TWI718293B - Thermosetting release coating agent, release film, and production method of release film - Google Patents

Abstract

The problem to be solved by the present invention is to provide a novel thermosetting release coating agent, which can form a hardened coating film on a plastic film at a relatively low temperature and in a short time, and the hardened coating film has excellent mold releasability and There are few oozing problems. The solution of the present invention is a thermosetting release coating agent comprising: (A) polyol, or (A1) polyol and (A2) polyol; (B) hydroxyl-containing polysiloxane; and, (C) ) Polyisocyanate; wherein the (A) polyol has at least 3 hydroxyl groups in the molecule, and the molecular weight is 80-5000, and the hydroxyl value is 30-2000 mgKOH/g; the (A1) polyol has at least 3 hydroxyl groups in the molecule The molecular weight is 200-5000, and the hydroxyl value is 30-840mgKOH/g; the (A2) polyol has at least 3 hydroxyl groups in the molecule, and the molecular weight is 80-200, and the hydroxyl value is 841-2000mgKOH/g. g.

Description

Thermosetting release coating agent, release film, and production method of release film

The present invention relates to a thermosetting release coating agent, a release film, and a method for manufacturing a release film using the coating agent

Plastic films such as polyethylene terephthalate are used in various industrial fields due to their excellent properties such as transparency, dimensional stability, mechanical properties, and chemical resistance. Specifically, for example, the use as a base film for the following optical film products: liquid crystal display (LCD) components prism sheet, light diffusion sheet, reflector, anti-reflective sheet, touch panel, explosion-proof Thin film, plasma display panel filter (PDP filter), etc.

In addition, plastic films are often used as base films for release films, and also as separators for various adhesive sheets or protective films for touch panels. In addition, mold release films are also used in the manufacturing steps of ceramic electronic parts and resin sheets.

As a mold release agent for mold release films, a silicone resin is known.

Patent Document 1 proposes a method of laminating a blended liquid composed of acrylic resin, melamine resin, and silicone resin. In addition, as described in Patent Document 2, an acid catalyst may be used in combination in order to improve the curability of the melamine resin. [Prior Art Document] (Patent Document)

Patent Document 1: Japanese Patent Laid-Open No. 11-170440 Patent Document 2: Japanese Patent Laid-Open No. 2002-19037

[Problem to be solved by the invention] However, silicone resin has the following problem: it often bleeds out to the surface of the coating film and transfers to the adhesive or resin sheet layered on the coating film Wait for the adhered object, and damage its characteristics. In addition, in the method of laminating a blending liquid composed of acrylic resin, melamine resin, and silicone resin, the temperature required for the curing of the blending liquid to be used is 190°C, which causes thermal damage to the substrate Larger issues. Furthermore, when the acid catalyst is used in combination, there is also the following problem: the deterioration of the stability (pot life) of the coating agent over time leads to an increase in viscosity and a decrease in workability.

The problem to be solved by the present invention is to provide a novel thermosetting release coating agent, which can form a hardened coating film on a plastic film at a lower temperature and in a shorter time than in the past, and the hardened coating film has excellent mold releasability And the aforementioned bleeding problem is less. [Technical means to solve the problem]

As a result of research conducted by the present inventors, it was found that the aforementioned problem can be solved by a thermosetting release coating agent, which includes a specific polyol, a specific polysiloxane resin, and a polyisocyanate. That is, this invention relates to the manufacturing method of the following thermosetting mold release coating agent and a mold release film.

According to the present invention, the following items are provided. (Item 1A) A thermosetting release coating agent comprising: (A) polyol, or (A1) polyol and (A2) polyol; (B) hydroxyl-containing polysiloxane; and, (C) polyol Isocyanate; wherein the (A) polyol has at least 3 hydroxyl groups in the molecule, and the molecular weight is 80-5000, and the hydroxyl value is 30-2000mgKOH/g; the (A1) polyol has at least 3 hydroxyl groups in the molecule And the molecular weight is 200-5000, and the hydroxyl value is 30-840 mgKOH/g; the (A2) polyol has at least 3 hydroxyl groups in the molecule, and the molecular weight is 80-200, and the hydroxyl value is 841-2000 mgKOH/g. (Item 1B) A thermosetting release coating agent comprising: (A) a polyol, which has at least 3 hydroxyl groups in its molecule, and has a molecular weight of 80-5000 and a hydroxyl value of 30-2000 mgKOH/g; B) Hydroxy-containing polysiloxane; and, (C) Polyisocyanate. (Item 1C) A thermosetting release coating agent comprising: (A1) a polyol, which has at least 3 hydroxyl groups in its molecule, has a molecular weight of 200 to 5000, and a hydroxyl value of 30 to 840 mgKOH/g; A2) Polyol, which has at least 3 hydroxyl groups in the molecule, has a molecular weight of 80-200, and a hydroxyl value of 841-2000 mgKOH/g; (B) hydroxyl-containing polysiloxane; and, (C) polyisocyanate. (Item 2) The thermosetting release coating agent according to the above item, wherein the polyol of the component (A) has a molecular weight of 200 to 5000 and a hydroxyl value of 30 to 840 mgKOH/g. (Item 3) The thermosetting release coating agent according to item 1 or 2, wherein the component (A) contains ring-opening polymerizable polyester polyol (a-1) and/or polycondensed polyester Polyol (a-2). (Item 4) The thermosetting release coating agent according to any one of the above items 1 to 3, wherein the component (B) includes an acrylic polymer part, a polyester part, a polyether part, and a raw material. At least one of the group consisting of alcohol moieties. (Item 5) The thermosetting release coating agent according to any one of items 1 to 4, which further contains (D) a curing catalyst. (Item 6) The thermosetting release coating agent according to any one of items 1 to 5, which further contains (E) an organic solvent. (Item 7) A release film containing the cured film of the thermosetting release coating agent described in any one of items 1 to 6 and a plastic film as constituent elements. (Item 8) The release film according to item 7 above, wherein the plastic film is a polyethylene terephthalate film. (Item 9) A method for manufacturing a release film, characterized in that: the thermosetting release coating agent described in any one of the above items 1 to 6 is coated on at least one side of the plastic film and heated deal with. (Item 10) The method of manufacturing a release film as described in Item 9, wherein the plastic film is a polyethylene terephthalate film.

In the present invention, one or more of the above-mentioned features can be further combined to provide technical items in addition to the explicitly stated combination. Those with ordinary knowledge in the technical field to which the present invention pertains can read and understand the following detailed descriptions as needed to recognize further embodiments and advantages in addition to the above. [Effect of Invention]

The thermosetting release coating agent of the present invention is excellent in stability over time (lifetime). In addition, it is possible to form a cured film with good releasability and solvent resistance at a relatively low temperature in a short time, so the productivity is high. In addition, since the silicone that transfers from the cured film of the release agent to the adherend has low transferability, it is particularly useful as a release agent for various release films.

The release film of the present invention has a cured film with good release properties and solvent resistance, and the release film can be coated with, for example, a casting solution for resin film or inorganic paste containing many organic solvents.的材料。 The material.

The release film of the present invention is useful as a release film for production steps of resin sheets, synthetic leather, decorative boards, carbon fiber prepregs, ceramic electronic parts, and the like. Moreover, it is also suitable as a release film (separator) for the protection of the adhesion layer of a polarizer/phase difference plate, etc. for a release film for transfer-related products.

Throughout this specification, unless otherwise specified, the expression of the singular form also includes the concept of the plural form. In addition, unless otherwise specified, the terms used in this specification are used in the meaning generally used in the technical field. Therefore, as long as there is no other definition, the meanings of all professional and technical terms used in this specification are the same as those generally understood by those with ordinary knowledge in the technical field to which the present invention belongs. In case of conflict, this specification (including definitions) takes precedence.

(Description of the preferred embodiment) A preferred embodiment of the present invention will be described below. The embodiments provided below are provided for a better understanding of the present invention, and the scope of the present invention should not be limited to the following description. Therefore, it can be understood that those with ordinary knowledge in the technical field to which the present invention pertains can make appropriate changes within the scope of the present invention with reference to the description in this specification. In addition, the following embodiments of the present invention can be used alone or in combination of these embodiments.

The thermosetting release coating agent of the present invention (hereinafter referred to as coating agent) is a composition containing a specific (A) polyol (hereinafter referred to as (A) component), (B) a hydroxyl-containing polyol Silicone (hereinafter referred to as (B) component) and (C) polyisocyanate (hereinafter referred to as (C) component).

The component (A) is a polyol which has at least 3 hydroxyl groups in the molecule, has a molecular weight of about 80 to 5000, and has a hydroxyl value of about 30 to 2000 mgKOH/g. Various known polyols can be used without particular limitation. In this specification, "molecular weight" means formula weight or number average molecular weight. When the structure of the compound can be reliably expressed by a specific chemical formula like trimethylolpropane, the aforementioned molecular weight is the formula weight. On the other hand, when the structure of the compound cannot be reliably represented by a specific chemical formula like a ring-opening polymerization type polyester polyol or a polycondensation type polyester polyol, the aforementioned molecular weight is a number average molecular weight. Usually the upper limit of the molecular weight is about 5000, 4500, 4000, 3500, 3000, 2500, 2000, 1500, 1000, 900, 800, 700, 600, 500, 400, 300, 200, 150, 134, 100, usually the molecular weight The lower limit is about 4500, 4000, 3500, 3000, 2500, 2000, 1500, 1000, 900, 800, 700, 600, 500, 400, 300, 200, 150, 134, 100, 90, 80. The range of molecular weight can be set by appropriately selecting from the upper limit and lower limit described above. Also, the upper limit of the normal hydroxyl value is 2000mgKOH/g, 1900mgKOH/g, 1800mgKOH/g, 1700mgKOH/g, 1600mgKOH/g, 1500mgKOH/g, 1400mgKOH/g, 1300mgKOH/g, 1250mgKOH/g, 1200mgKOH/g, 1100mgKOH /g, 1000mgKOH/g, 900mgKOH/g, 800mgKOH/g, 700mgKOH/g, 600mgKOH/g, 550mgKOH/g, 540mgKOH/g, 500mgKOH/g, 400mgKOH/g, 350mgKOH/g, 340mgKOH/g, 300mgKOH/g , 200mgKOH/g, 100mgKOH/g, 90mgKOH/g, 85mgKOH/g, 84mgKOH/g, 80mgKOH/g, 70mgKOH/g, 60mgKOH/g, 56mgKOH/g, 50mgKOH/g, 40mgKOH/g, usually about hydroxyl value The lower limit is 1900mgKOH/g, 1800mgKOH/g, 1700mgKOH/g, 1600mgKOH/g, 1500mgKOH/g, 1400mgKOH/g, 1300mgKOH/g, 1250mgKOH/g, 1200mgKOH/g, 1100mgKOH/g, 1000mgKOH/g, 900mgKOH/g , 800mgKOH/g, 700mgKOH/g, 600mgKOH/g, 550mgKOH/g, 540mgKOH/g, 500mgKOH/g, 400mgKOH/g, 350mgKOH/g, 340mgKOH/g, 300mgKOH/g, 200mgKOH/g, 100mgKOH/g, 90mgKOH /g, 85mgKOH/g, 84mgKOH/g, 80mgKOH/g, 70mgKOH/g, 60mgKOH/g, 56mgKOH/g, 50mgKOH/g, 40mgKOH/g, 30mgKOH/g. It is possible to appropriately select from the upper limit and lower limit described above to set the range of the hydroxyl value. From the viewpoint of having both the solvent resistance and peelability of the cured film, it is preferable that the molecular weight is about 90 to 2000 and the hydroxyl value is about 80 to 1900 mgKOH/g.

As a non-limiting specific example of the component (A), for example, ring-opening polymerization type polyester polyol (a-1) (hereinafter referred to as (a-1) component) and/or polycondensation type polyester polyol ( a-2) (hereinafter referred to as (a-2) component).

(a-1) The component, specifically, the reaction product of various well-known lactones and triol and/or tetraol, namely polylactone triol and/or polylactone tetraol, etc. are mentioned. However, it is not intended to be limited to this ingredient. Examples of the lactone include: β-propiolactone, γ-butyrolactone, δ-valerolactone, β-methyl-δ-valerolactone, ε-caprolactone, etc.; two or more kinds may be combined use. In addition, examples of the triol include glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, etc.; Examples of the monohydric alcohol include pentaerythritol, etc.; two or more types may be used in combination. As the commercially available products of (a-1) component, for example, PLACCEL 303, the same series L320AL, the same series 305, the same 308, the same series 309, the same series 312, the same series 320, the same series 410, etc. (all are contests) Made by Lu Co., Ltd.).

(a-2) The component, specifically, the reactant of various well-known low-molecular-weight diols, low-molecular-weight dicarboxylic acids, and triols can be mentioned. (A-2) Examples of the component are not limited to this component, and examples include polyester polyols, polyester tetraols, polyester triols, and the like. Examples of the low-molecular-weight diols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1 ,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, etc.; Two or more types can be used in combination. Examples of the low molecular dicarboxylic acid include adipic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, oxalic acid, malonic acid, Glutaric acid, pimelic acid, azelaic acid, sebacic acid and suberic acid, and the corresponding anhydrides, etc.; two or more of them can be used in combination. The triol is the same as described above. As a commercially available product of the component (a-2), for example, Kuraray Polyol F-510, F-1010 of the same series, F-2010 of the same series, F-3010 of the same series (all manufactured by Kuraray Co., Ltd.) Wait.

When the (a-1) component and (a-2) component are used in combination, the mass ratio of these components is not limited. Usually, the upper limit of the mass ratio (a-1)/(a-2) is 1/99. 5/95, 10/90, 15/85, 20/80, 25/75, 30/70, 35/65, 40/60, 45/55, 50/50, 55/45, 60/40, 65/ Around 35, 70/30, 75/25, 80/20, 85/15, 90/10, 95/5. Also, the lower limit of the mass ratio is 5/95, 10/90, 15/85, 20/80, 25/75, 30/70, 35/65, 40/60, 45/55, 50/50, 55/45 , 60/40, 65/35, 70/30, 75/25, 80/20, 85/15, 90/10, 95/5, 99/1. The range of the mass ratio can be set by appropriately selecting from the upper limit value and lower limit value described above. The preferable range of the mass ratio is about 1/99 to 99/1.

Among (A) components, polyols (hereinafter referred to as (a-3) components) other than both (a-1) components and (a-2) components may also be cited. Specifically, examples thereof include polyether triol, polyether tetraol, polycarbonate triol, castor oil polyol, and alkyl polyol. In the present specification, "alkyl polyol" refers to a compound containing only an alkyl group, an alkylene group, and a hydroxyl group in the compound, and the compound contains 3 or more hydroxyl groups. Examples of "alkyl polyols" are not limited to these compounds, and examples include trimethylolpropane, glycerin, and pentaerythritol. Examples of commercially available products of (a-3) include ADEKA POLYETHER G-300, G-400, G-700, AM-302, AM-502, AM-702, BM-54, GM-30 (all (Made by ADEKA Co., Ltd.), HS 6G-160, HS CM-025P, HS CM-075P (all are manufactured by Feng Guo Oil Co., Ltd.), trimethylolpropane (manufactured by Mitsubishi Gas Chemical Co., Ltd.), glycerin (Manufactured by Sakamoto Pharmaceutical Co., Ltd.), neopentylerythritol (manufactured by Guangrong Chemical Industry Co., Ltd.), etc. As component (A), component (a-1) and component (a-2) are not included, and as long as the requirements of component (A) are satisfied, even if component (a-3) is used alone, it can provide the desired thermosetting properties Release coating agent. Furthermore, when component (a-3) is used in combination with component (a-1) and/or component (a-2), the ratio of component (a-3) in component (A) does not Particularly limited, usually less than 50% by mass, for example, less than 45% by mass, less than 40% by mass, less than 35% by mass, less than 34% by mass, less than 30% by mass, less than 25% by mass, less than 20% by mass, less than 15% by mass %, less than 10% by mass, and less than 5% by mass.

In addition, as the (A) component, each may contain: (A1) a polyol, which has at least 3 hydroxyl groups in the molecule, has a molecular weight of 200 to 5000, and has a hydroxyl value of 30 to 840 mgKOH/g; and, (A2) a polyol Alcohol has at least 3 hydroxyl groups in its molecule, has a molecular weight of 80 to 200, and a hydroxyl value of 841 to 2000 mgKOH/g.

(B) As long as the component is a so-called hydroxyl-containing organic modified polysiloxane, various well-known polysiloxanes can be used without particular limitation. As the modified part, for example, at least one selected from the group consisting of an acrylic polymer part, a polyester part, a polyether part, and a carbinol part can be cited. The acrylic polymer portion may be, for example, a (co)polymer of acrylate and/or methacrylate. In addition, the modified part only needs to be introduced into any one of the single end, both ends, and branches of the polysiloxane chain.

Examples of commercially available products in which the aforementioned modified part is the component (B) of an acrylic polymer include: ZX-028-G (manufactured by T&K TOKA Co., Ltd.), BYK-SILCLEAN 3700 (manufactured by BYK Co., Ltd., Japan), SYMAC US-270 (manufactured by Toagosei Co., Ltd.), etc.; two or more types can be combined for use.

Examples of commercially available products in which the modified portion is the component (B) of polyester and the commercially available product in which the modified portion is the component (B) of polyether include BYK-370, BYK-375, BYK- 377, BYK-SILCLEAN3720 (manufactured by BYK Co., Ltd. in Japan), X-22-4952, KF-6123 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc.; more than two types can be used in combination.

Examples of commercially available products in which the aforementioned modified part is the component (B) of the original alcohol 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, X-22-176F (manufactured by Shin-Etsu Chemical Co., Ltd.), SILAPLANE FM-4411, SILAPLANE FM -4421, SILAPLANE FM-4425, SILAPLANE FM-0411, SILAPLANE FM-0421, SILAPLANE FM-DA11, SILAPLANE FM-DA21, SILAPLANE FM-DA26 (manufactured by JNC Co., Ltd.), etc.; more than two types can be used in combination.

(C) Component includes, for example, aromatic diisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, and xylene diisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine Aliphatic diisocyanates such as acid diisocyanate; alicyclic diisocyanates such as dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate, etc. Diisocyanates; and, triisocyanates such as isocyanurates, adducts, and biurets of the diisocyanates. Moreover, so-called polymeric isocyanates, such as polymethylene polyphenyl polyisocyanate, can also be used, for example. Two or more of these polyisocyanates can be used in combination.

The usage amount of component (A) and component (C) is not particularly limited. The upper limit of the molar ratio (NCO/OH) of the isocyanate group of component (C) to the hydroxyl group of component (A) is 3, 2.5, 2. 1.5, 1, 0.5, 0.4, 0.3. In addition, the lower limit of the molar ratio (NCO/OH) of the isocyanate group of the component (C) and the hydroxyl group of the component (A) is 2.5, 2, 1.5, 1, 0.5, 0.4, 0.3, and 0.2. In addition, it can be suitably selected from the upper limit and lower limit described above, and the range of the molar ratio (NCO/OH) of the isocyanate group of (C) component and the hydroxyl group of (A) component can be set. A preferable range of the molar ratio (NCO/OH) of the isocyanate group of the component (C) to the hydroxyl group of the component (A), especially from the viewpoint of solvent resistance, usually only the isocyanide of the component (C) The molar ratio (NCO/OH) of the acid group and the hydroxyl group of the component (A) may be about 0.2 to 3.

The usage amount of (B) component is not particularly limited. The upper limit of the usage amount of (B) component is usually calculated as solid content relative to the total mass of (A) component and (C) component (calculated as solid content) 10 mass%, 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, 0.8 mass%, 0.5 mass%, 0.2 mass %. In addition, the lower limit of the amount of (B) component used is usually 9 mass%, 8 mass%, 7 mass% in terms of solid content relative to the total mass of (A) component and (C) component (calculated as solid content) , 6% by mass, 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1% by mass, 0.8% by mass, 0.5% by mass, 0.2% by mass, and 0.1% by mass. In addition, it is possible to appropriately select from the upper limit value and the lower limit value described above to set the use amount range of the component (B). (B) A preferred example of the amount of component used, from the viewpoint of solvent resistance and mold release properties, usually relative to the total mass (calculated as solid content) of component (A) and component (C), as long as it becomes The range of about 0.1-10% by mass (calculated as solid content) is sufficient.

The coating agent of the present invention may contain various known (D) curing catalysts (hereinafter referred to as (D) component) as necessary. As the (D) component, for example, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec-7-ene ( DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) and other tertiary amine compounds; dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dimaleate Dibutyl tin acid, dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin sulfide, tributyl tin sulfide, tributyl tin oxide, tributyl tin acetate, triethyl tin ethoxy, tributyl tin ethoxy, dioctyl tin oxide , Dioctyltin dilaurate, dioctyltin dineodecanoate, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate and other tin compounds; dibutyltitanium dichloride, titanium Titanium compounds such as tetrabutyl ester, butoxy titanium trichloride; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, lead naphthenate, etc.; iron 2-ethylhexanoate, Iron-based compounds such as iron acetoacetone; cobalt-based compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; bismuth-based compounds such as bismuth 2-ethylhexanoate and bismuth naphthenate, etc.; two or more types can be combined use. Among them, from the viewpoint of curability, the tin-based compound and/or the iron-based compound are preferred. In addition, from the viewpoint of the life span of the coating agent, the iron-based compound described above is preferable.

When (D) component is used, its usage amount is not particularly limited. The upper limit of (D) component usage amount is usually 10 mass relative to the total mass of (A) and (C) components (calculated as solid content) %, 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, 0.5 mass%, 0.1 mass%. In addition, the lower limit of the amount of (D) component used is usually 9 mass%, 8 mass%, 7 mass%, 6 mass%, relative to the total mass of (A) and (C) components (calculated as solid content). 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, 0.5 mass%, 0.1 mass%, 0.01 mass%. In addition, it is possible to appropriately select from the upper limit value and the lower limit value described above to set the use amount range of the component (D). (D) A preferable example of the usage range of the component, from the viewpoint of the life span of the coating agent, the reaction curing speed, etc., is usually relative to the total mass of the components (A) and (C) (calculated as solid content) What is necessary is just to be in the range of about 0.01-10 mass% (calculated as solid content).

The coating agent of the present invention may contain various known (E) organic solvents (hereinafter referred to as (E) component) as necessary. Specifically, for example, methyl ethyl ketone, methyl isobutyl ketone, acetone, acetone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol dimethyl Base ether, toluene, xylene, isopropanol, ethanol, butanol, etc.; two or more kinds can be used in combination. Among them, from the viewpoint of the useful life of the coating agent of the present invention, it is preferable to include a ketone-based organic solvent, and among the ketone-based organic solvent, it is preferable to include acetylacetone.

When the (E) component is used, the usage amount is not particularly limited. Generally, the upper limit of the usage amount of the (E) component is based on the solid content concentration of the coating agent of the present invention to be 50% by mass, 45 Mass%, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 21% by mass, 20% by mass, 15% by mass, 10% by mass, and about 5% by mass are used. (E) The lower limit of the amount of component used is the solid content concentration of the coating agent of the present invention as 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, and 21% by mass in terms of solid content. , 20% by mass, 15% by mass, 10% by mass, 5% by mass, and 1% by mass. In addition, it is possible to appropriately select from the upper limit value and the lower limit value described above to set the use amount range of the (E) component. It is preferable to use the component (E) so that the solid content concentration of the coating agent of the present invention becomes 1 to 50% by mass.

The coating agent of the present invention may contain various known (F) glycols (hereinafter referred to as (F) component) as necessary. Specifically, for example, polycaprolactone diol, polyester diol (except polycaprolactone diol), polyether diol, polycarbonate diol, and the like can be cited. As a commercially available product of the component (F), for example, Kuraray Polyol P-510, the same series P-1010, the same series P-1020, the same series P-2010 (all manufactured by Kuraray Co., Ltd.), PLACCEL 205, the same series 208, the same series 210, the same series 212 (all manufactured by Daicel Co., Ltd.), ADEKA POLYETHER P-400, BPX-11 (all manufactured by ADEKA Co., Ltd.), Kuraray Polyol C-590, the same Series C-1090, the same series C-2090 (all manufactured by Kuraray Co., Ltd.), DURANOL T-5650J, the same series T-5652 (all manufactured by Asahi Kasei Chemical Co., Ltd.), PLACCEL CD210 (Daicel Co., Ltd.) Company manufacture), NIPPOLLAN 981, the same series 980R (manufactured by Tosoh Co., Ltd.), ethylene glycol, diethylene glycol, 14BG (all manufactured by Mitsubishi Chemical Co., Ltd.), CHDM-D (Nagaze Industrial Co., Ltd.) Manufacturing) and so on.

When the (F) component is used, the usage amount is not particularly limited. Generally, the upper limit of the usage amount of the (F) component is relative to the total mass (calculated as solid content) of the (A) component and the (F) component. It is 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, and 5% by mass; (F) the lower limit of the amount of component used , Relative to the total mass of (A) component and (F) component (calculated as solid content), it is 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, and 15% by mass , 10% by mass, 5% by mass, and 1% by mass. In addition, it is possible to appropriately select from the upper limit value and the lower limit value described above to set the use amount range of the (F) component. It is preferable to use the component (F) so as to be 1% by mass to 50% by mass.

The coating agent of the present invention is composed of (A) component, (B) component, and (C) component, and optionally selected from the group consisting of (D) component, (E) component and (F) component One or more of the ingredients are mixed together. The mixing means and mixing order are not particularly limited.

The coating agent of the present invention may contain binder resins (acrylic resins, urethane resins, polyester resins, epoxy resins, alkyd resins, etc.), fine particles, anti-slip agents, other than component (A) as necessary Preservatives, rust inhibitors, pH adjusters, antioxidants, pigments, dyes, lubricants, levelers, defoamers, etc.

The release film of the present invention is an article comprising a cured film and a plastic film as constituent elements, the cured film is composed of the thermosetting release coating agent of the present invention, and the release film of the present invention is It is obtained by coating the coating agent of the present invention on at least one side of a plastic film and performing heat treatment.

Examples of the aforementioned plastic film include polycarbonate film, polymethyl methacrylate film, polystyrene film, polyethylene terephthalate film, polyimide film, polyolefin film, and nylon film. , Epoxy resin film, melamine resin film, cellulose triacetate resin film, acrylonitrile/butadiene/styrene (ABS) resin film, acrylonitrile/styrene (AS) resin film, norbornene-based resin film, etc. . In addition, the plastic film can be subjected to surface treatment (corona discharge, etc.). In addition, the plastic film may be provided with a layer other than the coating composition composition of the present invention (for example, an easy-adhesion layer) on one or both sides of the plastic film. The plastic film is preferably polyethylene terephthalate from the viewpoint of transparency, dimensional stability, mechanical properties, and chemical resistance. In addition, the thickness of the plastic film is not particularly limited, and usually only needs to be about 10 to 100 μm.

The aforementioned coating means is not particularly limited, and examples thereof include a roll coater, a reverse roll coater, a gravure coater, a knife coater, and a bar coater. The coating amount is also not particularly limited, but it is usually within ^{a range of about 0.1 to 10 g/m 2} in the mass after drying, and preferably within a range of 0.2 to 5 g/m ² in the mass after drying.

The aforementioned heating conditions are also not particularly limited, and are usually 90 to 130°C for 30 seconds to 2 minutes. The coating agent of the present invention has relatively good rapid curing properties at relatively low temperatures. Therefore, the coating agent of the present invention is suitable for plastic films that are easily deformed by heat.

In addition, the release film of the present invention may be subjected to an aging treatment as needed. The conditions are not particularly limited, and it is about 1 to 24 hours at 20 to 50°C. By doing so, the solvent resistance of the cured film can be improved.

In order to facilitate the understanding of the present invention, preferred embodiments are shown and described above. The present invention is described below based on examples, but the above description and the following examples are provided for illustration only, and are not provided for limiting the present invention. Therefore, the scope of the present invention is not limited to the embodiments specifically described in this specification, nor is it limited to the examples, but only limited to the scope of the patent application. [Example]

The following examples and comparative examples illustrate the present invention in detail, but are not intended to limit the scope of the present invention. The explanation of the present invention is not limited to these examples and comparative examples, and the embodiments obtained by appropriately combining the technical means disclosed in the respective examples are also deemed to be included in the scope of the present invention. In addition, in the respective Examples and Comparative Examples, parts or% are based on mass.

In addition, the hydroxyl value can be measured by a method based on Japanese Industrial Standards (JIS) K0070. The number average molecular weight can be measured using gel permeation chromatography (GPC) and based on the calibration curve of polystyrene.

<Preparation of thermosetting release coating agent> (Example 1) 10.00 parts of Kuraray Polyol F-510 (manufactured by Kuraray Co., Ltd., manufactured by 3-methyl-1,5-pentane) was used as component (A) A polyester polyol with a number average molecular weight of 500 and a hydroxyl value of 340 mgKOH/g composed of diol, adipic acid and trimethylolpropane), 0.22 parts BYK-377 (manufactured by BYK Co., Ltd., Japan) as the component (B) , Polyether modified polysiloxane containing hydroxyl, solid content 100%), 11.86 parts of CORONATE HX as component (C) (manufactured by Tosoh Co., Ltd., isocyanurate of hexamethylene diisocyanate) , Solid content 100%), 0.02 parts of dioctyltin dilaurate as component (D) (100% solid content, referred to as DOTDL hereinafter), and 83.14 parts of mixed solvent as component (E) (hereinafter referred to as MEK/MIBK mixed solvent), the mass ratio of methyl ethyl ketone and methyl isobutyl ketone in the mixed solvent is 1:1. The above components were uniformly mixed to prepare a thermosetting release coating agent with a solid content concentration of 21%.

(Example 2) 10.00 parts of Kuraray Polyol F-510 as component (A) and 0.87 parts of BYK-370 as component (B) (manufactured by BYK Co., Ltd., polyester modified polysiloxane containing hydroxyl, solid (Component concentration 25%), 11.86 parts of CORONATE HX as (C) component, 0.02 parts of DOTDL as (D) component, and 82.48 parts of MEK/MIBK mixed solvent as (E) component. The above components were uniformly mixed to prepare a thermosetting release coating agent with a solid content concentration of 21%.

(Example 3) 10.00 parts of Kuraray Polyol F-510 as component (A) and 0.87 parts of BYK-SILCLEAN 3700 as component (B) (manufactured by BYK Co., Ltd. in Japan, polysiloxane-modified hydroxyl-containing acrylic polymer) , Solid content concentration 25%), 11.86 parts of CORONATE HX as component (C), 0.02 parts of DOTDL as component (D), and 82.48 parts of MEK/MIBK mixed solvent as component (E). The above components were uniformly mixed to prepare a thermosetting release coating agent with a solid content concentration of 21%.

(Example 4) 10.00 parts of Kuraray Polyol F-510 as component (A), 0.26 parts of BYK-377 as component (B), and 21.91 parts of TAKENATE D-110N as component (C) were used (Mitsui Chemicals Co., Ltd.) Manufacture, xylene diisocyanate adduct, solid content concentration 75%), 0.03 parts of DOTDL as component (D), and 95.06 parts of MEK/MIBK mixed solvent as component (E). The above components were uniformly mixed to prepare a thermosetting release coating agent with a solid content concentration of 21%.

(Example 5) 10.00 parts of Kuraray Polyol F-510 as component (A), 0.27 parts of BYK-377 as component (B), and 22.91 parts of TAKENATE D-120N as component (C) (Mitsui Chemicals Co., Ltd.) Manufacture, hydrogenated xylene diisocyanate adduct, solid content concentration 75%), 0.03 parts of DOTDL as (D) component, and 97.65 parts of MEK/MIBK mixed solvent as (E) component. The above components were uniformly mixed to prepare a thermosetting release coating agent with a solid content concentration of 21%.

(Example 6) 10.00 parts of Kuraray Polyol F-510 as component (A), 0.18 parts of BYK-377 as component (B), and 8.13 parts of MILLIONATE MR-200 as component (C) (Tosoh Corporation) Manufactured and polymerized diphenylmethane isocyanate (MDI), solid content concentration 100%), 0.02 parts of DOTDL as component (D), and 68.95 parts of MEK/MIBK mixed solvent as component (E). The above components were uniformly mixed to prepare a thermosetting release coating agent with a solid content concentration of 21%.

(Example 7) 10.00 parts of PLACCEL 303 (manufactured by Daicel Co., Ltd., polycaprolactone triol having a number average molecular weight of 300 and a hydroxyl value of 540 mgKOH/g) as component (A), 0.29 as component (B) Parts of BYK-377, 19.02 parts of CORONATE HX as (C) component, 0.03 parts of DOTDL as (D) component, and 110.39 parts of MEK/MIBK mixed solvent as (E) component. The above components were uniformly mixed to prepare a thermosetting release coating agent with a solid content concentration of 21%.

(Example 8) 10.00 parts of PLACCEL L320AL (manufactured by Daicel Co., Ltd., polycaprolactone triol with a number average molecular weight of 2000 and a hydroxyl value of 84 mgKOH/g) as component (A) and 0.13 as component (B) Parts of BYK-377, 2.96 parts of CORONATE HX as (C) component, 0.01 parts of DOTDL as (D) component, 49.29 parts of MEK/MIBK mixed solvent as (E) component. The above components were uniformly mixed to prepare a thermosetting release coating agent with a solid content concentration of 21%.

(Example 9) 10.00 parts of ADEKA POLYETHER AM-302 (manufactured by ADEKA Co., Ltd., polyether triol with a number average molecular weight of 3000 and a hydroxyl value of 56 mgKOH/g) as component (A) and 0.12 as component (B) Parts of BYK-377, 1.97 parts of CORONATE HX as (C) component, 0.01 parts of DOTDL as (D) component, and 45.54 parts of MEK/MIBK mixed solvent as (E) component. The above components were uniformly mixed to prepare a thermosetting release coating agent with a solid content concentration of 21%.

(Example 10) 10.00 parts of Kuraray Polyol F-510 as component (A), 0.26 parts of BYK-377 as component (B), and 21.91 parts of TAKENATE D-110N as component (C) were used as component (E) 94.96 parts of MEK/MIBK mixed solvent. The above components were uniformly mixed to prepare a thermosetting release coating agent with a solid content concentration of 21%.

(Example 11) 10.00 parts of Kuraray Polyol F-510 as component (A), 0.22 parts of BYK-377 as component (B), 11.86 parts of CORONATE HX as component (C), and 0.02 part as component (D) Part of ginseng (2,4-pentanedione) iron (III), solid content concentration 100%, hereinafter referred to as TPDI), 83.14 parts of MEK/MIBK mixed solvent as the (E) component. The above components were uniformly mixed to prepare a thermosetting release coating agent with a solid content concentration of 21%.

(Example 12) 10.00 parts of Kuraray Polyol F-510 as component (A), 0.26 parts of BYK-377 as component (B), and 21.91 parts of TAKENATE D-110N as component (C) were used as component (D) 0.03 parts of TPDI, 95.06 parts of MEK/MIBK mixed solvent as component (E). The above components were uniformly mixed to prepare a thermosetting release coating agent with a solid content concentration of 21%.

(Example 13) 10.00 parts of PLACCEL 303 as component (A), 0.36 parts of BYK-377 as component (B), 35.15 parts of TAKENATE D-110N as component (C), and 0.04 parts as component (D) TPDI, 129.52 parts of MEK/MIBK mixed solvent as component (E). The above components were uniformly mixed to prepare a thermosetting release coating agent with a solid content concentration of 21%.

(Example 14) 10.00 parts of PLACCEL 303 as component (A), 1.16 parts of BYK-SILCLEAN 3700 as component (B), and 0.07 parts of SILAPLANE FM-DA11 (manufactured by JNC Co., Ltd., original alcohol-modified silicone, Solid content concentration 100%), 35.15 parts of TAKENATE D-110N as component (C), 0.04 parts of TPDI as component (D), and 128.65 parts of MEK/MIBK mixed solvent as component (E). The above components were uniformly mixed to prepare a thermosetting release coating agent with a solid content concentration of 21%.

(Example 15) 10.00 parts of Kuraray Polyol F-510 as (A) component, 0.85 parts of BYK-SILCLEAN 3700 as (B) component, 0.05 parts of SILAPLANE FM-DA11, and 21.91 parts of TAKENATE D- as component (C) were used. 110N, 0.03 parts of TPDI as component (D), and 94.43 parts of MEK/MIBK mixed solvent as component (E). The above components were uniformly mixed to prepare a thermosetting release coating agent with a solid content concentration of 21%.

(Example 16) 10.00 parts of trimethylolpropane (manufactured by Mitsubishi Gas Chemical Co., Ltd., an alkyl triol with a molecular weight of 134 and a hydroxyl value of 1250 mgKOH/g) as component (A) and 2.28 as component (B) Parts of BYK-SILCLEAN 3700 and 0.14 parts of SILAPLANE FM-DA11, 81.66 parts of TAKENATE D-110N as component (C), 0.07 parts of TPDI as component (D), and 248.84 parts of MEK/MIBK mixed solvent as component (E). The above components were uniformly mixed to prepare a thermosetting release coating agent with a solid content concentration of 21%.

(Example 17) 10.00 parts of PLACCEL 303 and 5.00 parts of trimethylolpropane as component (A), 2.30 parts of BYK-SILCLEAN 3700 as component (B) and 0.14 parts of SILAPLANE FM-DA11 as component (C) were used 75.99 parts of TAKENATE D-110N, 0.07 parts of TPDI as (D) component, and 253.07 parts of MEK/MIBK mixed solvent as (E) component. The above components were uniformly mixed to prepare a thermosetting release coating agent with a solid content concentration of 21%.

(Example 18) 10.00 parts of PLACCEL 303 and 5.00 parts of trimethylolpropane as component (A), 2.30 parts of BYK-SILCLEAN 3700 as component (B) and 0.14 parts of SILAPLANE FM-DA11 as component (C) were used 75.99 parts of TAKENATE D-110N, 0.07 parts of TPDI as (D) component, 3.60 parts of acetylacetone as (E) component, and 249.47 parts of MEK/MIBK mixed solvent. The above components were uniformly mixed to prepare a thermosetting release coating agent with a solid content concentration of 21%.

(Comparative Example 1) 10.00 parts of Kuraray Polyol P-1010 (manufactured by Kuraray Co., Ltd., composed of 3-methyl-1,5-pentanediol and adipic acid, number average molecular weight) was used as component (A) 1000 and the hydroxyl value of 112mgKOH/g polyester diol), 0.14 parts of BYK-377 as (B) component, 3.95 parts of CORONATE HX as (C) component, 0.01 parts of DOTDL as (D) component, as (E ) 53.04 parts of MEK/MIBK mixed solvent of ingredients. The above components were uniformly mixed to prepare a thermosetting release coating agent with a solid content concentration of 21%.

(Comparative Example 2) In Example 1, BYK-377 was not used, and otherwise the same was performed to prepare a thermosetting release coating agent.

[Table 1]

(B)%: mass% of (B) component relative to (A) and (C) component (D)%: mass% of (D) component relative to (A) and (C) component

<Preparation of a release film> The coating agent of Example 1 was applied to a commercially available polyethylene terephthalate film (trade name: Lumirror T60, 50 μm thick) so that the coating film thickness after drying became 1 μm. ) And dried at 120°C for 1 minute to produce a release film with a cured film composed of the coating agent. Regarding Example 10, it was dried at 120°C for 10 minutes to produce a release film with a cured film composed of the coating agent; regarding the coating agents of other examples and comparative examples, Then, it carried out similarly to Example 1, and produced the release film.

<Solvent resistance of the cured film> After the release film of Example 1 was left at 23°C overnight, the cured film was rubbed with a cotton swab impregnated with methyl ethyl ketone. As a result, the cured film was hardened even after more than 100 rounds. Did not dissolve. On the other hand, the release film of Example 9 was evaluated in the same manner, and as a result, the base film was exposed at the 80th time. The release film of other examples was also evaluated for solvent resistance in the same manner, and even if it exceeded 100 rounds, the cured film did not dissolve. On the other hand, the release film of Comparative Example 1 was evaluated in the same manner. As a result, the base film was exposed at the second time. On the other hand, the film of Comparative Example 2 did not dissolve the cured film even if it went back and forth more than 100 times. The results are shown in Table 2.

<Evaluation of mold release> After leaving the release film of Example 1 overnight, a polyester adhesive tape (31B tape manufactured by Nitto Denko Co., Ltd.: 20mm width) was pressed onto the surface of the cured film with a 2kg roller. , Laminate on one side, and place it at 23°C for 1 hour. Then, using the Tensilon universal testing machine (product name: RTC-1250A, manufactured by ORIENTEC Co., Ltd.), the aforementioned adhesive tape was stretched (0.3m/min) at an angle of 180° in the horizontal direction, and the force required for peeling was measured ( N/20mm). In addition, the other Examples and Comparative Examples were also performed in the same manner to measure the peeling force. The release film of Comparative Example 1 was evaluated. As a result, cohesion failure occurred in the cured film, so it was regarded as unmeasurable. The results are shown in Table 2.

[Table 2]

In this case, priority is claimed for Japanese Patent Application 2016-90241 (application on April 28, 2016) and Japanese Patent Application 2016-157084 (application on August 10, 2016), and it shall be as if the entire contents of these have been specifically recorded in This content is quoted in this specification as a reference to this specification.

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Claims (9)

A thermosetting release coating agent comprising: (A) polyol, or (A1) polyol and (A2) polyol; (B) hydroxyl-containing polysiloxane; and (C) polyisocyanate; wherein, the (A) The polyol has at least 3 hydroxyl groups in the molecule, and the molecular weight is 80-5000, and the hydroxyl value is 30-2000mgKOH/g, and the component (A) contains ring-opening polymerizable polyester polyol (a-1) And/or polycondensed polyester polyol (a-2); the (A1) polyol has at least 3 hydroxyl groups in the molecule, and has a molecular weight of 200 to 5000, and a hydroxyl value of 30 to 840 mgKOH/g; the ( A2) The polyol has at least 3 hydroxyl groups in the molecule, and the molecular weight is 80-200, and the hydroxyl value is 841-2000 mgKOH/g. The thermosetting release coating agent according to claim 1, wherein the polyol of the component (A) has a molecular weight of 200 to 5000 and a hydroxyl value of 30 to 840 mgKOH/g. The thermosetting release coating agent according to claim 1 or 2, wherein the component (B) is selected from the group consisting of an acrylic polymer part, a polyester part, a polyether part, and a primary alcohol part At least one of. The thermosetting release coating agent according to claim 1 or 2, which further contains (D) a curing catalyst. The thermosetting release coating agent according to claim 1 or 2, which further contains (E) an organic solvent. A release film comprising the cured film of the thermosetting release coating agent described in any one of claims 1 to 5 and a plastic film as constituent elements. The release film according to claim 6, wherein the plastic film is a polyethylene terephthalate film. A method for manufacturing a release film, which is characterized in that: the thermosetting release coating agent described in any one of claims 1 to 5 is coated on at least one surface of a plastic film and heated. The method for manufacturing a release film according to claim 8, wherein the plastic film is a polyethylene terephthalate film.