CN106867004B

CN106867004B - Thermosetting mold release coating agent, mold release film, and polyethylene terephthalate mold release film

Info

Publication number: CN106867004B
Application number: CN201610911394.5A
Authority: CN
Inventors: 伊藤良树; 金子光耶子; 东本徹
Original assignee: Arakawa Chemical Industries Ltd
Current assignee: Arakawa Chemical Industries Ltd
Priority date: 2015-10-20
Filing date: 2016-10-19
Publication date: 2021-05-07
Anticipated expiration: 2036-10-19
Also published as: TW201728710A; TWI742005B; KR20170046089A; JP2017078161A; JP6299829B2; CN106867004A; KR102577864B1

Abstract

The invention provides a thermosetting release coating agent composition which can form a cured film with excellent release property and residual adhesion at a relatively low temperature and has small film curl after a coating film is formed. The thermosetting release coating agent contains a methylated melamine resin (A), a polyol (B) having a molecular weight of 100-3000, and an acid catalyst (C).

Description

Thermosetting mold release coating agent, mold release film, and polyethylene terephthalate mold release film

Technical Field

The present invention relates mainly to a thermosetting release coating agent, and a release film and a polyethylene terephthalate release film coated with the coating agent composition.

Background

Biaxially stretched polyester films, represented by polyethylene terephthalate films, are widely used in various industrial fields because they are excellent in properties such as transparency, dimensional stability, mechanical properties, and chemical resistance. In recent years, the optical films are widely used for various applications such as prism sheets, light diffusion sheets, reflection plates, base films for touch panels and the like, antireflection base films, display panel explosion-proof base films, PDP filter films, and the like, which are used for LCD members. In addition, the resin composition is also widely used as a release film, and is also widely used for electronic material applications as a release film for producing adhesive sheets, tapes, touch panel protective films, and ceramic capacitors.

The conventional release film is mainly a release film in which a silicone resin coating film having releasability is formed on a polyester film. However, it has been pointed out that in the case of using a silicone-based release agent, the small molecular weight silicone compound contained in the silicone-based release agent migrates to the adhesive surface of the adhesive sheet, causing residue, which may cause a decrease in the adhesive force of the adhesive or may cause problems in electronic parts adhered by the adhesive sheet. Further, it is known that since silicone resin has releasability, close adhesion to a substrate is poor.

In order to solve the above problem, a method of laminating a melamine resin-based release agent is disclosed (patent document 1). However, when the melamine resin is used, a high temperature of 150 ℃ or higher is required to form a coating film, and therefore, the polyester film as a substrate is damaged greatly. Further, the melamine resin has a problem of curling of the film due to curing shrinkage when forming a coating film or a film stored for a long time.

Documents of the prior art

Patent document

Japanese patent application laid-open No. 2014-151448 of patent document 1

Disclosure of Invention

Technical problem to be solved by the invention

The purpose of the present invention is to provide a heat-curable release coating agent which can form a cured film having excellent releasability and residual adhesion in a short time at a relatively low temperature, and at the same time, has less curling of the film after coating film formation (i.e., is excellent in low curling properties).

Means for solving the problems

The present inventors have found, as a result of their studies, that the above-mentioned problems can be solved by a composition comprising a specific melamine resin, a specific polyol and an acid catalyst in combination. Namely, the present invention relates to a heat-curable release coating agent and a release film shown below.

1. A thermosetting release coating agent, which contains (A) a methylated melamine resin, (B) a polyol having a molecular weight of 100-3000, and (C) an acid catalyst.

2. The thermally curable release coating agent as described in the above 1, wherein the component (A) is a fully ether-type methylated melamine resin.

3. The heat-curable release coating agent according to the above 1 or 2, wherein the component (B) is a polyol which is liquid at 25 ℃.

4. The heat-curable release coating agent according to the above 3, wherein the polyol which is liquid at 25 ℃ is at least one selected from the group consisting of dimer diol, hydrogenated dimer diol, castor oil and castor oil-type modified polyol.

5. The heat-curable release coating agent according to any one of the above 1 to 4, wherein the component (C) is a sulfonic acid catalyst and/or a phosphoric acid catalyst.

6. The thermosetting release coating agent according to any one of the above 1 to 5, wherein the mass ratio [ (A)/(B) ] of the component (A) and the component (B) is 25/75 to 75/25.

7. The heat-curable release coating agent according to any one of the above 1 to 6, wherein the content of the component (C) is 1 to 10 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B).

8. The thermosetting release coating agent according to any one of the above 1 to 7, wherein the thermosetting release coating agent further contains a hydroxyl group-containing modified silicone resin (D).

9. The heat-curable release coating agent as described in the above 8, wherein the content of the component (D) is 1 to 15 parts by mass relative to 100 parts by mass of the total amount of the components (A) and (B).

10. The thermosetting release coating agent according to any one of the above 1 to 9, wherein the thermosetting release coating agent further contains an organic solvent (E).

11. A release film comprising a release layer formed from the thermosetting release coating agent according to any one of the above 1 to 10 on at least one surface thereof.

12. A polyethylene terephthalate release film having a release layer formed of the thermosetting release coating agent according to any one of the above 1 to 10 on at least one surface thereof.

Effects of the invention

The heat-curable release coating agent of the present invention can form a cured film excellent in releasability, residual adhesion and low curling at a relatively low temperature. The coating agent is a release agent particularly suitable for a release film in which the substrate film is a polyester film. Examples of the uses of the release film include release films used in production processes of ceramic capacitors, synthetic leathers, cosmetic sheets, carbon fiber prepregs, and the like; or a release film used in transfer printing of a related article; and release films for protecting adhesive layers such as polarizing plates and retardation plates.

Detailed Description

The thermosetting release coating agent (hereinafter referred to simply as "coating agent") of the present invention contains a methylated melamine resin (A) (hereinafter referred to simply as "component (A)"), a polyol (B) (hereinafter referred to simply as "component (B)") having a molecular weight of 100 to 3000, and an acid catalyst (C) (hereinafter referred to simply as "component (C)").

(A) The component (A) is a compound represented by the following formula (1) and/or an oligomer or polymer thereof.

[ solution 1]

(in the formula (1), R¹～R⁶May be the same or different and each represents a hydrogen atom, a hydroxymethyl group (-CH)₂OH), methoxymethyl (-CH)₂OCH₃) Ethoxymethyl (-CH)₂OCH₂CH₃) N-butoxymethyl (-CH)₂OCH₂CH₂CH₂CH₃) And isobutoxymethyl (-CH)₂OCH(CH₃)CH₂CH₃) Any one of them. However, R¹～R⁶At least one of which is methoxymethyl. )

(A) The average polymerization degree of the oligomer or polymer of the component (A) is not particularly limited, but is usually about 1.1 to 10.

The component (a) is preferably a fully ether-type methylated melamine resin from the viewpoint of low-temperature and short-time curability. In particular, 2,4, 6-tris [ bis (methoxymethyl) amino ] -1,3, 5-triazine and/or oligomers or even polymers thereof are preferred.

(A) The components may also be commercially available, for example, サイメル 300, サイメル 301, サイメル 303LF, サイメル 350, サイメル 370N, サイメル 771, サイメル 325, サイメル 327, サイメル 703, サイメル 712, サイメル 701, サイメル 266, サイメル 267, サイメル 285, サイメル 232, サイメル 235, サイメル 236, サイメル 238, サイメル 272, サイメル 212, サイメル 253, サイメル 254, サイメル 202, サイメル 207 (manufactured by オルネクスジャパン strain), ニカラック MW-30M, ニカラック MW-30, ニカラック MW-30HM, ニカラック MW-390, ニカラック MW-100LM, ニカラック MX-750LM, ニカラック MW-22, ニカラック MS-21, ニカラック MS-11, ニカラック MW-24X, ニカラック MS-001, ニカラック MX-002, ニカラック MX-730, ニカラック MX-750, ニカラック MX-708, ニカラック MX-706, ニカラック MX-042, ニカラック MX-035, ニカラック MX-45, ニカラック MX-43, ニカラック MX-417 and ニカラック MX-410 (manufactured by Sansui and ケミカル, supra), and the like, and one or more thereof can be used. As the full ether type methylated melamine resin, サイメル 303LF or ニカラック MW-30 can be cited.

The component (B) is not limited as long as it is a polyol having a molecular weight of 100 to 3000, and various known polyols can be used. When a polyol having a molecular weight of less than 100 is used as the component (B), curling of the film tends to increase during the formation of a coating film. Further, when a polyol having a molecular weight of more than 3000 is used as the component (B), it is difficult to form a coating film under a low temperature short time condition. From this viewpoint, the molecular weight is preferably about 100 to 1500.

In addition, "molecular weight" in the present specification includes number average molecular weight for convenience. In particular, the component (b2) described later is preferably a component having a number average molecular weight. The number average molecular weight is a polystyrene equivalent value obtained by gel permeation chromatography (the same applies hereinafter).

The component (B) includes a polyol (B1) (hereinafter referred to as a component (B1)) as a single compound and/or a polyol (B2) (hereinafter referred to as a component (B2)) as a polymer.

As the component (b1), various known polyhydric alcohols as a single compound can be used without particular limitation. In the present specification, the term "single compound" refers to any of a monomer, a dimer and a trimer, and refers to a compound which can be regarded as a single compound as a whole.

Specific examples of the component (b1) include aliphatic diols such as 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol, 2-methyl-1, 5-pentanediol, 2-dimethyl-1, 3-propanediol, 1, 9-nonanediol, 1, 10-decanediol, butylethylpropanediol, and butylethylpentanediol; alicyclic diols such as 1, 4-cyclohexanedimethanol; one or more kinds of trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, dimer diol, hydrogenated dimer diol, triol, hydrogenated trimer triol, castor oil type modified polyol, and alkylene oxide adduct of bisphenol compound or its derivative can be used.

(b1) Among the components, polyols which are liquid at 25 ℃ are preferred from the viewpoint of low temperature, short time curing and low curling properties. In view of further facilitating the separation (light detachable), at least one selected from the group consisting of dimer diol, hydrogenated dimer diol, castor oil and castor oil-type modified polyol is more preferable.

Dimer diol is generally a reduced product of a reaction product of a cyclic and/or acyclic dimer acid obtained by dimerization of a higher unsaturated fatty acid and methanol. In addition, hydrodimer diol is the product of the hydrogenation reaction of dimer diol. The higher unsaturated fatty acid is not particularly limited, and examples thereof include unsaturated monocarboxylic acids having about 14 to 22 carbon atoms, and for example, tetradecadienoic acid, hexadecadienoic acid, linoleic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, arachidonic acid, myristic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, eicosenoic acid, erucic acid, cetenoic acid, brassidic acid and the like, and one or more thereof may be used. Among the above, oleic acid and/or linoleic acid are preferable. The dimerization reaction of the higher unsaturated fatty acid may be carried out by the method described in, for example, Japanese patent application laid-open No. 9-136861.

The component (b2) is not particularly limited as long as it is a polymer polyol, and various known polyols can be used. Specifically, for example, at least one selected from the group consisting of polyether polyols, polyester polyols, polycarbonate polyols, acrylic polyols (アクリルポリオール), polyolefin polyols, and the like can be cited.

Examples of the polyether polyol include polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polybutylene glycol, copolymers containing a plurality of alkylene oxides (alkylene oxide-another alkylene oxide) as monomer components such as ethylene oxide-propylene oxide copolymers, and the like, and one or more kinds thereof can be used. Commercially available products include アデカポリエーテル P-400, アデカポリエーテル G-400, アデカポリエーテル T-400 and アデカポリエーテル AM-302 (manufactured by strain アデカ).

Examples of the polyester polyol include: polycondensates of polyols with polycarboxylic acids; ring-opening polymers of cyclic esters (lactones); reaction products of polyols, polycarboxylic acids and cyclic esters, and the like. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 2-methyl-1, 3-propanediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, 1, 9-nonanediol, 1, 10-decanediol, glycerin, trimethylolpropane, trimethylolethane, cyclohexanediols (1, 4-cyclohexanediol, etc.), cyclohexanedimethanol (1, 4-cyclohexanedimethanol, etc.), bisphenols (bisphenol a, etc.), sugar alcohols (xylitol, sorbitol, etc.), and one or more thereof can be used. Examples of the polycarboxylic acid include aliphatic dicarboxylic acids such as malonic acid, maleic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid, alicyclic dicarboxylic acids such as 1, 4-cyclohexanedicarboxylic acid, and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and 2, 6-naphthalenedicarboxylic acid, and one or more kinds thereof can be used. Examples of the cyclic ester include propiolactone, β -methyl- δ -valerolactone, and ∈ -caprolactone, and one or more of them can be used. Commercially available polyester polyols include クラレポリオール P-510, クラレポリオール F-510 (manufactured by クラレ, Inc.), プラクセル 205(ダイセル, Inc.), and the like.

Examples of the polycarbonate polyol include a reaction product of a polyol and phosgene, and a ring-opened polymer of a cyclic carbonate (e.g., alkylene carbonate). The polyol includes the above-mentioned polyols. Examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, and hexamethylene carbonate. Commercially available polycarbonate polyols include クラレポリオール C-590 (manufactured by クラレ).

Examples of the acrylic polyol include homopolymers or copolymers of acrylic monomers having 1 or more hydroxyl groups in one molecule, and copolymers obtained by copolymerizing the above copolymers with other monomers, and one or more kinds thereof can be used. As a commercially available product of acrylic polyol, ARUFON UH-2041 (synthesized by Egyo of China) and the like can be cited.

Examples of the polyolefin polyol include polybutadiene having 2 or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, and chlorinated products thereof. Examples of commercially available products include NISSO-PB GI-1000 (manufactured by Nippon soda Co., Ltd.).

The physical properties of the component (b2) are not particularly limited, and the (number average) molecular weight is usually about 300 to 3000, preferably about 500 to 1500 in consideration of low temperature, short time curability and low curling property; the hydroxyl value (JISK-0070) is usually about 30 to 600mgKOH/g, preferably about 100 to 400 mgKOH/g; the average number of functional groups per molecule is usually about 2 to 6, preferably about 2 to 5.

(A) The ratio of the component (A) to the component (B) is not particularly limited, but is usually about 25/75 to 75/25, preferably about 30/70 to 70/30 in terms of the mass ratio [ (A)/(B) ] in consideration of the balance among curability, residual adhesiveness, mold releasability and low curling.

As the component (C), various known acid catalysts can be used without particular limitation. Specifically, examples thereof include: inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; or an organic acid. Examples of the organic acid include carboxylic acid catalysts such as oxalic acid, acetic acid, and formic acid; sulfonic acid catalysts such as methanesulfonic acid, trifluoromethanesulfonic acid, isoprene sulfonic acid, camphorsulfonic acid, hexane sulfonic acid, octane sulfonic acid, nonane sulfonic acid, decane sulfonic acid, hexadecane sulfonic acid, benzene sulfonic acid, p-toluene sulfonic acid, cumene sulfonic acid, dodecylbenzene sulfonic acid, naphthalene sulfonic acid, and nonylnaphthalene sulfonic acid; methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, octyl acid phosphate, 2-ethylhexyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonylphenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxypolyethylene glycol acid phosphate, bisphenol A acid phosphate, dimethyl acid phosphate, diethyl acid phosphate, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, di (2-ethylhexyl) acid phosphate, dilauryl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, and phenyl acid phosphate, Phosphoric acid catalysts such as distearyl acid phosphate, diphenyl acid phosphate, dinonyl phenyl acid phosphate and the like; one or more kinds of thermal acid generator (acid generator) may be used, for example, sulfonium salt, benzothiazolium salt, ammonium salt, phosphonium salt and the like.

The component (C) is preferably the organic acid from the viewpoint of compatibility. Particularly, in view of low-temperature curability, the sulfonic acid-based catalyst and/or the phosphoric acid-based catalyst are preferable.

(C) The content of the component (C) is not particularly limited, and may be in the range of about 1 to 10 parts by mass, preferably about 3 to 8 parts by mass, based on 100 parts by mass of the total of the components (a) and (B), in consideration of the balance among curability, residual adhesiveness, releasability, and low curling.

The coating agent of the present invention may contain a modified silicone resin (D) containing a hydroxyl group (hereinafter referred to as component (D)) for the purpose of adjusting the peeling force. It is considered that the component (D) is bonded to the component (A) through the hydroxyl group thereof, and as a result, the component (D) is less likely to migrate to an adherend, and the decrease in residual adhesion of the coating film can be suppressed.

The component (D) is not particularly limited as long as it is a modified silicone resin containing a hydroxyl group, and various known ones can be used. Specifically, for example, an alcohol-modified silicone resin, a polyester-modified hydroxyl-containing silicone resin, a polyether ester-modified silicone resin, a hydroxyl-containing silicone-modified acrylic resin, and the like can be used, and one or more kinds thereof can be used. Commercially available products of component (D) include X-22-4039, X-22-4015, X-22-4952, X-22-4272, X-22-170BX, X-22-170DX, KF-6000, KF-6001, KF-6002, KF-6003, KF-6123 (manufactured by shin-Etsu chemical Co., Ltd.), BYK-370, BYK-375, BYK-377, BYK-SILCLEAN3720, BYK-SILCLEAN3700 (manufactured by ビックケミー/ジャパン Co., Ltd.), サイラプレーン FM-4411, サイラプレーン FM-4421, サイラプレーン FM-4425, サイラプレーン -0411, サイラプレーン -0425, サイラプレーン -DA11, サイラプレーン -FM-DA 21, FM-21, KF-F-4411, FM- サイラプレーン FM-4421, FM-F-D サイラプレーン, FM-D3, FM-D3, and, サイラプレーン FM-DA26 (manufactured by JNC Co., Ltd.) and the like, and one or more thereof can be used.

(D) The amount of the component (D) is not particularly limited, and may be usually about 1 to 15 parts by mass, preferably about 1 to 10 parts by mass, based on 100 parts by mass of the total of the component (a) and the component (B), from the viewpoint of suppressing the decrease in residual adhesion of the coating film of the present invention.

The coating agent of the present invention may contain an organic solvent (E) (hereinafter referred to as component (E)). Specific examples thereof include methyl ethyl ketone, methyl isobutyl ketone, acetone, ethyl acetate, butyl acetate, toluene, xylene, isopropyl alcohol, ethanol, butanol, and the like, and one or more thereof can be used. Among the above solvents, at least one selected from the group consisting of methyl ethyl ketone, methyl isobutyl ketone, isopropyl alcohol, ethyl acetate and toluene is preferable from the viewpoint of solubility.

(E) The component (b) is not particularly limited, and generally, the solid content concentration of the coating agent of the present invention is usually in the range of about 1 to 50 mass%. By falling within the above numerical range, a good balance of curability of the cured film and close adhesiveness of the plastic film (particularly, polyethylene terephthalate film) can be obtained.

The coating agent of the present invention may contain various known additives, for example, a binder, a defoaming agent, an anti-slip agent, a preservative, a rust preventive, a pH adjuster, an antioxidant, a pigment, a dye, a lubricant, a leveling agent (レベリング agent), an anti-blocking agent, and the like. As the binder, various known acrylic resins, polyurethane resins, polyester resins, epoxy resins, alkyd resins, and the like can be used.

The release film of the present invention is a film having a release layer formed of the coating agent of the present invention on at least one surface, and is obtained by coating the coating agent of the present invention on various known base material films and curing the coating agent.

Examples of the base film include films made of plastics such AS polycarbonate, polymethyl methacrylate, polystyrene, polyethylene terephthalate (PET), polyimide, polyolefin, nylon, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, and norbornene resin. The substrate film may be subjected to surface treatment (corona discharge or the like). Among the above base films, polyethylene terephthalate is preferable from the viewpoint of the performance such as transparency, dimensional stability, mechanical properties, chemical resistance, and the like. The plastic film may be provided with a layer formed of a coating agent other than the thermosetting release coating agent of the present invention on one or both surfaces thereof.

The release layer (cured coating film) is obtained by applying the thermosetting release coating agent of the present invention to various substrates so that the mass of the coating agent after drying is 0.1 to 10g/m²About, preferably 0.2 to 5g/m²The amount of (c) is coated and the product is dried.

The coating method is not particularly limited and may be carried out by various known apparatuses. Specifically, examples thereof include a roll coater, a reverse roll coater, a gravure coater, a blade coater, and a bar coater.

The drying conditions are not particularly limited. The coating agent of the present invention is usually cured at 90 to 130 ℃ for 30 seconds to 2 minutes, and considering that the general coating film forming conditions are usually about 150 to 190 ℃ for 1 minute to 5 minutes, the coating agent of the present invention can be said to be cured at a relatively low temperature. Therefore, the coating agent can be suitably used for plastic films which are liable to be deformed by heat, particularly polyethylene terephthalate films.

Examples

The present invention will be described in further detail below with reference to examples and comparative examples, but the scope of the present invention is not limited to the examples and comparative examples. In each of examples and comparative examples, parts and% are by mass.

Example 1

サイメル 303LF (full ether type methylated melamine resin, オルネクスジャパン)50 parts, PRIPOL2033 (hydrogenated dimer diol number average molecular weight, 540: クローダジャパン), and p-toluenesulfonic acid 4 parts were mixed, and methyl ethyl ketone was further added to prepare a coating agent having a solid content of 20%.

Example 2

サイメル 303LF 50 parts, プラクセル 205 (polyester polyol having a number average molecular weight of 500 (manufactured by ダイセル Co.)) 50 parts, and p-toluenesulfonic acid 4 parts were mixed, and methyl ethyl ketone was further added to prepare a coating agent having a solid content of 20%.

Example 3

サイメル 303LF 50 parts, クラレポリオール C-1090 (polycarbonate polyol number average molecular weight 1000 (strain) クラレ)50 parts, and p-toluenesulfonic acid 4 parts were mixed, and methyl ethyl ketone was further added to prepare a coating agent having a solid content of 20%.

Example 4

サイメル 303LF 50 parts, アデカポリエーテル AM-302 (polyether polyol number average molecular weight 3000 (manufactured by アデカ)) 50 parts, and p-toluenesulfonic acid 4 parts were mixed, and methyl ethyl ketone was further added to prepare a coating agent having a solid content of 20%.

Example 5

サイメル 303LF 50 parts, HS 2G-270B (castor oil polyol number average molecular weight 450 rich, manufactured by NOSE OIL KOKAI CO., LTD.) 50 parts, and p-toluenesulfonic acid 4 parts were mixed, and methyl ethyl ketone was further added to prepare a coating agent having a solid content of 20%.

Example 6

サイメル 303LF 80 parts, PRIPOL 203320 parts, and p-toluenesulfonic acid 4 parts were mixed, and methyl ethyl ketone was further added to prepare a coating agent having a solid content of 20%.

Example 7

サイメル 303LF 70 parts, PRIPOL 203330 parts, and p-toluenesulfonic acid 4 parts were mixed, and methyl ethyl ketone was further added to prepare a coating agent having a solid content of 20%.

Example 8

サイメル 303LF 30 parts, PRIPOL 203370 parts, and p-toluenesulfonic acid 4 parts were mixed, and methyl ethyl ketone was further added to prepare a coating agent having a solid content of 20%.

Example 9

サイメル 303LF 20 parts, PRIPOL 203380 parts, and p-toluenesulfonic acid 4 parts were mixed, and methyl ethyl ketone was further added to prepare a coating agent having a solid content of 20%.

Example 10

サイメル 303LF 50 parts, PRIPOL 203350 parts, and p-toluenesulfonic acid 1 part were mixed, and methyl ethyl ketone was further added to prepare a coating agent having a solid content of 20%.

Example 11

サイメル 303LF 50 parts, PRIPOL 203350 parts, and p-toluenesulfonic acid 10 parts were mixed, and methyl ethyl ketone was further added to prepare a coating agent having a solid content of 20%.

Example 12

サイメル 325 (80% solid content of imino methylated melamine resin オルネクスジャパン (manufactured by KAKII CHEMICAL CO., LTD.) 62.5 parts (50 parts in terms of solid content), PRIPOL 203350 parts, and 8 parts of methyl acid phosphate (trade name AP-1, manufactured by KAKII CHEMICAL INDUSTRY (manufactured by KAKII CHEMICAL CO., LTD)) were mixed, and methyl ethyl ketone was further added thereto to prepare a coating agent having a solid content of 20%.

Example 13

A coating agent having a solid content of 20% was prepared by mixing 56.8 parts (50 parts in terms of solid content) of サイメル 370N (88% in terms of solid content of methylol methylated melamine resin, manufactured by オルネクスジャパン K.) and PRIPOL 203350 parts with AP-18 parts and adding methyl ethyl ketone thereto.

Example 14

サイメル 303LF 70 parts, PRIPOL 203330 parts, p-toluenesulfonic acid 2 parts, and octyl acid phosphate (trade name AP-8, manufactured by Daba chemical Co., Ltd.) 2 parts were mixed, and methyl ethyl ketone was further added to prepare a coating agent having a solid content of 20%.

Example 15

サイメル 303LF 50 parts, PRIPOL 203350 parts, p-toluenesulfonic acid 4 parts, BYK-370 (25% solid content of polyester-modified hydroxyl group-containing silicone resin, ビックケミー. ジャパン) (manufactured by LTD.) 4 parts (1 part in terms of solid content) were mixed, and methyl ethyl ketone was further added to prepare a coating agent having a solid content of 20%.

Example 16

サイメル 303LF 50 parts, PRIPOL 203350 parts, p-toluenesulfonic acid 4 parts, BYK-375 (25% solid content of polyether ester-modified hydroxyl group-containing silicone resin, ビックケミー. ジャパン) (manufactured by LTD.) 4 parts (1 part in terms of solid content) were mixed, and methyl ethyl ketone was further added to prepare a coating agent having a solid content of 20%.

Example 17

サイメル 303LF 50 parts, PRIPOL 203350 parts, p-toluenesulfonic acid 4 parts, and BYK-377 (solid content 100% of polyether-modified hydroxyl group-containing silicone resin, ビックケミー. ジャパン, Ltd.) were mixed together, and methyl ethyl ketone was further added to prepare a coating agent having a solid content of 20%.

Example 18

サイメル 303LF 50 parts, PRIPOL 203350 parts, p-toluenesulfonic acid 4 parts, BYK-SILCLEAN3700 parts (ビックケミー, ジャパン, Ltd.) of silicone-modified acrylic resin containing hydroxyl group as solid content 25% and 1 part in terms of solid content) were mixed, and methyl ethyl ketone was further added to prepare a coating agent having a solid content of 20%.

Example 19

サイメル 303LF 50 parts, PRIPOL 203350 parts, p-toluenesulfonic acid 4 parts, and サイラプレーン FM-4411 (alcohol-modified silicone resin solid content 100%: JNC (manufactured by JNC Co., Ltd.) were mixed together, and methyl ethyl ketone was further added to prepare a coating agent having a solid content of 20%.

Example 20

サイメル 303LF 50 parts, PRIPOL 203350 parts, p-toluenesulfonic acid 4 parts, and BYK-3775 parts were mixed, and methyl ethyl ketone was further added to prepare a coating agent having a solid content of 20%.

Example 21

サイメル 303LF 50 parts, HS 2G-270B 50 parts, p-toluenesulfonic acid 4 parts, BYK-3771 parts were mixed, and methyl ethyl ketone was further added to prepare a coating agent having a solid content of 20%.

Comparative example 1

サイメル 303LF (100 parts) and p-toluenesulfonic acid (4 parts) were mixed, and methyl ethyl ketone was further added to prepare a coating agent having a solid content of 20%.

Comparative example 2

サイメル 303LF 50 parts and PRIPOL 203350 parts were mixed, and methyl ethyl ketone was further added to prepare a coating agent having a solid content of 20%.

Comparative example 3

ユーバン 20SE60 (60% of the solid content of butylated melamine resin: manufactured by Mitsui chemical Co., Ltd.) 83 parts (50 parts in terms of solid content), PRIPOL 203350 parts, and 4 parts of p-toluene sulfonic acid were mixed, and methyl ethyl ketone was further added to prepare a coating agent having a solid content of 20%. Comparative example 4

サイメル 303LF 50 parts, アデカポリエーテル AM-702 (polyether polyol number average molecular weight 6800 (strain) アデカ)50 parts, and p-toluenesulfonic acid 4 parts were mixed, and methyl ethyl ketone was further added to prepare a coating agent having a solid content of 20%.

Comparative example 5

サイメル 303LF 50 parts, クラレポリエーテル P-6010 (polyester polyol number average molecular weight 6000 (strain) クラレ)50 parts, and P-toluenesulfonic acid 4 parts were mixed, and methyl ethyl ketone was further added to prepare a coating agent having a solid content of 20%.

Comparative example 6

サイメル 303LF 70 parts, 2-methyl-1, 3-propanediol 30 parts, p-toluenesulfonic acid 5 parts, and KF-9701 (silanol-terminated silicone resin solid content 100%: manufactured by shin-Etsu chemical Co., Ltd.) 5 parts were mixed, and methyl ethyl ketone was further added to prepare a coating agent having a solid content of 20%.

TABLE 1

サイメル 303 LF: full ether type methylated melamine resin

サイメル 325, 325: methylated melamine resin of imino type

サイメル 370N: methylolated melamine resin

ユーバン 20SE 60: butylated melamine resin

PRIPOL 2033: hydrodimer diol (molecular weight 540)

プラクセル 205: polyester polyol (molecular weight 500)

C-1090: polycarbonate polyol (molecular weight 1000)

AM-302: polyether polyol (molecular weight 3000)

HS 2G-270B: castor oil type polyol (molecular weight 450)

AM-702: polyether polyol (molecular weight 6800)

P-6010: polyester polyol (molecular weight 6000)

PTS: p-toluenesulfonic acid

AP-1: methyl acid phosphate

AP-8: octyl acid phosphate ester

BYK-370: polyester-modified hydroxyl-containing silicone resin

BYK-375: polyether ester modified hydroxyl-containing organic silicon resin

BYK-377: polyether modified hydroxyl-containing organic silicon resin

BYK-SILCLEAN 3700: hydroxyl-containing organic silicon modified acrylic resin

FM-4411: alcohol-modified silicone resin

KF-9701: silanol-terminated silicone resins

In the table, "parts by mass" are calculated as solid content.

Preparation of Release film

The coating agent of example 1 was applied to a polyethylene terephthalate film (film thickness: 25 μm) to a thickness of 1 μm of a dry coating film, and dried at 120 ℃ for 1 minute to obtain a release film. The same procedure was carried out for the coating agents of the other examples and comparative examples to obtain release films.

Curing Properties

The cured coating of the release film according to example 1 was wiped with a cotton swab soaked with methyl ethyl ketone, and the curability of the coating agent according to example 1 was evaluated by measuring the number of repeated wiping until the substrate was exposed. The same procedure was carried out for the release films of the other examples and comparative examples to evaluate curability.

Very good: wiping for more than 100 times without exposing the coating

O: when the coating film is wiped for 60 times or more and 99 times or less, the coating film is exposed

And (delta): when the coating film is wiped 20 times or more and 59 times or less, the coating film is exposed

X: when the coating film is wiped for 1 to 19 times, the coating film is exposed

Crimping

A test piece having a size of 10 cm. times.10 cm was cut from the release film of example 1, and stored in a dryer at 120 ℃ for 10 minutes. Then, the film was placed on a horizontal table, and the floating size (curl) of the four corners was measured. The curl was measured in the same manner as in the release films of the other examples and comparative examples.

Very good: the average value of the floating heights of the four corners is less than 1mm

O: the average value of the floating heights of the four corners is more than 1mm and less than 3mm

And (delta): the average value of the floating heights of the four corners is more than 3mm and less than 5mm

X: the average value of the floating height of the four corners is more than 5mm

Peeling force

A polyester tape (31B tape manufactured by Ridong electric Co., Ltd.: 25mm wide) was pressure-bonded to the cured film of the release film of example 1 with a 2kg roll, and stored at 23 ℃ for 30 minutes. Then, the tape was peeled at an angle of 180 ℃ and a peeling speed of 0.3m/min, and the force (mN/25mm) required for peeling was measured. The release films of the other examples and comparative examples were subjected to the same procedure to measure the peeling force.

Residual adhesion rate

A polyester tape (31B tape manufactured by Nindon electric Co., Ltd.: 25mm width) was adhered to the surface of the cured film of the release film according to example 1, and stored at 23 ℃ for 1 day. After storage, the tape was removed and attached to an SUS plate with a 2kg roller. Then, the tape was peeled from the SUS plate at an angle of 180 ℃ and a peeling speed of 0.3m/min, and the force required for peeling was measured. As a blank group, the peel force when the tape and the SUS plate were directly attached and peeled off under the same conditions was measured, and the ratio (%) of the former peel force to the latter peel force was determined as the residual adhesion rate. The larger the value, the less the adhesive force of the tape is reduced.

TABLE 2

Claims

1. A thermosetting release coating agent, which contains (A) a methylated melamine resin, (B) a polyol having a molecular weight of 450-3000, and (C) an acid catalyst.

2. The thermally curable release coating agent according to claim 1, wherein the component (A) is a fully ether-type methylated melamine resin.

3. The heat-curable release coating agent according to claim 1 or 2, wherein the component (B) is a polyol which is liquid at 25 ℃.

4. The heat-curable release coating agent according to claim 3, wherein the polyol which is liquid at 25 ℃ is at least one selected from the group consisting of dimer diol, hydrogenated dimer diol, castor oil and castor oil-based modified polyol.

5. The heat-curable release coating agent according to claim 1 or 2, wherein the component (C) is a sulfonic acid catalyst and/or a phosphoric acid catalyst.

6. The heat-curable release coating agent according to claim 3, wherein the component (C) is a sulfonic acid catalyst and/or a phosphoric acid catalyst.

7. The heat-curable release coating agent according to claim 4, wherein the component (C) is a sulfonic acid catalyst and/or a phosphoric acid catalyst.

8. The heat-curable mold release coating agent according to claim 1 or 2, wherein the mass ratio [ (A)/(B) ] of the component (A) to the component (B) is 25/75 to 75/25.

9. The heat-curable mold release coating agent according to claim 3, wherein the mass ratio [ (A)/(B) ] of the component (A) to the component (B) is 25/75-75/25.

10. The heat-curable mold release coating agent according to claim 4, wherein the mass ratio [ (A)/(B) ] of the component (A) to the component (B) is 25/75-75/25.

11. The heat-curable mold release coating agent according to claim 5, wherein the mass ratio [ (A)/(B) ] of the component (A) to the component (B) is 25/75-75/25.

12. The heat-curable mold release coating agent according to claim 6 or 7, wherein the mass ratio [ (A)/(B) ] of the component (A) to the component (B) is 25/75 to 75/25.

13. The heat-curable release coating agent according to claim 1 or 2, wherein the content of the component (C) is 1 to 10 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B).

14. The heat-curable release coating agent according to claim 3, wherein the content of the component (C) is 1 to 10 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B).

15. The heat-curable release coating agent according to claim 4, wherein the content of the component (C) is 1 to 10 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B).

16. The heat-curable release coating agent according to claim 5, wherein the content of the component (C) is 1 to 10 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B).

17. The heat-curable release coating agent according to claim 6 or 7, wherein the content of the component (C) is 1 to 10 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B).

18. The heat-curable release coating agent according to claim 8, wherein the content of the component (C) is 1 to 10 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B).

19. The heat-curable release coating agent according to any one of claims 9 to 11, wherein the content of the component (C) is 1 to 10 parts by mass relative to 100 parts by mass of the total amount of the components (A) and (B).

20. The heat-curable release coating agent according to claim 12, wherein the content of the component (C) is 1 to 10 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B).

21. The heat-curable release coating agent according to claim 1 or 2, further comprising a modified silicone resin (D) containing a hydroxyl group.

22. The heat-curable release coating agent according to claim 3, further comprising a modified silicone resin (D) containing a hydroxyl group.

23. The heat-curable release coating agent according to claim 4, further comprising a modified silicone resin (D) containing a hydroxyl group.

24. The heat-curable release coating agent according to claim 5, further comprising a modified silicone resin (D) containing a hydroxyl group.

25. The heat-curable release coating agent according to claim 6 or 7, further comprising a modified silicone resin (D) containing a hydroxyl group.

26. The heat-curable release coating agent according to claim 8, further comprising a modified silicone resin (D) containing a hydroxyl group.

27. The thermally curable release coating agent according to any one of claims 9 to 11, further comprising a modified silicone resin (D) containing a hydroxyl group.

28. The heat-curable release coating agent according to claim 12, further comprising a modified silicone resin (D) containing a hydroxyl group.

29. The heat-curable release coating agent according to claim 13, further comprising a modified silicone resin (D) containing a hydroxyl group.

30. The thermally curable release coating agent according to any one of claims 14 to 16, further comprising a modified silicone resin (D) containing a hydroxyl group.

31. The heat-curable release coating agent according to claim 17, further comprising a modified silicone resin (D) containing a hydroxyl group.

32. The heat-curable release coating agent according to claim 18, further comprising a modified silicone resin (D) containing a hydroxyl group.

33. The heat-curable release coating agent according to claim 19, further comprising a modified silicone resin (D) containing a hydroxyl group.

34. The thermally curable release coating agent according to claim 20, further comprising a modified silicone resin (D) containing a hydroxyl group.

35. The heat-curable release coating agent according to claim 21, wherein the content of the component (D) is 1 to 15 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B).

36. The heat-curable release coating agent according to any one of claims 22 to 24, wherein the content of the component (D) is 1 to 15 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B).

37. The heat-curable release coating agent according to claim 25, wherein the content of the component (D) is 1 to 15 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B).

38. The heat-curable release coating agent according to claim 26, wherein the content of the component (D) is 1 to 15 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B).

39. The heat-curable release coating agent according to claim 27, wherein the content of the component (D) is 1 to 15 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B).

40. The heat-curable release coating agent according to claim 28 or 29, wherein the content of the component (D) is 1 to 15 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B).

41. The heat-curable release coating agent according to claim 30, wherein the content of the component (D) is 1 to 15 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B).

42. The heat-curable release coating agent according to any one of claims 31 to 34, wherein the content of the component (D) is 1 to 15 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B).

43. The heat-curable release coating agent according to claim 1 or 2, further comprising an organic solvent (E).

44. The thermally curable release coating agent according to claim 3, further comprising an organic solvent (E).

45. The thermally curable release coating agent according to claim 4, further comprising an organic solvent (E).

46. The thermally curable release coating agent according to claim 5, further comprising an organic solvent (E).

47. The heat-curable release coating agent according to claim 6 or 7, further comprising an organic solvent (E).

48. The thermally curable release coating agent according to claim 8, further comprising an organic solvent (E).

49. The thermally curable release coating agent according to any one of claims 9 to 11, further comprising an organic solvent (E).

50. The thermally curable release coating agent according to claim 12, further comprising an organic solvent (E).

51. The thermally curable release coating agent according to claim 13, further comprising an organic solvent (E).

52. The thermally curable release coating agent according to any one of claims 14 to 16, further comprising an organic solvent (E).

53. The thermally curable release coating agent according to claim 17, further comprising an organic solvent (E).

54. The thermally curable release coating agent according to claim 18, further comprising an organic solvent (E).

55. The thermally curable release coating agent according to claim 19, further comprising an organic solvent (E).

56. The thermally curable release coating agent according to claim 20, further comprising an organic solvent (E).

57. The thermally curable release coating agent according to claim 21, further comprising an organic solvent (E).

58. The thermally curable release coating agent according to any one of claims 22 to 24, further comprising an organic solvent (E).

59. The thermally curable release coating agent according to claim 25, further comprising an organic solvent (E).

60. The thermally curable release coating agent according to claim 26, further comprising an organic solvent (E).

61. The thermally curable release coating agent according to claim 27, further comprising an organic solvent (E).

62. The heat-curable release coating agent according to claim 28 or 29, further comprising an organic solvent (E).

63. The thermally curable release coating agent according to claim 30, further comprising an organic solvent (E).

64. The thermally curable release coating agent according to any one of claims 31 to 35, further comprising an organic solvent (E).

65. The heat-curable release coating agent according to claim 36, further comprising an organic solvent (E).

66. The thermally curable release coating agent according to any one of claims 37 to 39, further comprising an organic solvent (E).

67. The thermally curable release coating agent according to claim 40, further comprising an organic solvent (E).

68. The thermally curable release coating agent according to claim 41, further comprising an organic solvent (E).

69. The thermally curable release coating agent according to claim 42, further comprising an organic solvent (E).

70. A release film comprising a release layer formed from the thermosetting release coating agent according to any one of claims 1 to 69 on at least one surface thereof.

71. A polyethylene terephthalate release film having a release layer formed from the thermosetting release coating agent according to any one of claims 1 to 69 on at least one surface thereof.