JP2022081220A - Method for producing release film - Google Patents

Abstract

To provide a method for producing a release film that has excellent releasability and solvent resistance.SOLUTION: A method for producing a release film is provided, comprising the steps of: applying a composition for forming release layer and containing a melamine compound (A), a polyol (B), an acid catalyst (C), and a hydroxyl group-containing modified silicone resin (D) to at least one face of a resin film under a condition satisfying a particular relational expression; then heating them.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a release film having excellent mold release resistance and solvent resistance.

The release film has a release layer on the resin film. As the release film, for example, as disclosed in JP-A-2019-194337 (Patent Document 1), JP-A-2014-54811 (Patent Document 2), etc., the surface of the pressure-sensitive adhesive layer of the protective film is used. It can be used as a separator that protects until time, or as a carrier film for producing ceramic green sheets such as laminated ceramic capacitors and ceramic substrates, as disclosed in Japanese Patent Application Laid-Open No. 2002-192510 (Patent Document 3). Alternatively, as disclosed in JP-A-2005-342981 (Patent Document 4), JP-A-2020-131440 (Patent Document 5), JP-A-2015-107606 (Patent Document 6), etc., the resin is organic. A resin solution dissolved in a solvent is applied onto a release film and dried to form a resin film, and the resin film is wound up, which is used as a carrier film for so-called cast film formation.

As the release layer of the release film, a release layer containing a silicone compound is generally used because it exhibits excellent release properties. However, in the carrier film applications as shown in Patent Documents 4 to 6 described above, the release layer is swollen and dissolved by the organic solvent contained in the resin solution forming the resin film, so that the release film is releasable. May be lost or the silicone compound may be mixed into the resin film to change the physical properties of the surface of the resin film, and improvement has been sought. That is, there has been a demand for a release film having a release layer having excellent mold release resistance and solvent resistance.

As a release film having a release layer having excellent solvent resistance, for example, Japanese Patent Application Laid-Open No. 2019-166656 (Patent Document 7) describes a ceramic obtained by curing a composition containing a binder component and a silicone skioxane. A release film for producing a green sheet is disclosed, and JP-A-2017-78161 (Patent Document 8) discloses a heat containing a methylated melamine resin, a polyol having a molecular weight of 100 to 3000, an acid catalyst, and a hydroxyl group-containing modified silicone resin. A release film having a release layer made of a curable release coating agent is disclosed, and Japanese Patent Application Laid-Open No. 2018-104661 (Patent Document 9) discloses a methylated melamine resin, a hydroxyl group-containing modified silicone resin and / or a silicone-modified hydroxyl group. A release film comprising a heat-curable release coating agent composition containing an acrylic resin and an acid catalyst is disclosed, and Japanese Patent Application Laid-Open No. 2020-23690 (Patent Document 10) discloses a methylated melamine resin and a hydroxyl group-containing organic modification. Disclosed is a release film comprising a water-based antistatic release coating composition containing silicone, an acid catalyst, and a conductive polymer. According to these release films, stable quality can be obtained with respect to releasability, but the quality with respect to solvent resistance may not be stable, and further improvement has been required.

JP-A-2019-194337 Japanese Unexamined Patent Publication No. 2014-54811 JP-A-2002-192510 Japanese Unexamined Patent Publication No. 2005-342981 Japanese Unexamined Patent Publication No. 2020-131440 Japanese Unexamined Patent Publication No. 2015-107606 JP-A-2019-166656 Japanese Unexamined Patent Publication No. 2017-78161 Japanese Unexamined Patent Publication No. 2018-104661 Japanese Unexamined Patent Publication No. 2020-23690

An object of the present invention is to provide a method for producing a release film having excellent mold release resistance and solvent resistance.

The above object of the present invention is achieved by the following invention.
A composition for forming a release layer containing a melamine compound (A), a polyol (B), an acid catalyst (C), and a hydroxyl group-containing modified silicone resin (D) is provided with at least a resin film under the condition of satisfying the following relational expression. A method for producing a release film, which comprises applying it to one surface and then heating it.

(In the formula, X represents the mass portion of the component (D) with respect to 100 parts by mass of the component (A) contained in the composition for forming a release layer, and Y represents (A), (B), (C), and (. D) represents the elapsed time (unit: hr) from the preparation of the release layer forming composition containing each component to the application.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for producing a release film having excellent mold release resistance and solvent resistance.

Hereinafter, the present invention will be described in detail.

As the melamine compound (A) contained in the composition for forming a release layer in the present invention, a compound known as melamine and a derivative thereof can be used, which is obtained by condensing melamine and formaldehyde, and triazine in one molecule. A melamine compound having one or more rings and one or more methylol groups and / or alkoxymethyl groups is preferable. Of these, the compound represented by the following general formula 1 is preferable because it has excellent curability of the release layer forming composition.

In the general formula 1, R ¹ to R ⁶ are independently hydrogen atoms, methylol groups (-CH ₂ OH), methoxymethyl groups (-CH ₂ OCH ₃ ), and ethoxymethyl groups (-CH ₂ OCH ₂ CH ₃ ), respectively. , N-Butoxymethyl group (-CH ₂ OCH ₂ CH ₂ CH ₂ CH ₃ ) and isobutoxymethyl group (-CH ₂ OCH ₂ CH (CH ₃ ) ₂ ). However, at least one of R ¹ to R ⁶ is a methoxymethyl group.

Among the components (A), R ¹ to R ⁶ are imino-based methylated melamine compounds having hydrogen atoms and methoxymethyl groups, and R ¹ to R ⁶ are methylol-based methylated melamine compounds having methylol groups and methoxymethyl groups. , R ¹ to R ⁶ are all methoxymethyl groups, and a fully alkylated methylated melamine compound is preferable because ^a release film having a release layer having excellent release resistance and solvent resistance can be obtained. A fully alkylated methylated melamine compound in which all of ^R6 are methoxymethyl groups is particularly preferable.

The component (A) is commercially available. For example, as a fully alkylated methylated melamine compound, Cymel (registered trademark) 300 manufactured by Ornex Japan Co., Ltd., Cymel 303LF, Cymel 350, and Nikalac manufactured by Sanwa Chemical Co., Ltd. Examples of imino-based methylated melamine compounds such as MW-22, Nicarac MW-30, Nicalac MW-30M, and Nicalac MW-30MLF include Cymel 325N, Cymel 327, and Cymel 703 manufactured by Ornex Japan Co., Ltd. Nikalac MZ-351 manufactured by Sanwa Chemical Co., Ltd., Nikalac MX-730, etc., as methylal-based methylated melamine compounds, Cymel 370N manufactured by Ornex Japan Co., Ltd., Nikalac MS-11 manufactured by Sanwa Chemical Co., Ltd., Nicarac MS-12LF and the like can be exemplified, and any of them can be preferably used.

In the present invention, the composition for forming a release layer may contain the above-mentioned component (A) alone or may contain two or more kinds.

As the polyol (B) contained in the composition for forming a release layer in the present invention, a known compound having two or more hydroxy groups in the molecule can be used. Examples of such polyols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, trimethylolpropane (TMP), pentaerythritol, and the like. Examples thereof include low molecular weight polyols having a molecular weight of less than 500 such as sorbitol, mannitol, and glycerin, polyether polyols, polyester polyols, polycarbonate polyols, acrylic polyols, polyolefin polyols, polycaprolactone polyols, and castor oil-based polyols having a molecular weight of 500 or more. , Not limited to these.

The component (B) is commercially available. For example, exenol (registered trademark) 230, 420, 430, 828, 1020, 1030, 3020, 5030 manufactured by AGC Co., Ltd. can be used as a polyether polyol, and (30, 3020, 5030) can be used as a polyester polyol. Kurare Co., Ltd. P-510, P-1010, P-3010, P-5010, F-510, F-2010, P-520, P-530, etc., Toyokuni Seiyu Co., Ltd. HS 2F-305S, HS 2F -420SHS 2N-521A, etc., Nipponporan (registered trademark) 4002, 4073, 5035, etc. manufactured by Toso Co., Ltd., and as polycarbonate polyols, C-590, C-1090, C-2090, C-3090, etc. manufactured by Kuraray Co., Ltd., etc. , Polycaprolactone polyols such as PLAXEL (registered trademark) 205, 205U, 208, 309, 320, 410, CD210 manufactured by Daicel Co., Ltd., and ARUFON (registered trademark) UH-2041 (Toa Synthetic Co., Ltd.) as acrylic polyols. )) Etc., as polyolefin polyols, NISSO-PB (registered trademark) GI-1000 (manufactured by Nippon Soda Co., Ltd.), etc. , H-420, H-1823, AC-005, AC-009, Y-403, F-15, F-40, F-97 and the like can be exemplified, and any of them can be preferably used.

In the present invention, the composition for forming a release layer may contain the above-mentioned component (B) alone or may contain two or more kinds.

The content of the component (B) in the composition for forming the release layer is not particularly limited, but since a release film having a release layer having excellent solvent resistance can be obtained, 100 parts by mass of the component (A) can be obtained. On the other hand, it is preferably 1 to 100 parts by mass, more preferably 5 to 70 parts by mass, and further preferably 10 to 50 parts by mass.

As the acid catalyst (C) contained in the composition for forming a release layer in the present invention, known inorganic acids and organic acids, and salts and hydrates thereof can be used. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, and examples of the organic acid include carboxylic acids such as formic acid, acetic acid, and oxalic acid, methanesulfonic acid, trifluoromethanesulfonic acid, octanesulfonic acid, nonanesulfonic acid, and decanesulfonic acid. Examples thereof include aliphatic sulfonic acids such as acid and hexadecane sulfonic acid, benzene sulfonic acid, p-toluene sulfonic acid (PTSA), dodecylbenzene sulfonic acid (DBSA), and aromatic sulfonic acid such as naphthalene sulfonic acid. Not limited. When a fully alkylated methylated melamine compound is used as the component (A), using an aliphatic sulfonic acid or an aromatic sulfonic acid as the component (C) is excellent in curability of the composition for forming a release layer at a low temperature. Therefore, aromatic sulfonic acid is particularly preferable because it is excellent in compatibility with the component (A) and the component (B).

In the present invention, the composition for forming a release layer may contain the above-mentioned component (C) alone, or may contain two or more of them.

The content of the component (C) in the release layer forming composition is not particularly limited, but since the release layer forming composition is excellent in curability at a low temperature, the content of the component (A) is 100 parts by mass. It is preferably 0.5 to 25 parts by mass, more preferably 1 to 20 parts by mass.

The hydroxyl group-containing modified silicone resin (D) contained in the composition for forming a release layer in the present invention means a resin having a polyorganosiloxane skeleton in the main chain or side chain and containing a hydroxyl group. Specific examples thereof include, but are not limited to, a hydroxyl group-containing silicone-modified acrylic resin, a hydroxyl group-containing polyether-modified silicone resin, a hydroxyl group-containing polyester-modified silicone resin, a hydroxyl group-containing polyether polyester-modified silicone resin, and an alcohol-modified silicone resin.

The component (D) is commercially available, and specifically, JNC Co., Ltd. silaplane (registered trademark) FM-0411, FM-0425, FM-DA11, FM-DA26, FM-4411, and FM-4425 ( X-22-4039, X-22-4015, X-22-170BX, X-22-170DX, KF-6000, KF-6001, KF-6002 manufactured by Shin-Etsu Chemical Industry Co., Ltd., such as hydroxyl group-containing modified silicone resin). , And KF-6003 (above, alcohol-modified silicone resin), and X-22-4952, X-22-4272, and KF-6123 (above, hydroxyl-containing polyether-modified silicone resin), etc., Big Chemy Japan Co., Ltd. BYK (registered trademark) -370 (polyester-modified silicone resin containing hydroxyl group), BYK-375 (polyester-modified silicone resin containing hydroxyl group), BYK-377 (polyester-modified silicone resin containing hydroxyl group), BYK-SILCLEAN (registered trademark). ) 3700 (hydroxyl-containing silicone-modified acrylic resin), BYK-SILCLEAN3720 (hydroxyl-containing polyether-modified silicone resin) and the like can be exemplified, and any of them can be preferably used.

In the present invention, the composition for forming a release layer may contain the above component (D) alone, or may contain two or more of them.

The content of the component (D) in the composition for forming a release layer is not particularly limited, but since a release film having a release layer having excellent releasability can be obtained, 100 parts by mass of the component (A) can be obtained. On the other hand, 1 to 50 parts by mass is preferable, and 10 to 45 parts by mass is more preferable.

The composition for forming a release layer in the present invention may contain a solvent in addition to the above-mentioned components (A) to (D). The solvent is not particularly limited, and is an ester solvent such as ethyl acetate and butyl acetate, a ketone solvent such as acetone, 2-butanone and cyclohexanone, an aliphatic hydrocarbon solvent such as hexane, heptane and cyclohexane, toluene and xylene. Aromatic hydrocarbon solvents such as methanol, ethanol, 1-butanol, 2-propanol and other alcohol solvents, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and other glycol ethers. From known solvents such as system solvents, N, N-dimethylformamide, N-methyl-2-pyrrolidone, tetrahydrofuran, water, etc., a solvent capable of dissolving each component (A) to (D) can be used.

In the present invention, the composition for forming a release layer may contain the above solvent alone or may contain two or more of them.

The content of the solvent in the composition for forming a release layer is not particularly limited, and the content can be adjusted so as to have a viscosity and a solid content concentration suitable for the coating method described later.

In addition to the above-mentioned components, the composition for forming a release layer includes an ultraviolet absorber, an antioxidant, a silane coupling agent, a pigment, a dye, a pH adjuster, a surfactant, a defoaming agent, a thickener, and a softening agent. , Lubricants, antistatic agents, antiblocking agents, resins (acrylic resin, urethane resin, polyester resin, alkyd resin, etc.) and other known additives may be contained.

In the present invention, the resin film to which the composition for forming a release layer is applied includes a polyolefin resin such as polyethylene and polypropylene, a polyvinyl chloride resin, a vinyl chloride resin such as a vinyl chloride copolymer, an epoxy resin, and a polyarylate resin. , Polysulfone resin, polyether sulfone resin, polyimide resin, fluororesin, phenoxy resin, triacetyl cellulose resin, polyethylene terephthalate resin, polyphenylen sulphide resin, polyethylene naphthalate resin, polycarbonate resin, acrylic resin, cellophane, nylon resin, polystyrene Examples thereof include films of various known resins such as based resins and ABS resins. The thickness of the resin film is not particularly limited, but is preferably 2 to 300 μm because of the excellent flexibility and handleability of the release film obtained in the present invention, more preferably 3 to 200 μm, and particularly preferably. Is 4 to 100 μm. The resin film may have a known layer such as an easy-adhesive layer, a hard coat layer, an antireflection layer, an antiglare layer, and an antistatic layer on at least one surface thereof, and may be subjected to corona treatment, plasma treatment, etc. Known surface modification treatments such as primer treatment and saponification treatment may be performed.

In the present invention, the composition for forming a release layer may be applied to only one surface of the resin film, or may be applied to both sides of the resin film. Examples of the coating method include, but are not limited to, dip coating, slide coating, curtain coating, bar coating, air knife coating, roll coating, gravure coating, spray coating and the like, and known coating methods can be used. The amount of the release layer forming composition applied is not particularly limited, and as described later, the release layer formed on the resin film after heating may be adjusted to have a desired thickness.

In the present invention, the mass portion X of the component (D) with respect to 100 parts by mass of the component (A) contained in the composition for forming a release layer, and the time Y (from the preparation of the composition for forming a release layer to the application). When the product of unit: hr) satisfies the relational expression of 12.5 <X × Y <525, a release film having a release layer having excellent solvent resistance can be obtained, and more preferably 17. 5 <X × Y <400, and particularly preferably 25 <X × Y <325. When X × Y ≦ 12.5 or X × Y ≧ 525, the solvent resistance of the release layer is lowered.

The above formula states that the solvent resistance of the release layer is improved by applying it after a lapse of time, rather than applying it to the resin film immediately after preparing the release layer forming composition. It is shown and is completely different from the conventional idea of pot life. Further, in the above formula, the elapsed time required from the preparation of the release layer forming composition to the application to the resin film changes depending on the content of the component (D) in the release layer forming composition. It shows a completely new fact of doing. The temperature at which the composition for forming a release layer is stored until it is applied is preferably room temperature (1 to 30 ° C.).

After applying the release layer forming composition on the resin film, heating is performed. By heating, the component (A) and the component (B) are cured to form a release layer. When the release layer forming composition contains a solvent, the component (A) and the component (B) are cured after the solvent is dried by heating to form a release layer. The heating method is not particularly limited, and known methods such as heating with a heater and a heat medium, irradiation with energy rays such as infrared rays, hot air, and electromagnetic induction heating can be used. The heating temperature is not particularly limited, but it is preferable to heat the coated surface to 80 ° C. or higher, more preferably 90 ° C. or higher, and particularly preferably 100 ° C. or higher, because a release film having excellent solvent resistance can be obtained. The upper limit is not particularly limited, but the curing of the component (A) and the component (B) proceeds sufficiently at 150 ° C. or lower, so that the temperature is preferably 150 ° C. or lower. The heating time is not particularly limited, but is preferably 0.25 minutes or longer, more preferably 0.5 minutes or longer, and particularly preferably 1 minute or longer, because a release film having a release layer having excellent solvent resistance can be obtained. .. The upper limit is not particularly limited, but 10 minutes or less is preferable from the viewpoint of productivity.

The thickness of the release layer formed on the resin film is not particularly limited, but 0.1 to 10 μm is preferable because the release layer has excellent solvent resistance, and 0.2 to 8 μm is preferable. More preferably, 0.3 to 7 μm is particularly preferable.

The release film obtained by the present invention may have a functional layer on a surface opposite to the surface having the release layer. Such a functional layer contains a known conductive material such as an easy-adhesive layer, a hard coat layer, an antireflection layer, an antiglare layer, and a conductive layer (conductive metal oxide, conductive polymer, mesh metal fine wire pattern, etc.). Layers), pressure-sensitive adhesive layers (layers containing known pressure-sensitive adhesives such as acrylic pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, and urethane pressure-sensitive adhesives), polarizing layers, light-shielding layers, and decorative layers are examples, but are not limited thereto. ..

The use of the release film obtained by the present invention is not limited, and the surface of the pressure-sensitive adhesive layer of a carrier film for casting film formation, a carrier film for molding a ceramic green sheet, a protective film, an adhesive film such as OCA, etc. is used until use. Suitable for use as a separator for protection, a carrier film or cover film for a photosensitive resin layer of a dry film resist, a protective film for a photomask to prevent the resist from adhering to a photomask, a release film for prepreg processing, etc. Can be done.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.

<Preparation of Compositions 1 to 18 for Forming Release Layer>
Prepare the melamine compound (A), the polyol (B), the acid catalyst (C), and the hydroxyl group-containing modified silicone resin (D) by mass (as a solid content) shown in Table 1, and prepare them by 350 mass of 2-butanone. The components and 2-propanol were dissolved in a 1: 1 mixed solvent in an amount of 350 parts by mass to obtain compositions 1 to 18 for forming a release layer.

<Making mold release films 1-47>
The release layer forming compositions 1 to 18 shown in Table 1 are uniformly coated on a polyethylene terephthalate film having a thickness of 12 μm by gravure coating, and heated at 120 ° C. for 2 minutes using a hot air dryer to have a thickness of 2. A release layer of 9.0 μm was formed, and release films 1 to 47 were obtained. For the release layer forming compositions 1 to 6, a release film was prepared by changing the time from preparation to application. Table 2 shows the values of (A) the mass part X of the component (D) with respect to 100 parts by mass of the component, the time Y (unit: hr) from the preparation of the release layer forming composition to the application, and the values of X × Y. Shown in.

<Evaluation of releasability>
In an environment of 23 ° C. and 50% RH, 2 kg of polyester adhesive tape (manufactured by Nitto Denko Corporation, product number No. 31B, 25 mm width, base material thickness 50 μm) is applied to the surface of the release films 1 to 47 having the release layer. The hand rollers of No. 1 were reciprocated once and pasted together. After storing the release film to which the polyester adhesive tape is attached in an environment of 23 ° C. and 50% RH for 30 minutes, a peeling tester (manufactured by Imada Co., Ltd.) is used at a peeling angle of 180 ° and a peeling speed of 300 mm / min. The polyester adhesive tape side was peeled off, and the peeling strength (N / 25 mm) was measured. When the peel strength is less than 0.20N / 25mm, the releasability is excellent, when it is 0.20N / 25mm or more and less than 0.30N / 25mm, the releasability is good, 0.30N / 25mm or more and 0.40N / 25mm. When it was less than, the releasability was evaluated, and when it was 0.40 N / 25 mm or more, the releasability was evaluated. The results are shown in Table 2. Since the release layer of the release film 46 was peeled from the polyethylene terephthalate film in the process of measuring the release strength, the release strength could not be measured and the release property evaluation could not be performed.

<Solvent resistance evaluation>
In the above-mentioned peel strength evaluation, the same applies except that the bonded portion was wiped with gauze containing toluene 50 times before the polyester adhesive tape was bonded to the surface of the release film having the release layer. , The peel strength of the release films 1 to 47 was remeasured. Solvent resistance is excellent when the peel strength measured after wiping with gauze soaked in toluene is 1 times or more and less than 2 times the peel strength measured before wiping, and solvent resistance is when it is 2 times or more and less than 4 times. When the properties were good and 4 times or more and less than 8 times, the solvent resistance was evaluated, and when the properties were 8 times or more, the solvent resistance was not evaluated. The results are shown in Table 2. Since the release film 46 could not be evaluated for releasability, the release film 47 could not be evaluated for releasability, and therefore no solvent resistance evaluation was performed.

From the results in Table 2, the effectiveness of the present invention can be seen.

Claims (1)

A composition for forming a release layer containing a melamine compound (A), a polyol (B), an acid catalyst (C), and a hydroxyl group-containing modified silicone resin (D) is provided with at least a resin film under the condition of satisfying the following relational expression. A method for producing a release film, which comprises applying it to one surface and then heating it.

(In the formula, X represents the mass portion of the component (D) with respect to 100 parts by mass of the component (A) contained in the composition for forming a release layer, and Y represents (A), (B), (C), and (. D) represents the elapsed time (unit: hr) from the preparation of the release layer forming composition containing each component to the application.