JP2022106533A - Mold release layer forming composition and manufacturing method of mold release film - Google Patents

Abstract

To provide a mold release layer formation composition capable of manufacturing a mold release film excellent in mold releasability and solvent resistance and a manufacturing method of the mold release film.SOLUTION: Provided are a composition for forming a release layer containing a melamine compound (A), a xylene polyol (B), an acid catalyst (C), and a hydroxyl group-containing modified silicone resin (D), and a manufacturing method of a mold release film characterized by coating the composition for forming the release layer on at least one surface of a resin film and heating thereafter.SELECTED DRAWING: None

Description

The present invention relates to a composition for forming a release layer capable of producing a release film having excellent mold release property and solvent resistance, and a method for producing a release film.

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 multilayer 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 resin film surface, and improvement has been sought. That is, there has been a demand for a release film having a release layer having excellent releasability 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 silsesquioxane. A release film for producing a green sheet is disclosed, and Japanese Patent Application Laid-Open No. 2020-23690 (Patent Document 8) discloses an aqueous charge containing a methylated melamine resin, a hydroxyl group-containing organically modified silicone, an acid catalyst, and a conductive polymer. A release film comprising a preventive release coating composition is disclosed. Further, Japanese Patent Application Laid-Open No. 2017-78161 (Patent Document 9) contains a thermosetting release coating agent 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 mold layer is disclosed, and Japanese Patent Application Laid-Open No. 2018-104661 (Patent Document 10) contains a methylated melamine resin, a hydroxyl group-containing modified silicone resin and / or a silicone-modified hydroxyl group-containing acrylic resin, and an acid catalyst. A release film composed of a thermosetting release coating composition is disclosed, and in these patent documents, solvent resistance is used as an index for evaluation of curability. 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.

On the other hand, Japanese Patent Application Laid-Open No. 2019-11748 (Patent Document 11) states that it is a non-silicone type, has excellent heat resistance, solvent resistance, adhesion between the release layer and the base material, and antistatic property, and has a light peeling force. As the release film, an antistatic layer and a release layer are sequentially provided on at least one side of the polyester film, and the release layer is a cured layer of a resin composition containing a non-reactive polyolefin, a reactive polyolefin, and a cross-linking agent. A release film is disclosed, and xylylene diisocyanate and N, N, N', N'-tetraglycidyl-m-xylene diamine are described as examples of the cross-linking agent.

Japanese Unexamined Patent Publication No. 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. 2020-23690 Japanese Unexamined Patent Publication No. 2017-78161 JP-A-2018-104661 Japanese Unexamined Patent Publication No. 2019-11748

An object of the present invention is to provide a release layer forming composition capable of producing a release film having excellent mold release property and solvent resistance, and a method for producing a release film.

The above object of the present invention is achieved by the following invention.
(1) A composition for forming a release layer containing a melamine compound (A), a xylene polyol (B), an acid catalyst (C), and a hydroxyl group-containing modified silicone resin (D).
(2) A method for producing a release film, which comprises applying the release layer forming composition according to (1) above to at least one surface of a resin film, and then heating the resin film.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a composition for forming a release layer and a method for producing a release film, which can produce a release film having excellent releasability 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, melamine and a known compound as a derivative thereof can be used, 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 ). , 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 mold release property and solvent resistance can be obtained. A fully alkylated methylated melamine compound in which all of ^R6 is a methoxymethyl group 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, Nicarac MW-30M, and Nicarac 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.

The xylene polyol (B) contained in the composition for forming a release layer in the present invention means a compound having a xylene skeleton in its molecular structure and having two or more hydroxy groups. Of these, a compound in which a multimer composition in which m-xylene is crosslinked with a methylene bond or an ether bond is modified with an alkylphenol or a polyol is preferable, and a multimer composition in which m-xylene is crosslinked with a methylene bond or an ether bond is modified with a polyol. Compounds are particularly preferred.

The component (B) is commercially available. For example, as a compound obtained by modifying a multimer composition in which m-xylene is crosslinked with a methylene bond or an ether bond with an alkylphenol, Nikanol (registered trademark) HP-120 manufactured by Fudo Co., Ltd., Examples thereof include PR-1440 and PR-1440M, and examples of the compound obtained by modifying a multimeric composition in which m-xylene is crosslinked with a methylene bond or an ether bond with a polyol include Nicanol K-100 and K-140 manufactured by Fudo Co., Ltd. , K-140E 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 release layer forming composition is not particularly limited, but since a release film having a release layer having excellent solvent resistance can be obtained, the content of the component (A) is 100 parts by mass. 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.

In the present invention, the composition for forming a release layer may contain a polyol other than the above component (B). 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, castor oil-based polyols, and other polyols having a molecular weight of 500 or more. , Not limited to these.

Polyester polyols other than the above component (B) are commercially available. For example, as polyether polyols, polyester polyols such as Excelol (registered trademark) 230, 420, 430, 828, 1020, 1030, 3020, 5030 manufactured by AGC Co., Ltd. As, P-510, P-1010, P-3010, P-5010, F-510, F-2010, P-520, P-530, etc. manufactured by Kurare Co., Ltd., HS2F-305S manufactured by Toyokuni Oil Co., Ltd. , HS2F-420S, HS2N-521A, etc., Nippon So Co., Ltd. (registered trademark) 4002, 4073, 5035, etc. As a polycaprolactone polyol such as -3090, Praxel (registered trademark) 205, 205U, 208, 309, 320, 410, CD210, etc. manufactured by Daicel Co., Ltd., and as an acrylic polyol, ARUFON (registered trademark) UH-2041 (Toa). As a polyolefin polyol such as Synthetic Co., Ltd., NISSO-PB (registered trademark) GI-1000 (manufactured by Nippon Soda Co., Ltd.), etc., and as a castor oil-based polyol, Ito Oil Co., Ltd. URIC H-30, Examples thereof include H-62, H-420, H-1823, AC-005, AC-009, Y-403, F-15, F-40, F-97, and any of them can be preferably used.

As the acid catalyst (C) contained in the release layer forming composition 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 acids and hexadecane sulfonic acids, benzene sulfonic acids, p-toluene sulfonic acids (PTSA), dodecylbenzene sulfonic acids (DBSA), and aromatic sulfonic acids such as naphthalene sulfonic acids. 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 release layer forming composition at a low temperature. Therefore, it is preferable, and aromatic sulfonic acid is particularly preferable because it has excellent 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 kinds.

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 release layer forming composition 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 ( Hydroxyl group-containing modified silicone resin), etc., manufactured by Shin-Etsu Chemical Co., Ltd. X-22-4039, X-22-4015, X-22-170BX, X-22-170DX, KF-6000, KF-6001, KF-6002 , 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 Chemie Japan Co., Ltd. BYK (registered trademark) -370 (hydroxyl-containing polyester-modified silicone resin), BYK-375 (hydroxyl-containing polyether polyester-modified silicone resin), BYK-377 (hydroxyl-containing polyether-modified silicone resin), 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-mentioned component (D) alone or may contain two or more kinds.

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, the content of the component (A) is 100 parts by mass. 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 release layer forming composition may contain the above solvent alone or may contain two or more kinds of the above solvent.

The content of the solvent in the release layer forming composition 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 release layer forming composition includes an ultraviolet absorber, an antioxidant, a silane coupling agent, a pigment, a dye, a pH adjuster, a surfactant, an antifoaming 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 vinyl chloride resin such as a polyvinyl chloride resin and 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, polyphenylensulfide resin, polyethylene naphthalate resin, polycarbonate resin, acrylic resin, cellophane, nylon resin, polystyrene Examples of films of various known resins such as based resins and ABS resins can be exemplified. The thickness of the resin film is not particularly limited, but is preferably 2 to 300 μm because the release film obtained in the present invention is excellent in flexibility and handleability, more preferably 3 to 200 μm, and particularly preferably. Is 4 to 100 μm. The resin film may have known layers 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 of the resin film, 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 only to one surface of the resin film, or may be applied to both sides of the resin film. Examples of the coating method include dip coating, slide coating, curtain coating, bar coating, air knife coating, roll coating, gravure coating, spray coating and the like, but the coating method is not limited to these, 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.

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, after the solvent is dried by heating, the components (A) and (B) are cured 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, and thus 150 ° C. or lower is preferable. The heating time is not particularly limited, but 0.25 minutes or more is preferable, 0.5 minutes or more is more preferable, and 1 minute or more is particularly preferable 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 solvent resistance of the release layer is excellent, 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, 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, or an pressure-sensitive adhesive film such as OCA 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 photo mask to prevent the photo resist from adhering to a photo mask, 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 16 for Forming Release Layer>
The components (A), (B), (C), and (D) are prepared in parts by mass (as solids) shown in Table 1, and they are 350 parts by mass of 2-butanone and 350 parts by 2-propanol. It was dissolved in a 1: 1 mixed solvent by mass to obtain compositions 1 to 16 for forming a release layer. In Table 1, Y-50 is a multimeric composition obtained by cross-linking m-xylene manufactured by Fudo Co., Ltd. with a methylene bond or an ether bond, and has a xylene skeleton but has only one or less hydroxy groups. ..

<Making release films 1 to 16>
The release layer forming compositions 1 to 16 shown in Table 1 are uniformly coated on a polyethylene terephthalate film having a thickness of 12 μm by gravure coating, and heated at 130 ° C. for 2 minutes using a hot air dryer to have a thickness of 2. A release layer of 0.0 μm was formed, and release films 1 to 16 were obtained.

<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) was applied to the surface of the release films 1 to 16 having the release layer. The hand roller was 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, and when the peel strength 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 15 was peeled off 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 peeling strength evaluation, the same applies except that the bonded portion was wiped 50 times with gauze containing toluene 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 16 was remeasured. Solvent resistance is excellent when the peel strength measured after wiping with a gauze soaked in toluene is 1 to 2 times the peel strength measured before wiping, and solvent resistance is 2 times or more and less than 4 times. It was evaluated that the property was good, and that the solvent resistance was good when it was 4 times or more and less than 8 times, and that the solvent resistance was not possible when it was 8 times or more. The results are shown in Table 2. Since the release film 15 could not be evaluated for releasability, the release film 16 could not be evaluated for releasability. Therefore, neither of them was evaluated for solvent resistance.

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

Claims (2)

A composition for forming a release layer containing a melamine compound (A), a xylene polyol (B), an acid catalyst (C), and a hydroxyl group-containing modified silicone resin (D). A method for producing a release film, which comprises applying the release layer forming composition according to claim 1 to at least one surface of a resin film, and then heating the resin film.