pressure when manufacturing the polyester resin is not limited and can be set appropriately depending on the raw materials. The pressure is preferably 1.33×10 ^-3 to 1.33×10 ^-5 MPa, and more preferably 6.67×10 ^-4 to 6.67×10 ^-5 MPa.

As a method for synthesizing polyester resin, the method described in [0033] to [0070] of Japanese Patent Publication No. 5575671 can also be used, the contents of which are incorporated herein by reference.

[Content of each ingredient]

The content of the polyester resin in the polyester substrate is preferably 85% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more, with respect to the total mass of the polymer in the polyester substrate, 98% by mass or more is particularly preferable.

The upper limit of the content of the polyester resin is not particularly limited and can be appropriately set, for example, in the range of 100% by mass or less with respect to the total mass of the polymer in the polyester base material.

When the polyester base material contains polyethylene terephthalate, the content of polyethylene terephthalate is preferably 90% by mass to 100% by mass, and 95% by mass to 100% by mass, relative to the total mass of the polyester resin in the polyester base material. is more preferable, 98 to 100 mass% is more preferable, and 100 mass% is especially preferable.

The polyester substrate may contain components other than the polyester resin (for example, catalyst, unreacted raw material components, particles, and water).

From the viewpoint of improving the smoothness of the release film, it is preferable that the polyester base material does not substantially contain particles. Examples of particles include particles included in the particle-containing layer described later.

“Does not substantially contain particles” means that when elements derived from particles are quantitatively analyzed for a polyester base by fluorescence X-ray analysis, the particle content is 50 ppm by mass or less relative to the total mass of the polyester base. It is defined, preferably 10 mass ppm or less, and more preferably less than the detection limit. This means that without actively adding particles to the polyester substrate, contamination components derived from foreign substances, raw material resin, or contamination attached to the lines or equipment during the manufacturing process of the polyester substrate are peeled off and the polyester substrate is removed. This is because there are cases where it gets mixed up.

[Properties of polyester base]

(Orientation)

The polyester base material is preferably a biaxially oriented polyester base material.

“Biaxial orientation” means the property of having molecular orientation in the biaxial direction. Molecular orientation is measured using a microwave transmission type molecular orientation meter (for example, MOA-6004, manufactured by Oji Keisoku Kiki Co., Ltd.). The angle formed by the two axes is preferably within the range of 90°±5°, more preferably within the range of 90°±3°, and more preferably within the range of 90°±1°. The biaxially oriented polyester base material in the release film of the present disclosure preferably has molecular orientation in the longitudinal direction and the width direction. The biaxially oriented polyester base material can be manufactured by the method described later.

(density)

The density of the polyester base material is preferably 1.39 g/cm ³ to 1.41 g/cm ³ , more preferably 1.395 g/cm ³ to 1.405 g/cm ³ , and 1.398 g/cm ³ to 1.400 g/cm ³ . It is more desirable.

The density of the polyester base material can be measured using an electronic hydrometer (product name "SD-200L", manufactured by Alpha Mirage).

(thickness)

The thickness of the polyester base material is preferably 100 μm or less, more preferably 50 μm or less, and still more preferably 40 μm or less, since peelability can be controlled. The lower limit of the thickness is not particularly limited, but since strength is improved and processability is improved, 3 μm or more is preferable, 10 μm or more is more preferable, and 20 μm or more is still more preferable.

The thickness of the polyester substrate is measured by producing a section with a cross-section perpendicular to the main surface of the release film and using a scanning electron microscope (SEM) or a transmission electron microscope (TEM). , is taken as the arithmetic mean value of the thickness of the five sections of the above section.

<Peel layer>

The peeling layer is provided to enable peeling of the peeling film. When a release film is used to produce a ceramic green sheet, the ceramic green sheet is formed on the release surface, which is the surface opposite to the polyester substrate of the release layer. That is, a ceramic green sheet is provided on the peeling surface of the peeling film so that peeling is possible.

In addition, the release layer may be provided directly on the surface of the polyester substrate or may be provided on the polyester substrate through another layer, but it is preferable to provide it directly on the surface of the polyester substrate because of its superior smoothness. .

The release layer is formed by crosslinking a composition containing a silicone compound and an oxazoline compound. Hereinafter, the composition containing a silicone compound and an oxazoline compound is also referred to as a “composition for forming a peeling layer.”

[Silicone compound]

The composition for forming a release layer contains a silicone compound. If a silicone compound is contained, the peeling layer has excellent peelability.

The silicone compound is not particularly limited as long as it is a compound having a siloxane bond in the molecule. The silicone compound is preferably a compound having a dimethylsiloxane structure because of its superior peelability. The silicone compound may be a low molecule, an oligomer, or a resin, but is preferably an oligomer or a resin.

The weight average molecular weight of the silicone compound is preferably 150 or more, more preferably 350 or more, and still more preferably 650 or more. The upper limit of the weight average molecular weight is not particularly limited, and is, for example, 1 million. The weight average molecular weight of the silicone compound is preferably 100,000 or less, and more preferably 10,000 or less.

In the present disclosure, weight average molecular weight (Mw) means a value measured by gel permeation chromatography (GPC). In addition, when the molecular weight is 1000 or less, the molecular weight is calculated based on the type and number of atoms constituting the compound.

Measurement by GPC uses HLC (registered trademark)-8020GPC (Tosoh Co., Ltd.) as a measuring device, and TSKgel (registered trademark) Super Multipore HZ-H (4.6 mmID × 15 cm, Tosoh Co., Ltd.) as a column. ) are used, and as an eluent, THF (tetrahydrofuran) is used. In addition, as measurement conditions, the sample concentration is 0.45 mass%, the flow rate is 0.35 ml/min, the sample injection amount is 10 μL, and the measurement temperature is 40°C, and the measurement is performed using an RI detector.

The calibration curve is "standard sample TSK standard, polystyrene" from Tosoh Co., Ltd.: "F-40", "F-20", "F-4", "F-1", "A-5000", "A- 2500", "A-1000", and "n-propylbenzene".

As the silicone compound, a crosslinkable silicone compound is preferable because it has better solvent resistance. The component that the silicone compound crosslinks may be an oxazoline compound or a component contained in another peeling layer, and it is preferable that the crosslinkable site is introduced into at least one of the terminal and side chains of the silicone compound.

Examples of silicone compounds include polydimethylsiloxane and hydrodienesiloxane, which have a vinyl group introduced into at least one of the terminal and side chains. These silicone compounds have superior solvent resistance because a crosslinked product is obtained by reacting using a platinum catalyst.

Moreover, examples of the silicone compound include polydimethylsiloxane having a hydroxyl group at the terminal, and polydimethylsiloxane having a hydrogen atom at the terminal. These silicone compounds have superior solvent resistance because a crosslinked product is obtained by carrying out a condensation reaction using an organic tin catalyst.

Additionally, the silicone compound may be a silicone compound that can be crosslinked by the action of ultraviolet rays or electron beams. Examples of silicone compounds that can be crosslinked by the action of ultraviolet rays or electron beams include silicone compounds capable of radical polymerization and silicone compounds having an epoxy group. More specifically, acrylate-modified polydimethylsiloxane, and glycidoxy-modified polydimethylsiloxane.

Among them, the silicone compound preferably contains an acidic group from the viewpoint of crosslinkability with the oxazoline compound, and it is more preferable that the silicone compound contains an acidic group in at least one of the terminal and side chains of the silicone compound. When the silicone compound contains an acid group, the hydrophobized surface is hardened by crosslinking, thereby further improving solvent resistance.

Examples of the acid group include a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group. Among them, it is preferable that the acid group is a carboxy group from the viewpoint of crosslinkability with the oxazoline compound. That is, it is preferable that the silicone compound has a carboxy group.

Among the compositions for forming a peeling layer, only one type of silicone compound may be used, and two or more types may be used.

In the composition for forming a release layer, the silicone compound is preferably a silicone compound containing an acid group, and a combination of a silicone compound containing an acid group and a silicone compound not containing an acid group may be used.

The content of the silicone compound is preferably 1% by mass to 90% by mass, based on the total solid content of the composition for forming a release layer, and is 5% by mass to 76% by mass because of superior peelability and solvent resistance. It is more desirable. In addition, in the present disclosure, the solid content means the total mass excluding liquid components such as water and solvent contained in the composition for forming a peeling layer.

[Oxazoline Compound]

The composition for forming a peeling layer contains an oxazoline compound. If an oxazoline compound is contained, the peeling layer has excellent solvent resistance.

Since the oxazoline compound has a function as a cross-linking agent, it is believed that by including a cross-linking agent based on the oxazoline compound in the peeling layer, the peeling layer becomes more hydrophobic and has excellent solvent resistance. In addition, since the crosslinked product based on the oxazoline compound has excellent flexibility, for example, when a stretching step is performed after applying the composition for forming a release layer on a polyester film described later, the composition for forming a release layer Since the film formed by applying also follows and is stretched, it is difficult for microscopic defects such as cracks to occur in the peeling layer. As a result, it is thought that even when applied for manufacturing ceramic green sheets, microscopic irregularity defects are suppressed.

The oxazoline compound is not particularly limited as long as it is a compound having an oxazoline group, and may be a low molecular weight compound with a weight average molecular weight of less than 1000, or a high molecular weight compound with a weight average molecular weight of more than 1000. However, because of its superior solvent resistance, it is a high molecular compound. It is desirable.

Examples of low-molecular-weight compounds having an oxazoline group include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, and 2-isozoline. Propenyl-2-oxazoline, 2-isopropenyl-4-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2 -Isopropenyl-5-ethyl-2-oxazoline, 2,2'-bis-(2-oxazoline), 2,2'-methylene-bis-(2-oxazoline), 2,2'-ethylene -bis-(2-oxazoline), 2,2'-trimethylene-bis-(2-oxazoline), 2,2'-tetramethylene-bis-(2-oxazoline), 2,2'-hexa Methylene-bis-(2-oxazoline), 2,2'-octamethylene-bis-(2-oxazoline), 2,2'-ethylene-bis-(4,4'-dimethyl-2-oxazoline) ), 2,2'-p-phenylene-bis-(2-oxazoline), 2,2'-m-phenylene-bis-(2-oxazoline), 2,2'-m-phenylene- Bis-(4,4'-dimethyl-2-oxazoline), bis-(2-oxazolinylcyclohexane)sulfide, and bis-(2-oxazolinylnobornene)sulfide.

When the oxazoline compound is a high molecular compound, it may be a high molecular compound having an oxazoline group. Examples include a copolymer containing the low molecular weight compound having the oxazoline group as a structural unit.

The polymer compound having an oxazoline group is preferably a polymer containing an oxazoline group and a polyalkylene oxide chain, and more preferably an acrylic polymer containing an oxazoline group and a polyalkylene oxide chain.

The polymer compound having an oxazoline group is preferably a copolymer containing a structural unit derived from the low molecular weight compound having an oxazoline group and a structural unit derived from a (meth)acrylic acid ester containing a polyalkylene oxide chain.

Examples of the polyalkylene oxide chain include polymethylene oxide, polyethylene oxide, polypropylene oxide, and polybutylene oxide. The number of repeating units of the polyalkylene oxide chain is preferably 3 to 100.

Examples of (meth)acrylic acid ester containing a polyalkylene oxide chain include methoxypolyethylene glycol (meth)acrylic acid, ethoxypolyethylene glycol (meth)acrylic acid, and methoxypolypropylene glycol (meth)acrylic acid. Lycol, and (meth)acrylic acid ethoxypolypropylene glycol are included.

The polymer compound having an oxazoline group is a structural unit derived from the low molecular weight compound having an oxazoline group, and a structure derived from monomers other than the structural unit derived from a (meth)acrylic acid ester containing a polyalkylene oxide chain. It may include units.

Other monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and iso. Alkyl group-containing monomers such as butyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and cyclohexyl (meth)acrylate; Hydroxy-containing monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate; Epoxy group-containing monomers such as glycidyl (meth)acrylate and allyl glycidyl ether; Carboxyl group-containing monomers such as (meth)acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and styrenesulfonic acid, and their salts (for example, sodium salts, potassium salts, ammonium salts, and tertiary amine salts); (meth)acrylamide, N-alkyl(meth)acrylamide, N,N-dialkyl(meth)acrylamide, N,N-dialkyl(meth)acrylate (examples of alkyl groups: methyl group, ethyl group, n-view amide group-containing monomers such as ethyl group, isobutyl group, etc.), acryloylmorpholine, N-methylol (meth)acrylamide, and N-phenyl (meth)acrylamide; monomers of acid anhydrides such as maleic anhydride and itaconic anhydride; Vinyl isocyanate, allyl isocyanate, styrene, α-methyl styrene, vinyl methyl ether, vinyl ethyl ether, vinyl trialkoxysilane, alkyl maleic acid monoester, alkyl fumaric acid monoester, alkyl ita Examples include conic acid monoester, (meth)acrylonitrile vinylidene chloride, ethylene, propylene, vinyl chloride, vinyl acetate, and butadiene.

The polymer compound having an oxazoline group is preferably water-soluble from the viewpoint of environmental impact.

The weight average molecular weight of the polymer compound having an oxazoline group is not particularly limited, but is preferably 40,000 or more, more preferably 40,000 to 200,000, and even more preferably 70,000 to 150,000.

The polymer compound having an oxazoline group may be a commercial product. Commercially available products include, for example, Epochros K-2010E, Epochros K-2020E, Epochros K-2030E, Epochros WS-700, and Epochros WS-300 (above, manufactured by Nippon Shokubai Co., Ltd.). .

In the composition for forming a peeling layer, only one type of oxazoline compound may be used, and two or more types may be used.

The content of the oxazoline compound is preferably 1% by mass or more, based on the total solid content of the composition for forming a release layer, and is more preferably 10% by mass or more from the viewpoint of superior solvent resistance. The upper limit of the content of the oxazoline compound is, for example, 80 mass%. Since the peelability is more excellent, the content of the oxazoline compound is preferably less than 30% by mass, and more preferably 28% by mass or less.

In the composition for forming a release layer, the mass ratio of the content of the silicone compound to the content of the oxazoline compound is preferably 0.05 to 10, and is more preferably 0.1 to 10 because of superior peelability and solvent resistance. It is more preferable that it is 0.3 to 6. When the mass ratio is 0.1 or more, peelability improves. On the other hand, when the mass ratio is 10 or less, solvent resistance improves.

[Acid-generating compounds]

The composition for forming a peeling layer preferably contains an acid-generating compound. If an acid-generating compound is contained, the crosslinking reaction by the oxazoline compound is promoted, and thus the solvent resistance of the peeling layer is further improved.

An acid-generating compound is a compound that generates acid by heat. Examples of acid-generating compounds include onium compounds.

Suitable examples of onium compounds include ammonium salts, sulfonium salts, oxonium salts, iodonium salts, phosphonium salts, nitronium salts, nitrosonium salts, and diazonium salts.

Specific examples of onium compounds include monoammonium phosphate, diammonium phosphate, ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium p-toluenesulfonate, ammonium sulfamate, ammonium imidedisulfonate, tetrabutylammonium chloride, and benzyltrimethyl chloride. Ammonium salts such as ammonium, triethylbenzylammonium chloride, tetrabutylammonium boron tetrafluoride, intrabutylammonium hexafluoride, tetrabutylammonium perchlorate, and tetrabutylammonium sulfate; Trimethylsulfonium iodide, boron trimethylsulfonium tetrafluoride, boron diphenylmethylsulfonium tetrafluoride, boron tetrafluoride benzyltetramethylenesulfonium, antimony hexafluoride 2-butenyltetramethylenesulfonium, antimony hexafluoride 3 -Sulfonium salts such as methyl-2-butenyltetramethylenesulfonium; oxonium salts such as boron tetrafluoride and diphenyl iodonium; iodonium salts such as diphenyl iodonium chloride and boron diphenyl iodonium tetrafluoride; Phosphonium salts such as antimonycyanomethyl tributylphosphonium hexafluoride and boron tetrafluoride ethoxycarbonylmethyl tributylphosphonium; Nitronium salts such as boron nitronium tetrafluoride; Nitrosonium salts such as nitrosonium boron tetrafluoride; and diazonium salts such as 4-methoxybenzene diazonium chloride.

Among them, the onium compound is preferably an ammonium salt, a sulfonium salt, an iodonium salt, or a phosphonium salt, more preferably an ammonium salt, and still more preferably an ammonium phosphate, from the viewpoint of shortening the curing time.

In the composition for forming a peeling layer, only one type of acid-generating compound may be used, and two or more types may be used.

The content of the acid-generating compound is preferably 0.1% by mass to 5.0% by mass, based on the total solid content of the composition for forming a release layer, and is 0.8% by mass to 7% by mass because of superior peelability and solvent resistance. It is more preferable.

[Non-silicone resin containing acid radicals]

It is preferable that the composition for forming a release layer further contains an acidic radical-containing non-silicone resin. Non-silicone resin containing an acid group means a non-silicone resin containing an acid group.

If a non-silicone resin containing an acid group is contained, the crosslinking density increases and the solvent resistance further improves. In addition, it is believed that the silicone compound contained in the composition for forming a release layer is localized in the surface layer to hydrophobize the surface, and the non-silicone resin crosslinks with the oxazoline compound inside the release layer, resulting in better peelability and solvent resistance. .

Examples of the acid group include a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group. Among them, it is preferable that the acid group is a carboxy group from the viewpoint of crosslinkability with the oxazoline compound.

Non-silicone resin refers to a resin other than a silicone resin, and refers to a resin that does not contain a silicone structure in the molecule. Non-silicone resins include urethane resins, olefin resins, alkaline resins, acrylic resins, polyester resins, melamine resins, epoxy resins, phenol resins, and styrene-butadiene copolymers, and urethane resins and It is preferable that it is at least one type selected from the group consisting of olefin resins. Since urethane resins and olefin resins have flexible main chains, their crosslinked products with oxazoline compounds are thought to have excellent flexibility. Therefore, for example, when a stretching process is performed after applying the composition for forming a peeling layer on a polyester film, which will be described later, the film formed by applying the composition for forming a peeling layer is also followed and stretched, so that the peeling Minor defects such as cracks are unlikely to occur in the layer. As a result, it is thought that even when applied for manufacturing ceramic green sheets, minute irregularity defects are suppressed.

Among them, from the viewpoint of suppressing defects in the ceramic green sheet, it is preferable that the non-silicone resin containing an acid group is at least one selected from the group consisting of a urethane resin containing an acid group and an olefin resin containing an acid group. Specific examples of acid groups are as above.

The urethane resin is not limited as long as it is a polymer having a urethane bond in the main chain, and known urethane resins such as the reaction product of a polyisocyanate compound and a polyol compound can be used.

Urethane resin can improve its solvent resistance by, for example, adjusting the crosslinking reaction with the oxazoline compound by adjusting the structure and flexibility of the polyol compound and polyisocyanate compound that serve as raw materials, respectively. . From the point of superior solvent resistance, it is preferable that the urethane resin contains a polyester structure.

Commercially available acid group-containing urethane resins include, for example, Hydran (registered trademark) AP-20, AP-40N, and AP-201 (manufactured by DIC Corporation), Takelac (registered trademark) W-605, W- 5030 and W-5920 (above, manufactured by Mitsui Chemicals), Super Flex (registered trademark) 210 and 130, and Elastron (registered trademark) H-3-DF, E-37 and H-15 (above, Dai (made by Ichi Gogyo Seiyaku Temple).

The olefin resin may be a resin containing a structural unit derived from olefin in the main chain. By having a structural unit derived from olefin in the main chain, the crosslinking reaction with the oxazoline compound can be adjusted and solvent resistance can be improved.

The olefin is not particularly limited, but alkenes having 2 to 6 carbon atoms are preferable, ethylene, propylene, or hexene are more preferable, and ethylene is still more preferable.

The structural unit derived from the olefin contained in the polyolefin is preferably 50 mol to 99 mol%, and more preferably 60 mol to 98 mol%, relative to all structural units of the polyolefin.

Examples of the acid group-containing olefin resin include copolymers obtained by modifying the above-described olefin resin with an acid-modifying component such as an unsaturated carboxylic acid or its anhydride.

Commercially available products of acid group-containing olefin resins include, for example, the Zaixen (registered trademark) series such as Zaixen AC, A, L, NC, and N (manufactured by Sumitomo Seika Co., Ltd.), Chemipearl S100, S120, S200, and S300. , Chemipearl (registered trademark) series such as S650 and SA100 (manufactured by Mitsui Chemicals Co., Ltd.), Hi-Tech (registered trademark) series such as Hi-Tech S3121 and S3148K (manufactured by Toho Chemicals Co., Ltd.), Arobase SE-1013 , Arobase (registered trademark) series such as SE-1010, SB-1200, SD-1200, DA-1010 and DB-4010 (manufactured by Unitica Co., Ltd.), Harden AP-2, NZ-1004 and NZ- 1005 (manufactured by Toyobo Co., Ltd.), and Sepoljeon G315 and VA407 (manufactured by Sumitomo Seika Co., Ltd.).

Additionally, acid-modified olefin resins described in [0022] to [0034] of Japanese Patent Application Laid-Open No. 2014-076632 can also be preferably used.

Additionally, as described above, the silicone compound contained in the composition for forming a release layer may be a silicone compound containing an acid group.

In the release film of the present disclosure, it is preferable that the composition for forming a release layer satisfies at least one of Condition 1 and Condition 2 below.

Condition 1: The silicone compound contains an acid group.

Condition 2: The composition for forming a release layer further contains an acidic radical-containing non-silicone resin.

The release film of the present disclosure includes a polyester base material and a release layer, and the release layer is formed by crosslinking a composition containing a silicone compound and an oxazoline compound, and the composition for forming the release layer satisfies the conditions 1 and 1 above. It is preferable that it is a peeling film that satisfies at least one of 2.

Among the composition for forming a release layer, only one type of non-silicone resin containing an acid group may be used, and two or more types may be used.

In the composition for forming a release layer, the content of the acidic radical-containing non-silicone resin is preferably 0% by mass to 80% by mass with respect to the total solid content of the composition for forming a release layer, and has superior peelability and solvent resistance. , it is more preferable that it is 15 mass% to 68 mass%.

In the composition for forming a release layer, the mass ratio of the content of the acid group-containing non-silicone resin to the content of the silicone compound is preferably 0.1 to 50, and is more preferably 1 to 30 because of the excellent peelability and solvent resistance. desirable. When the mass ratio is 1 or more, solvent resistance improves. On the other hand, when the mass ratio is 30 or less, peelability improves.

[additive]

The peeling layer may contain additives other than the above components. As additives, additives such as surfactants, light and heavy peeling additives for adjusting the peeling force, adhesion improvers, and antistatic agents may be added.

As the surfactant, the same surfactant applied to the particle-containing layer can be used. The preferred embodiment of the surfactant that may be contained in the release layer is the same as the preferred embodiment of the surfactant that may be contained in the particle-containing layer.

Additionally, the composition for forming a release layer may contain a crosslinking agent other than the oxazoline compound.

Other crosslinking agents are not particularly limited and known ones can be used.

Other crosslinking agents include, for example, melamine compounds, epoxy compounds, isocyanate compounds, and carbodiimide compounds.

For details on the melamine compound, epoxy compound, and isocyanate compound, the descriptions [0081] to [0083] of Japanese Patent Application Laid-Open No. 2015-163457 can be referred to. The crosslinking agent described in [0082] to [0084] of International Publication No. 2017/169844 can also be preferably used. As a carbodiimide compound, the description of [0038] to [0040] in Japanese Patent Application Publication No. 2017-087421 can be referred to.

For carbodiimide compounds and isocyanate compounds, the crosslinking agents described in [0074] to [0075] of International Publication No. 2018/034294 can also be preferably used.

When the composition for forming a release layer contains another crosslinking agent, the content of the other crosslinking agent is preferably 0.1% by mass to 20% by mass with respect to the total solid content of the composition for forming a release layer.

[Properties of peeling layer]

(thickness)

The thickness of the peeling layer can be set according to the purpose of use and is not particularly limited, but is preferably 0.001 μm to 0.2 μm, and is preferably 0.01 μm to 0.2 μm in that the peel performance and peeling surface smoothness are well balanced. It is more preferable, and 0.03 μm to 0.1 μm is more preferable.

The thickness of the peeling layer is measured by producing a section with a cross-section perpendicular to the main surface of the peeling film and using a scanning electron microscope (SEM) or a transmission electron microscope (TEM). This is taken as the arithmetic mean value of the thickness of the five sections of the above section.

<Particle-containing layer>

The release film of the present disclosure preferably further includes a particle-containing layer, and more preferably includes a release layer, a polyester substrate, and a particle-containing layer in this order.

The particle-containing layer refers to a layer containing particles.

If the release film is provided with a particle-containing layer, the transportability of the release film can be improved. Specifically, it is possible to improve winding quality (suppress blocking), suppress the occurrence of scratches and defects during conveyance, and reduce conveyance wrinkles during high-speed conveyance.

The particle-containing layer may be provided directly on the surface of the polyester substrate or may be provided on the surface of the polyester substrate through another layer, but it is preferable to provide it directly on the surface of the polyester substrate because of better adhesion.

Additionally, the particle-containing layer preferably contains particles and a binder, and may further contain additives.

Hereinafter, particles, binders, and additives will be described.

(particle)

The average particle diameter of the particles contained in the particle-containing layer is not particularly limited, and is preferably 10 nm to 2 μm, more preferably 30 nm to 1.5 μm, and 30 nm to 500 nm because of better transportability and suppressed transfer traces. is more preferable.

In addition, from the viewpoint of superior transportability and suppression of transfer traces, it is preferable that the average particle diameter of the particles contained in the particle-containing layer is larger than the thickness of the particle-containing layer.

As particles contained in the particle-containing layer, one type may be used alone, or two or more types of particles may be used.

When the particle-containing layer contains two or more types of particles with different particle diameters, the particle-containing layer preferably contains at least one type of particle whose average particle diameter is within the above range, and the two or more types of particles with different particle diameters all have an average particle diameter of It is more preferable that the particles fall within the above range.

Examples of particles contained in the particle-containing layer include organic particles and inorganic particles. Among them, when manufacturing a ceramic green sheet, organic particles are preferable from the viewpoint of suppressing the defective rate of the ceramic capacitor manufactured using the obtained ceramic green sheet.

As organic particles, resin particles are preferable. Resins constituting the resin particles include, for example, acrylic resins such as polymethyl methacrylate resin (PMMA), polyester resins, silicone resins, styrene resins, and styrene-acrylic resins. The resin particles may have a crosslinked structure. Examples of resin particles having a crosslinked structure include divinylbenzene crosslinked particles.

In addition, in this disclosure, an acrylic resin means a resin containing a structural unit derived from acrylate or methacrylate.

Examples of inorganic particles include silica particles (silicon dioxide particles), titania particles (titanium oxide particles), calcium carbonate, barium sulfate, and alumina particles (aluminum oxide particles). Among them, the inorganic particles are preferably silica particles from the viewpoint of further improving haze and durability.

The shape of the particles is not particularly limited, and examples include fine particles, spherical shapes, cubic shapes, spindle shapes, scale shapes, aggregated shapes, and irregular shapes. An agglomerated phase means a state in which primary particles are aggregated. The shape of the particles in the agglomerated phase is not limited, but spherical or indeterminate shapes are preferred.

As the aggregated particles, fumed silica particles are preferable. Available commercial products include, for example, the Aerosil series from Nippon Aerosil Co., Ltd.

As non-agglomerated particles, colloidal silica particles are preferred. As commercially available products, for example, the Snotex series manufactured by Nissan Chemical Co., Ltd. can be mentioned.

The particle content in the particle-containing layer is preferably 0.1% by mass to 30% by mass, and 1% by mass to 25% by mass, relative to the total mass of the particle-containing layer, from the viewpoint of transportability and suppressing transfer traces. It is more preferable, and 1% by mass to 15% by mass is more preferable.

Moreover, the content of the particles is preferably 0.0001 mass to 0.01 mass%, and more preferably 0.0005 mass to 0.005 mass%, relative to the total mass of the peeling film.

(Non-polyester resin (binder))

The particle-containing layer preferably contains a non-polyester resin. The non-polyester resin contained in the particle-containing layer has a function as a binder.

Non-polyester resin means resin other than polyester resin. Specifically, the non-polyester resin is at least one selected from the group consisting of acrylic resin, urethane resin, olefin resin, polyvinyl alcohol resin, styrene butadiene resin, and acrylonitrile butadiene resin. It is preferable, and since the effect of this disclosure is more excellent, it is preferable that it is at least 1 type of resin selected from the group consisting of an acrylic resin, a urethane resin, and an olefin resin.

Here, the solubility parameters (SP values) of non-polyester resins (particularly acrylic resins, urethane resins, and olefin resins) and polyester resins are different. That is, since the compatibility of the acrylic resin, urethane resin, and olefin resin with the polyester resin is insufficient, it becomes difficult for impurities such as oligomers to precipitate from the polyester substrate via the particle-containing layer onto the conveying surface. It is assumed that this makes it difficult for protrusions resulting from impurities contained in the polyester base material to occur on the conveyance surface.

Non-polyester resins such as the above-described acrylic resins, urethane resins, and olefin resins are not particularly limited, and known resins can be used.

It is preferable that the non-polyester resin is an acid group-containing non-polyester resin.

Additionally, the particle-containing layer may contain polyester resin.

The acrylic resin is a resin containing a structural unit derived from (meth)acrylate, and may be copolymerized with a vinyl monomer such as styrene. The acrylic resin is not particularly limited, but preferably contains a structural unit derived from (meth)acrylate having an alkyl group of 1 to 12 carbon atoms, and a unit derived from (meth)acrylate having an alkyl group of 1 to 8 carbon atoms. It is more preferable to include structural units.

The acrylic resin may have an acid-modifying component. The acrylic resin may contain a structural unit derived from (meth)acrylic acid as an acid-modified component. Additionally, (meth)acrylic acid may form an acid anhydride or may be neutralized with at least one selected from alkali metals, organic amines, and ammonia.

The acid value of the acrylic resin is preferably 30 mgKOH/g or less, and more preferably 20 mgKOH/g or less. The lower limit of the acid value is not particularly limited and is, for example, 0 mgKOH/g, but in terms of application as an aqueous dispersion, 2 mgKOH/g or more is preferable. By setting the acid value of the acrylic resin within the above range and/or including a structural unit derived from (meth)acrylate having an alkyl group of 1 to 12 carbon atoms, the resin can be made more difficult to be compatible with polyester resin. , precipitation of impurities such as oligomers contained in the polyester substrate in the particle-containing layer can be further suppressed, and defects in the ceramic green sheet can be further suppressed.

The olefin resin may be a resin containing a structural unit derived from olefin in the main chain. By having a structural unit derived from olefin in the main chain, a resin that is difficult to mix with polyester resin can be made, impurities such as oligomers contained in the polyester base material are suppressed from precipitation in the particle-containing layer, and in the ceramic green sheet, defects can be suppressed.

The olefin is not particularly limited, but alkenes having 2 to 6 carbon atoms are preferable, ethylene, propylene, or hexene are more preferable, and ethylene is still more preferable.

The structural unit derived from the olefin contained in the polyolefin is preferably 50 mol to 99 mol%, and more preferably 60 mol to 98 mol%, relative to all structural units of the polyolefin.

As the olefin resin, an olefin resin containing an acid group is preferable. Examples of the acidic radical-containing olefin resin include those similar to the acidic radical-containing olefin resin that may be contained in the composition for forming the peeling layer.

The urethane resin is not limited as long as it is a polymer having a urethane bond in the main chain, and known urethane resins such as the reaction product of a polyisocyanate compound and a polyol compound can be used.

Since it is easy to form a film by application, the urethane resin is preferably an acid group-containing urethane resin or a form containing urethane resin and a dispersant. Specific examples of acid groups are as above.

Urethane resin can be made into a resin that is difficult to compatible with the polyester resin contained in the base material, for example, by adjusting the structure and hydrophobicity (hydrophilicity) of the polyol compound and polyisocyanate compound as raw materials. Precipitation of impurities such as oligomers contained in the polyester substrate in the particle-containing layer is suppressed, and defects in the ceramic green sheet can be suppressed. Since defect suppression can be further improved, the urethane resin may contain a polyester structure.

Examples of the acidic radical-containing urethane resin include those similar to the acidic radical-containing urethane resin that may be contained in the composition for forming the peeling layer.

The non-polyester resin contained in the particle-containing layer may have a crosslinked structure. That is, the particle-containing layer may be a crosslinked membrane.

In order to form a non-polyester resin having a crosslinked structure, a method of forming a particle-containing layer using a composition for forming a particle-containing layer containing a crosslinking agent can be used, as will be described later.

The particle-containing layer may contain one type of binder alone, or may contain two or more types of binders. Moreover, the particle-containing layer may contain one type of non-polyester resin alone, or may contain two or more types of non-polyester resin.

The content of the binder (preferably non-polyester resin) is preferably 30% by mass to 99.8% by mass, and more preferably 50% by mass to 99.5% by mass, relative to the total mass of the particle-containing layer, from the viewpoint of suppressing defects. do.

(additive)

The particle-containing layer may contain additives other than the above particles and binder.

Additives contained in the particle-containing layer include, for example, surfactants, waxes, antioxidants, ultraviolet absorbers, colorants, reinforcing agents, plasticizers, antistatic agents, flame retardants, rust inhibitors, and anti-fungal agents.

The particle-containing layer preferably contains a surfactant because the smoothness of areas other than the areas where projections formed by particles exist on the transport surface are improved.

The surfactant is not particularly limited and includes silicone-based surfactants, fluorine-based surfactants, and hydrocarbon-based surfactants. Among them, it is preferable that the surfactant is a hydrocarbon-based surfactant.

The silicone-based surfactant is not particularly limited as long as it is a surfactant that has a silicon-containing group as a hydrophobic group, and examples include polydimethylsiloxane, polyether-modified polydimethylsiloxane, and polymethylalkylsiloxane. .

Commercially available silicone surfactants include, for example, BYK (registered trademark) -306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-347, BYK-348, and BYK. -349 (above, manufactured by BYK), and KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643 , KF-6020,

The fluorine-based surfactant is not particularly limited as long as it is a surfactant that has a fluorine-containing group as a hydrophobic group, and examples include perfluorooctanesulfonic acid and perfluorocarboxylic acid.

Commercially available fluorine-based surfactants include, for example, Megapak (registered trademark) F-114, F-410, F-440, F-447, F-553, and F-556 (manufactured by DIC), and , Surfron (registered trademark) S-211, S-221, S-231, S-233, S-241, S-242, S-243, S-420, S-661, S-651, and S- 386 (manufactured by AGC Semi Chemical Co., Ltd.).

In addition, as a fluorine-based surfactant, from the viewpoint of improving environmental compatibility, compounds having a linear perfluoroalkyl group with 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), can be replaced. It is preferred to use a surfactant derived from the material.

Examples of hydrocarbon-based surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.

Examples of anionic surfactants include alkyl sulfate, alkylbenzenesulfonate, alkyl phosphate, and fatty acid salt.

Nonionic surfactants include, for example, polyalkylene glycol mono or dialkyl ether, polyalkylene glycol mono or dialkyl ester, and polyalkylene glycol monoalkyl ester/monoalkyl ether. You can.

Examples of cationic surfactants include primary to tertiary alkylamine salts and quaternary ammonium compounds.

Examples of amphoteric surfactants include surfactants that have both an anionic moiety and a cationic moiety in the molecule.

Commercially available anionic surfactants include, for example, Rapizol (registered trademark) A-90, A-80, BW-30, B-90, and C-70 (manufactured by Nichiyu Co., Ltd.); NIKKOL (registered trademark) OTP-100 (above, manufactured by Nikko Chemical Co., Ltd.), KOHACOOL (registered trademark) ON, L-40, and Phosphanol (registered trademark) 702 (above, Toho Kagaku Kogyo Co., Ltd.) ), Byulite (registered trademark) A-5000, and SSS (above, manufactured by Sanyo Kasei Kogyo Co., Ltd.).

Commercially available nonionic surfactants include, for example, Naroacti (registered trademark) CL-95, HN-100 (product name: Sanyo Kasei Kogyo Co., Ltd.), Lisorex BW400 (product name: Kokyu Alcohol Kogyo Co., Ltd.) ), EMALEX (registered trademark) ET-2020 (above, manufactured by Nippon Emulsion Co., Ltd.), and Surfinol (registered trademark) 104E, 420, 440, 465, and Dynol (registered trademark) 604, 607. (Above, manufactured by Nisshin Kagaku Kogyo Co., Ltd.).

Among hydrocarbon-based surfactants, anionic surfactants and/or nonionic surfactants are preferable, and anionic surfactants are more preferable.

The anionic hydrocarbon-based surfactant preferably has a plurality of hydrophobic end groups because smoothness is further improved. The hydrophobic end group may be a part of the hydrocarbon group possessed by the hydrocarbon-based surfactant. For example, a hydrocarbon-based surfactant having a hydrocarbon group having a branched chain structure at the end has a plurality of hydrophobic end groups.

Examples of anionic hydrocarbon-based surfactants having a plurality of hydrophobic end groups include di-2-ethylhexyl sodium sulfosuccinate (having four hydrophobic end groups) and di-2-ethyloctyl sodium sulfosuccinate (having four hydrophobic end groups). has 4), and branched alkylbenzenesulfonate (has 2 hydrophobic terminal groups).

One type of surfactant may be used, or two or more types may be used in combination.

When the particle-containing layer contains a surfactant, the content of the surfactant is preferably 0.1% by mass to 10% by mass relative to the total mass of the particle-containing layer, and is 0.1% by mass to 5% by mass because surface smoothness is superior. is more preferable, and 0.5 mass% to 2 mass% is more preferable.

There are no particular restrictions on the wax, and it may be a natural wax or a synthetic wax. Natural waxes include carnauba wax, candelilla wax, beeswax, montan wax, paraffin wax, and petroleum wax. In addition, the lubricant described in [0087] of International Publication No. 2017/169844 can also be used.

The wax content is preferably 0% by mass to 10% by mass with respect to the total mass of the particle-containing layer.

[Properties of particle-containing layer]

(thickness)

For example, when the particle-containing layer is formed by applying a composition containing particles and a non-polyester resin onto one side of a polyester film, the thickness of the particle-containing layer is often 1 μm or less.

Additionally, when a polyester film on which a particle-containing layer is laminated is formed by co-extrusion, the thickness of the particle-containing layer is often 1 μm to 10 μm.

The thickness of the particle-containing layer is preferably 1 nm to 3 μm, and when manufacturing by coating, from the viewpoint of manufacturing suitability and haze reduction, 1 nm to 500 nm is preferable, 1 nm to 250 nm is more preferable, and 10 nm to 100 nm is preferable. It is more preferable, and 20 nm to 100 nm is particularly preferable.

The thickness of the particle-containing layer is the thickness of the five points of the section, which is measured by producing a section with a cross section perpendicular to the main surface of the release film and using a scanning electron microscope (SEM) or a transmission electron microscope (TEM). It is taken as the arithmetic average.

<Properties of peeling film>

[thickness]

The thickness of the release film is preferably 100 μm or less, more preferably 50 μm or less, and still more preferably 40 μm or less because of excellent peelability. Moreover, the thickness of the release film is preferably 3 μm or more, more preferably 10 μm or more, and still more preferably 20 μm or more, since strength is improved and processability is improved.

The thickness of the release film is measured using the continuous stylus total film thickness. Specifically, it is carried out at five different locations. The arithmetic mean value of the obtained measured values is taken as the thickness.

[Method for producing release film]

The manufacturing method of the release film of this disclosure is demonstrated.

The method for producing the release film of the present disclosure is not particularly limited as long as the release film described above is obtained, and known methods can be used.

For example, the method for producing a release film of the present disclosure is a method for producing a release film including a polyester substrate and a release layer, using a composition for forming a release layer containing a silicone compound and an oxazoline compound. It includes the process of forming.

Among them, since the release film can be produced with good productivity, a preferred method for producing the release film is:

An extrusion molding process for forming an unstretched polyester film by extrusion molding,

A first stretching step of stretching an unstretched polyester film in one of the conveyance direction and the width direction to form a uniaxially stretched polyester film, and stretching the uniaxially stretched polyester film in the other of the conveyance direction and the width direction. A second stretching process of stretching to form a biaxially stretched polyester film is carried out step by step or simultaneously,

A release layer that forms a release layer by applying a release layer forming composition to one surface of the polyester film between the extrusion molding process and the stretching process, between the first stretching process and the second stretching process, or after the stretching process. A manufacturing method including a forming process can be mentioned.

By the above manufacturing method, a release film containing a polyester base material and a release layer is obtained. That is, the polyester substrate is preferably an unstretched polyester film stretched in the conveyance direction and the width direction, respectively.

In addition, the method for producing a release film of the present disclosure forms a particle-containing layer on the other surface of the polyester film between the extrusion molding process and the stretching process, between the first stretching process and the second stretching process, or after the stretching process. A particle-containing layer forming step of applying the composition to form a particle-containing layer may be further included.

By the above manufacturing method, a polyester substrate, a release layer disposed on one side of the polyester substrate, and a particle-containing layer disposed on the side opposite to the side on which the polyester substrate release layer is disposed. A release film comprising

Hereinafter, each step in a preferred embodiment of the manufacturing method of the present disclosure will be described. In addition, the manufacturing method of the present disclosure is not limited to one preferred embodiment, and the following steps can be appropriately omitted.

[Extrusion molding process]

The extrusion molding process is a process of forming an unstretched polyester film by extrusion molding.

More specifically, it is a process of extruding a molten resin containing a raw polyester resin into a film form to form an unstretched polyester film. The polyester resin as a raw material has the same meaning as the polyester resin described in the item [Polyester resin] above.

In addition, in order to produce a polyester film that does not substantially contain particles, it is preferable to use polyester pellets that do not contain particles during extrusion molding.

The extrusion molding method is a method of molding a raw material resin into a desired shape by, for example, extruding a molten body of the raw material resin using an extruder.

The molten body extruded from the extrusion die is cooled and molded into a film shape. For example, the molten body can be molded into a film by contacting the molten body with a casting roll and cooling and solidifying the molten body on the casting roll. When cooling the molten body, it is also desirable to blow wind (preferably cold wind) onto the molten body.

[Stretching process]

The stretching process is a first stretching process of stretching the unstretched polyester film in either the transport direction or the width direction to form a uniaxially stretched polyester film, and stretching the uniaxially stretched polyester film in the transport direction and width. This is a process of carrying out the second stretching process step by step or simultaneously to form a biaxially stretched polyester film by stretching in the other direction.

One of the first stretching process and the second stretching process is a longitudinal stretching process for stretching the polyester film in the conveyance direction (hereinafter also referred to as “vertical stretching”), and the other of the first stretching process and the second stretching process is , This is a transverse stretching process in which a polyester film is stretched in the width direction (hereinafter also referred to as “transverse stretching”). During stretching, polyester polymers are aligned in each direction.

The stretching process may be simultaneous biaxial stretching in which longitudinal stretching and transverse stretching are performed simultaneously, or may be sequential biaxial stretching in which longitudinal stretching and transverse stretching are performed in stages. As a mode of sequential biaxial stretching, for example, a mode in which vertical stretching and transverse stretching are performed in that order; A mode in which vertical stretching, horizontal stretching, and vertical stretching are performed in that order; And, an aspect in which the stretching is carried out in the order of vertical stretching, longitudinal stretching, and transverse stretching can be mentioned. Among them, the sequential biaxial stretching is preferably carried out in the order of vertical stretching and transverse stretching.

Hereinafter, a mode in which longitudinal stretching and transverse stretching are performed in that order will be described, but the manufacturing method is not limited to that mode.

The draw ratio in the longitudinal stretching process is set appropriately, but is preferably 2.0 to 5.0 times, more preferably 2.5 to 4.0 times, and further preferably 2.8 to 4.0 times.

The stretching speed in the longitudinal stretching process is preferably 800%/sec to 1500%/sec, more preferably 1000%/sec to 1400%/sec, and more preferably 1200%/sec to 1400%/sec. Here, the "stretching speed" refers to the value expressed as a percentage divided by the length Δd in the conveyance direction of the polyester film stretched for 1 second in the longitudinal stretching process by the length d0 in the conveyance direction of the polyester film before stretching. am.

In the longitudinal stretching process, it is preferable to heat the unstretched polyester film. This is because vertical stretching becomes easier through heating.

In the transverse stretching process, it is preferable to preheat the uniaxially stretched polyester film before transverse stretching. By preheating the uniaxially stretched polyester substrate, the uniaxially stretched polyester substrate can be easily horizontally stretched.

The stretch ratio (transverse stretch ratio) in the width direction of the uniaxially stretched polyester film in the transverse stretching process is not particularly limited, but is preferably larger than the stretch ratio in the longitudinal stretching process.

The draw ratio in the transverse stretching process is preferably 3.0 times to 6.0 times, more preferably 3.5 times to 5.0 times, and further preferably 3.5 times to 4.5 times.

The stretching speed in the transverse stretching process is preferably 8%/sec to 45%/sec, more preferably 10%/sec to 30%/sec, and more preferably 15%/sec to 20%/sec.

[Particle-containing layer formation process]

The particle-containing layer forming process is a process of forming a particle-containing layer by applying a composition for forming a particle-containing layer to one surface of a polyester film.

The particle-containing layer forming process is performed, for example, between the extrusion molding process and the first stretching process, between the first stretching process and the second stretching process, or after the stretching process. The particle-containing layer forming step is preferably performed between the first stretching step and the second stretching step. The particle-containing layer disposed on one side of the polyester substrate through the particle-containing layer forming step has the same meaning as the layer described in the above particle-containing layer section.

Hereinafter, the mode of applying the composition for forming a particle-containing layer will be described.

First, the composition for forming the particle-containing layer will be described.

The composition for forming a particle-containing layer can be prepared by mixing the components described in the particle-containing layer section above and a solvent.

Examples of solvents include water and alcohol solvents.

The composition for forming a particle-containing layer may contain one type of solvent alone, or may contain two or more types of solvents.

The content of the solvent is preferably 80% by mass to 99.5% by mass, and more preferably 90% by mass to 99% by mass, relative to the total mass of the composition for forming the particle-containing layer.

That is, in the composition for forming a particle-containing layer, the total content of components (solid content) other than the solvent is preferably 0.5% by mass to 20% by mass, and 1% by mass to 10% by mass, based on the total mass of the composition for forming a particle-containing layer. % is more preferable.

For each component other than the solvent in the composition for forming a particle-containing layer, the content of each component relative to the total mass of the solid content of the composition for forming a particle-containing layer is the same as the preferable content of each component relative to the total mass of the particle-containing layer described above. It is desirable to adjust the content of each component in the composition for forming a particle-containing layer so that

Additionally, the composition for forming the particle-containing layer may contain a crosslinking agent.

Examples of the crosslinking agent include the oxazoline compound and the other crosslinking agents.

The content of the crosslinking agent is preferably 0% by mass to 50% by mass with respect to the total mass of the particle-containing layer.

The mass ratio of the crosslinking agent to the binder in the composition for forming a particle-containing layer is preferably 2% by mass to 50% by mass.

The method of applying the composition for forming the particle-containing layer is not particularly limited, and known methods can be used. Examples of the application method include spray coating, slit coating, roll coating, blade coating, spin coating, bar coating, and dip coating.

The heating temperature in forming the particle-containing layer is preferably 180°C or lower, more preferably 150°C or lower, and still more preferably 120°C or lower. The lower limit is not particularly limited and may be 60°C or higher.

Additionally, in order to improve the adhesion between the polyester film and the particle-containing layer, pretreatment such as anchor coat, corona treatment, and plasma treatment may be performed on the surface of the polyester film before providing the particle-containing layer.

[Peel layer formation process]

The peeling layer forming process is a process of forming a peeling layer by applying a composition for forming a peeling layer to a polyester film.

The release layer forming process is performed between the extrusion molding process and the first stretching process, between the first stretching process and the second stretching process, or after the stretching process.

Among them, from the viewpoint of adhesion between the release layer and the polyester substrate, it is preferable that the release layer forming step is performed between the extrusion molding step and the first stretching step, or between the first stretching step and the second stretching step. .

That is, the step of forming the release layer is preferably a step of forming a release layer by applying a release layer forming composition to one side of an unstretched polyester film or a uniaxially stretched polyester film.

When the release layer forming process is performed after the stretching process, it is preferably performed after the cooling process described later, and it is more preferable that it is performed after the winding process and the trimming process described later.

The release layer formed on the surface of the polyester film through the release layer forming process has the same meaning as the layer described in the section on the release layer.

First, the composition for forming a peeling layer will be described.

The composition for forming a release layer preferably contains the components described in the section for the release layer above and a solvent.

Examples of solvents include water, alcohol, ether, ketone, and aromatic hydrocarbons.

The composition for forming a peeling layer may contain one type of solvent alone, or may contain two or more types of solvents.

The content of the solvent is preferably 80% by mass to 99.5% by mass, and more preferably 90% by mass to 99% by mass, with respect to the total mass of the composition for forming a peeling layer.

That is, in the composition for forming a release layer, the total content of components (solid content) other than the solvent is preferably 0.5% by mass to 20% by mass, and 1% by mass to 10% by mass, relative to the total mass of the composition for forming a release layer. % is more preferable.

For each component other than the solvent in the composition for forming a release layer, the content of each component relative to the total mass of solids in the composition for forming a release layer is the same as the preferable content of each component relative to the total mass of the release layer described above. It is preferable to adjust the content of each component in the composition for forming a peeling layer so that it becomes stable.

The method of applying the composition for forming a release layer is not particularly limited, and known methods can be used. Specific examples of the application method are as described in the particle-containing layer forming process.

The heating temperature in forming the peeling layer is preferably 180°C or lower, more preferably 150°C or lower, and still more preferably 120°C or lower. The lower limit is not particularly limited and may be 60°C or higher.

Additionally, in order to improve the adhesion between the polyester film and the release layer, pretreatment such as anchor coat, corona treatment, and plasma treatment may be performed on the surface of the polyester film before providing the release layer.

[Heat setting process]

The method for producing the release film may include a heat setting step as a heat treatment for the polyester film obtained in the stretching step after the stretching step.

In the heat setting process, the polyester film obtained through the stretching process can be heated and heat set. By crystallizing the polyester resin through heat setting, shrinkage of the polyester substrate can be suppressed.

The surface temperature (heat setting temperature) of the polyester film in the heat setting process is not particularly limited, but is preferably less than 240°C, more preferably 235°C or less, and still more preferably 230°C or less. The lower limit is not particularly limited, but is preferably 190°C or higher, more preferably 200°C or higher, and even more preferably 210°C or higher.

The heating time in the heat setting process is preferably 5 seconds to 50 seconds, more preferably 5 seconds to 30 seconds, and still more preferably 5 seconds to 10 seconds.

[Thermal relaxation process]

The method for producing a release film of the present disclosure may include a heat relaxation step after the heat setting step.

In the heat relaxation process, it is preferable to heat relax the polyester film heat-set by the heat-setting process by heating it at a lower temperature than the heat-setting process. Residual distortion of polyester film can be alleviated through thermal relaxation.

The surface temperature (thermal relaxation temperature) of the polyester film in the heat relaxation process is preferably 5°C or more lower than the heat setting temperature, more preferably 15°C or more lower, and 25°C or more lower. Preferred, and a temperature lower than 30° C. is particularly preferred. That is, the thermal relaxation temperature is preferably 235°C or lower, more preferably 225°C or lower, more preferably 210°C or lower, and especially preferably 200°C or lower.

The lower limit of the thermal relaxation temperature is preferably 100°C or higher, more preferably 110°C or higher, and still more preferably 120°C or higher.

[Cooling process]

The method for producing a release film of the present disclosure may include a cooling step of cooling the heat-relaxed polyester film.

The cooling rate of the polyester film in the cooling process is preferably more than 2000°C/min but less than 4000°C/min, more preferably 2000°C/min to 3500°C/min, and more than 2200°C/min but less than 3000°C/min. is more preferable, and 2300°C/min to 2800°C/min is particularly preferable.

In the cooling process, it is also desirable to include a process for expanding the heat-relaxed polyester film in the width direction (expansion process).

The expansion rate of the polyester film in the width direction by the expansion process, that is, the ratio of the polyester film width at the end of the cooling process to the polyester film width before the start of the cooling process, is preferably 0% or more. And, 0.001% or more is more preferable, and 0.01% or more is more preferable.

The upper limit of the expansion rate is not particularly limited, but is preferably 1.3% or less, more preferably 1.2% or less, and still more preferably 1.0% or less.

[Winding process]

The manufacturing method of the release film of this disclosure may have a winding process of obtaining a roll-shaped polyester film by winding up the polyester film obtained through the said process.

[Trimming process]

The manufacturing method of the present disclosure may include a trimming step of continuously cutting the polyester film along the conveyance direction and cutting off at least one end in the width direction of the polyester film before performing the above-described winding step.

[Other conditions]

The conveyance speed of the polyester film in each process other than the vertical stretching process of the production method of the release film of the present disclosure is not particularly limited, but in the transverse stretching process, heat setting process, heat relaxation process, and cooling process. , in terms of productivity and quality, 50 m/min to 200 m/min is preferable, and 80 m/min to 150 m/min is more preferable.

In addition, in the above production method, a method of forming a particle-containing layer by applying a composition for forming a particle-containing layer has been described in the particle-containing layer forming step. However, the method of forming the particle-containing layer is not limited to the above embodiment and a known method can be used. You can. For example, a method of forming an unstretched polyester film in which a particle-containing layer is laminated by co-extrusion molding is included.

In particular, the method for producing the release film of the present disclosure,

A vertical stretching step of stretching the unstretched polyester film in the conveyance direction,

A step of forming a particle-containing layer by applying a composition for forming a particle-containing layer to one side of the uniaxially stretched polyester film obtained in the longitudinal stretching process;

A step of forming a release layer by applying a release layer forming composition to the other side of the uniaxially stretched polyester film obtained in the longitudinal stretching step;

It is preferable to include a transverse stretching step of stretching the uniaxially stretched polyester film having the particle-containing layer and the peeling layer in the width direction while heating.

[Use of release film]

The release film is preferably a release film (carrier film) used in ceramic green sheet production. The ceramic green sheet manufactured using the above release film can be suitably used in the manufacture of ceramic capacitors, which require multilayering of internal electrodes in accordance with miniaturization and increase in capacity.

In addition, the release film of the present disclosure includes a protective film for dry film resist, a film for forming sheets such as decorative layers and resin sheets, a release film for process manufacturing such as a semiconductor manufacturing process, a release film for a polarizing plate manufacturing process, and, It can also be used as a separator for adhesive films for labels, medical and office supplies, etc.

[Laminate]

The laminate of the present disclosure includes the release film and a layer containing ceramic.

The details of the release film are as above.

The layer containing ceramic is preferably provided directly on the surface of the release film.

Ceramics included in the ceramic-containing layer include, for example, ferroelectric materials such as barium titanate, and paraelectric materials such as titanium oxide and calcium titanate.

The layer containing ceramic preferably includes a binder. The binder is not particularly limited, and examples include polyvinyl butyral.

The laminate of the present disclosure can be manufactured, for example, by applying a ceramic slurry containing ceramic and a solvent onto the peeling surface of the peeling film, and drying the solvent contained in the ceramic slurry. Examples of solvents include ethanol and toluene.

The method for applying the ceramic slurry is not particularly limited, and for example, known methods such as the reverse roll method can be applied.

Example

The present disclosure will be described in more detail below with reference to examples. The materials, usage amounts, ratios, processing details, and processing procedures shown in the following examples can be changed as appropriate without departing from the spirit of the present disclosure. Accordingly, the scope of the present disclosure is not limited to the specific examples shown below.

<Example 1>

(Extrusion molding process)

Pellets of polyethylene terephthalate were produced using the titanium compound described in Japanese Patent Publication No. 5575671 (citric acid chelated titanium complex, VERTEC AC-420, manufactured by Johnson-Mathy Corporation) as a polymerization catalyst. The obtained pellets were dried until the water content was 50 ppm or less, and then placed into the hopper of a twin-screw kneading extruder. Next, it was melted at 280°C and extruded. The molten body (melt) was passed through a filter (hole diameter 3 μm) and then extruded from a die into a cooling drum at 25°C to obtain a film made of unstretched polyethylene terephthalate (unstretched film). Additionally, the extruded molten body (melt) was brought into close contact with the cooling drum by the electrostatic application method.

(Vertical stretching process)

A uniaxially stretched polyester film was produced by stretching the unstretched film in the longitudinal direction (conveyance direction) at 90°C and 3.4 times the conditions.

(Particle-containing layer formation process, peeling layer formation process)

Composition A1 for forming a particle-containing layer shown below was applied to one side of the polyester film uniaxially stretched in the longitudinal direction using a bar coater. The composition L1 for forming a release layer shown below was applied using a bar coater to the surface of the uniaxially stretched polyester film opposite to the surface on which the particle-containing layer was applied. The formed coating film was dried with hot air at 100°C to form a particle-containing layer and a peeling layer. That is, composition A1 for forming a particle-containing layer and composition L1 for forming a release layer were in-line coated on a uniaxially stretched polyester film. At this time, the application amounts of composition A1 for forming a particle-containing layer and composition L1 for forming a peeling layer were adjusted so that the thickness of the particle-containing layer after transverse stretching described later was 40 nm and the thickness of the peeling layer was 100 nm.

The polyester film that has undergone the longitudinal stretching process, the peeling layer forming process, and the particle-containing layer forming process is stretched in the width direction using a tenter under the conditions of a stretching temperature of 120°C, a stretching ratio of 4.2 times, and a stretching speed of 50%/sec. Thus, a biaxially stretched polyester film was produced. Next, it was heat-set at a temperature of 227°C for 6 seconds and further thermally relaxed by 4% at 190°C. After that, it was cooled at a rate of 2500°C/min, both ends of the film were trimmed, extrusion processing (knurling) was performed, and then the film was wound at a tension of 40 kg/m. The thickness of the obtained peeling film was 31 μm, the width was 1.5 m, and the winding length was 7000 m.

[Preparation of composition L1 for forming a release layer]

・Silicon compound: Silicone A (product name "X-22-3701E", manufactured by Shin-Etsu Chemical Co., Ltd., silicone compound having a carboxyl group, solid content concentration 10% by mass diluted in water)... 80 parts by mass

· Oxazoline compound: Oxazoline A (product name “Epocross K-2010E”, Tg: -50°C, manufactured by Nippon Shokubai Co., Ltd., solid content concentration 40% by mass aqueous dispersion)… 23.1 parts by mass

· Diammonium phosphate (product name “Diammonium phosphate”, manufactured by Nippon Kagaku Kogyo Co., Ltd., solid content concentration 3% by mass, diluted in water)… 20 parts by mass

・Acid group-containing non-silicone resin: Urethane resin A (product name "Super Flex (registered trademark) 210", manufactured by Daiichi Kogyo Seiyaku Co., Ltd., ester-based urethane aqueous dispersion, solids concentration of 35% by mass mixed with water) Concentration adjusted to 25% by mass)... 86.4 parts by mass

・Surfactant A (product name "Naroact CL95", manufactured by Sanyo Kasei Kogyo Co., Ltd., nonionic surfactant, solid content concentration 1% by mass aqueous solution)... 32 parts by mass

· Surfactant B (product name "Rapisol (registered trademark) A-90", di-2-ethylhexyl sodium sulfosuccinate, manufactured by Nichiyu Co., Ltd., solid content concentration 1 mass% water dilution)... 24 parts by mass

·Distilled water… 734 parts by mass

[Preparation of composition A1 for forming particle-containing layer]

· Cross-linked PMMA particles (Eposta (registered trademark) MX050W, manufactured by Nippon Shokubai Co., Ltd., average particle diameter 70 nm, solid content concentration 10% by mass aqueous dispersion)... 8 parts by mass

·Urethane resin C (product name “Hydran (registered trademark) AP-40N”, manufactured by DIC Corporation, aqueous dispersion with solid content concentration adjusted to 25% by mass)… 157 parts by mass

· Surfactant B (product name "Rapisol (registered trademark) A-90", di-2-ethylhexyl sodium sulfosuccinate, manufactured by Nichiyu Co., Ltd., solid content concentration 1 mass% water dilution)... 56 parts by mass

·water… 779 parts by mass

<Example 2 to Example 21, Comparative Example 1>

Regarding the solid content contained in the composition for forming a release layer, the type and content (% by mass) of each component were changed to those shown in Table 1, and the type of resin contained in the composition for forming a particle-containing layer was changed to those shown in Table 1. Except this, a release film was produced in the same manner as in Example 1.

<Comparative Example 2 ~ Comparative Example 3>

With respect to the solid content contained in the composition for forming a release layer, the type and content (% by mass) of each component are changed to those shown in Table 1, a particle-containing layer is not provided, and uniaxial stretching is performed before applying the composition for forming a release layer. A release film was produced in the same manner as in Example 1, except that the surface of the polyester film was subjected to corona treatment.

The details of each component listed in Table 1 are as follows.

(silicon compound)

Silicone A: Silicone resin having a carboxyl group (product name “X-22-3701E”, manufactured by Shin-Etsu Chemical Co., Ltd.)

Silicone B: Acrylic silicone composite resin (product name “Ceranate WSA1070”, manufactured by DIC Co., Ltd.)

・Silicone C: Product name "X-62-7655" (a silicone-containing material, manufactured by Shin-Etsu Chemical Co., Ltd.) and product name "X-62-7622" (a silicone-containing material, Shin-Etsu Chemical Co., Ltd.) A mixture of product name "CAT-7605" (catalyst, manufactured by Shin-Etsu Chemical Co., Ltd.) at a mass ratio of 95:5:1.

(Cross-linking agent)

・Oxazoline A: Oxazoline compound (product name “Epocross K-2010E”, manufactured by Nippon Shokubai Co., Ltd.)

・Oxazoline B: Oxazoline compound (product name “Epocross K-2020E”, manufactured by Nippon Shokubai Co., Ltd.)

・Oxazoline C: Oxazoline compound (product name “Epocross K-2030E”, manufactured by Nippon Shokubai Co., Ltd.)

・Oxazoline D: Oxazoline compound (product name “Epocross WS-700”, manufactured by Nippon Shokubai Co., Ltd.)

・Oxazoline E: Oxazoline compound (product name “Epocross WS-500”, manufactured by Nippon Shokubai Co., Ltd.)

・Oxazoline F: Oxazoline compound (product name “Epocross WS-300”, manufactured by Nippon Shokubai Co., Ltd.)

·Melamine A: Hexamethoxymethylolmelamine

・Melamine B: Product name “Nikalak (registered trademark) MW-035”, manufactured by Sanwa Chemical Co., Ltd., melamine resin

(acid-generating compound)

·Diammonium phosphate

(non-silicone resin)

・Urethane Resin A: Product name “Super Flex (registered trademark) 210”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

・Urethane Resin B: Product name “Adeka Bone Titer (registered trademark) HUX-524”, manufactured by ADEKA Co., Ltd.

・Urethane resin C: Product name “Hydran (registered trademark) AP-40N”, manufactured by DIC Corporation

· Urethane resin D: isophorone diisocyanate: terephthalic acid: isophthalic acid: ethylene glycol: diethylene glycol: dimethylolpropanoic acid = 12:19:18:21:25:5 ( polyester-based urethane resin formed by mol%)

・Olefin resin: Product name “Jaixen (registered trademark) NC”, manufactured by Sumitomo Seika Co., Ltd.

・Polyester resin: Product name “Vironal MD1245”, manufactured by Toyobo Co., Ltd.

・SBR resin: Product name “NIPOL LX415”, manufactured by Nippon Xeon Co., Ltd.

Acrylic resin: Acrylic resin prepared by the method described below

· Long-chain alkyl group-containing resin: a long-chain alkyl group-containing resin prepared according to the method described in [0122] of International Publication No. 2020/017289.

-Preparation of acrylic resin-

In a three-necked flask, methyl methacrylate, hydroxyethyl methacrylate, and urethane acrylate oligomer (product name "Artrezine (registered trademark) UN-3320HA", manufactured by Negami Kogyo Co., Ltd., number of acryloyl groups) 6) was added at a mass ratio of 94/1/5, and 2 parts by mass of sodium dodecylbenzenesulfonate was added for a total of 100 parts by mass of the monomer to obtain a monomer solution. In another reaction vessel, 60 parts by mass of the monomer solution, 200 parts by mass of isopropyl alcohol, and 5 parts by mass of potassium persulfate were added, heated to 60°C, and stirred for 20 minutes to obtain mixed solution A. Next, a mixed solution consisting of 40 parts by mass of the monomer solution, 50 parts by mass of isopropyl alcohol, and 5 parts by mass of potassium persulfate was prepared, and it was added dropwise to the mixed solution A over 2 hours using a dropping funnel. After completion of dropwise addition, reaction was performed for 2 hours while heated at 60°C. After cooling the obtained reaction liquid to 25°C, 60 parts by mass of 25% ammonia water and 900 parts by mass of pure water were added, and isopropyl alcohol and unreacted monomers were distilled off under reduced pressure while heating to 60°C to obtain an aqueous dispersion of acrylic resin. got it

(Surfactants)

・Surfactant A: Product name “Naroact CL95”, manufactured by Sanyo Kasei Kogyo Co., Ltd.

・Surfactant B: Product name “Rapizol (registered trademark) A-90”, manufactured by Nichiyu Co., Ltd.

・Surfactant C: Product name “Plus Coat RY-2”, manufactured by Gokagaku Kogyo Co., Ltd.

Using the produced release film, evaluation was performed regarding peelability, solvent resistance, and defects. The evaluation method is as follows.

<Peelability>

100 parts by mass of barium titanate powder (BaTiO ₃ ; manufactured by Sakai Chemical Industry Co., Ltd., product name "BT-03") as a ceramic powder, and polyvinyl butyral resin (product name "S-REC (registered trademark) B·K BM-) as a binder. 2", manufactured by Sekisui Chemical Industries, Ltd.), 8 parts by mass, 4 parts by mass of dioctyl phthalate as a plasticizer (product name "dioctyl phthalate grade 1", manufactured by Kanto Chemical Corporation), and a mixed solution of toluene and ethanol (mass ratio) 6:4) 135 parts by mass were mixed. A ceramic slurry was prepared by dispersing the mixed solution using a ball mill in the presence of zirconia beads and removing the beads from the obtained dispersion.

The release films produced in Examples and Comparative Examples were cut to a width of 250 mm and a length of 10 m. The cut release film was stored in an environment at room temperature and humidity (25°C, 50% RH) for one week. The prepared ceramic slurry was applied to the entire peeled surface of the peeled film after storage so that the film thickness after drying was 3 μm using a die coater. Afterwards, the obtained coating film was dried at 100°C for 2 minutes using a dryer. As a result, a release film with a ceramic green sheet was obtained.

A polyester adhesive tape (model number "No. 31B", manufactured by Nitto Denko Co., Ltd.) was attached to the surface of the ceramic green sheet in the release film with the ceramic green sheet. In that state, after standing at room temperature (25°C) for 24 hours, the release film with the ceramic green sheet was cut to a width of 20 mm to produce a test sample. The adhesive tape side of the test sample was fixed to the surface of the glass plate, and using an A&DJ Tensilon universal testing machine, the peeling angle was 180° and the peeling speed was 100 mm/min, and the peeling film with the ceramic green sheet was peeled off. The peeling film was peeled, and the force required for peeling was measured. Peelability was evaluated based on the force required for peeling. The evaluation criteria are as follows.

A: The force required for peeling was 45 mN or less.

B: The force required for peeling was more than 45 mN and less than 100 mN.

C: The force required for peeling was over 100 mN.

<Solvent resistance>

For the release films produced in Examples and Comparative Examples, using a wess containing a mixed solution of methyl ethyl ketone and toluene (mass ratio 1:1), the surface of the release layer was subjected to a load of 1000 g/cm ² vertically 5 times. Polished horizontally 5 times. After that, the surface of the peeling layer was observed with the naked eye, and solvent resistance was evaluated based on the dissolution state of the peeling layer. The evaluation criteria are as follows.

A: The peeling layer is not dissolved at all.

B: The peeling layer was partially dissolved

C: The peeling layer was completely dissolved.

<Defect Evaluation 1>

A release film with a ceramic green sheet was obtained in the same manner as the method described in the evaluation of peelability, except that the application amount of the ceramic slurry was adjusted so that the film thickness after drying of the ceramic slurry was 1 μm. After being wound into a roll shape, a fluorescent lamp is illuminated from the release film side of the unwinding release film with ceramic green sheet, and an area of 1 m ² on the surface of the ceramic green sheet is observed with the naked eye to detect minute irregularities such as pinholes ( The presence or absence of (hereinafter referred to as uneven defects) was confirmed. Based on the number of defects identified, the defects were evaluated. The evaluation criteria are as follows.

A: No uneven defects were confirmed on the ceramic green sheet.

B: 1 to 10 uneven defects were confirmed on the ceramic green sheet.

C: More than 11 uneven defects were confirmed on the ceramic green sheet.

<Defect Evaluation 2>

The peeling films obtained in each example and each comparative example were stored in a room temperature and humidity environment for 3 months. Using the release film after storage for 3 months, the release film with a ceramic green sheet was prepared in the same manner as the method described in the evaluation of peelability, except that the application amount of the ceramic slurry was adjusted so that the film thickness after drying of the ceramic slurry was 1 μm. got it Evaluation was performed in the same manner as defect evaluation 1. The evaluation criteria are as follows.

A: No uneven defects were confirmed on the ceramic green sheet.

B: 1 to 10 uneven defects were confirmed on the ceramic green sheet.

C: More than 11 uneven defects were confirmed on the ceramic green sheet.

The evaluation results are shown in Table 1. In Table 1, in the column of the release layer, the type and content (% by mass) of each component contained in the composition for forming the release layer are described. Content is the content of solid content of each component. In the particle-containing layer column, the type of resin contained in the composition for forming the particle-containing layer is described.

Non-silicone resin means a resin other than a silicone resin, and "Y" is written when it contains an acid group, and "N" is written when it does not contain an acid group. In addition, “non-silicone resin/acidic group-containing silicone compound” means the mass ratio of the content of the acidic radical-containing non-silicone resin to the content of the silicone compound. “Silicone compound/oxazoline compound” means the mass ratio of the content of the silicone compound to the content of the oxazoline compound.

[Table 1]

The release films of Examples 1 to 21 include a polyester base material and a release layer, and the release layer is formed by crosslinking a composition containing a silicone compound and an oxazoline compound, so that it has peelability and solvent resistance. I could see that this was excellent.

On the other hand, it was found that the release films of Comparative Examples 1 and 2 were inferior in peelability because the composition for forming the release layer did not contain a silicone compound.

It was found that the release film of Comparative Example 3 had poor solvent resistance because the composition for forming the release layer did not contain an oxazoline compound.

In Example 8, it was found that since the composition for forming a release layer contained an acidic radical-containing urethane resin, the occurrence of uneven defects was suppressed compared to Examples 5 and 6. In addition, in Example 4, it was found that since the composition for forming a release layer contained an olefin resin containing an acid group, the occurrence of uneven defects was suppressed compared to Examples 5 and 6.

In Example 17, it was found that the composition for forming a release layer had excellent solvent resistance compared to Example 16 because the mass ratio of the content of the acid group-containing non-silicone resin to the content of the silicone compound was 1 or more.

In Example 17, it was found that the peelability was excellent compared to Example 18 because the mass ratio of the content of the acid group-containing non-silicone resin to the content of the silicone compound in the composition for forming a release layer was 30 or less.

From Examples 15 to 18, it was found that when the content of the silicone compound in the composition for forming a release layer was 5% by mass to 76% by mass, the peelability and solvent resistance were more excellent.

In Example 17, it was found that the composition for forming a release layer had excellent solvent resistance compared to Example 16 because the mass ratio of the content of the silicone compound to the content of the oxazoline crosslinking agent was 0.1 or more.

In Example 17, it was found that the peelability was excellent compared to Example 18 because the mass ratio of the content of the silicone compound to the content of the oxazoline crosslinking agent in the composition for forming a release layer was 10 or more.

In Examples 8 and 20, it was found that the generation of uneven defects was suppressed compared to Example 19 because the particle-containing layer contained a non-polyester resin.

Claims (16)

Comprising a polyester base material and a release layer,
A release film in which the release layer is formed by crosslinking a composition containing a silicone compound and an oxazoline compound. In claim 1,
A release film wherein the composition contains an acid-generating compound. In claim 2,
A release film wherein the acid-generating compound is ammonium phosphate. The method according to any one of claims 1 to 3,
A release film wherein the polyester substrate is substantially free of particles. The method according to any one of claims 1 to 3,
A release film wherein the composition satisfies at least one of Condition 1 and Condition 2 below.
Condition 1: The silicone compound contains an acid group.
Condition 2: The composition further contains an acid group-containing non-silicone resin. In claim 5,
The composition further contains an acid group-containing non-silicone resin,
A release film, wherein the acidic group-containing non-silicone resin is at least one selected from the group consisting of an acidic group-containing urethane resin and an acidic group-containing olefin resin. In claim 5,
The composition further contains an acid group-containing non-silicone resin,
A release film wherein, in the composition, the mass ratio of the content of the acid group-containing non-silicone resin to the content of the silicone compound is 1 to 30. The method according to any one of claims 1 to 3,
A release film whose mass ratio of the content of the silicone compound to the content of the oxazoline compound in the composition is 0.1 to 10. The method according to any one of claims 1 to 3,
A release film wherein the release layer has a thickness of 0.001 μm to 0.2 μm. The method according to any one of claims 1 to 3,
Further comprising a particle-containing layer,
A release film comprising the release layer, the polyester substrate, and the particle-containing layer in this order. In claim 10,
A release film in which the particle-containing layer contains a non-polyester resin. In claim 11,
A release film wherein the non-polyester resin is at least one type of resin selected from the group consisting of an acrylic resin, a urethane resin, and an olefin resin. The method according to any one of claims 1 to 3,
For manufacturing ceramic green sheets, release films. A method for producing a release film comprising a polyester substrate and a release layer,
A method for producing a release film, comprising the step of forming a release layer using a composition for forming a release layer containing a silicone compound and an oxazoline compound. In claim 14,
A method for producing a release film, wherein the step of forming the release layer is a step of forming the release layer by applying the release layer forming composition to one side of an unstretched polyester film or a uniaxially stretched polyester film. A laminate comprising the release film according to any one of claims 1 to 3 and a layer containing ceramic.