JP2018028049A - Thermosetting release coating agent, release film, and method for producing release film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel thermosetting mold release coating agent capable of forming a cured coating film having excellent releasability and less problem of bleed-out on a plastic film at a relatively low temperature and in a short time. SOLUTION: (A) a polyol having at least 3 hydroxyl groups in a molecule, a molecular weight of 80 to 5000, and a hydroxyl value of 30 to 2000 mgKOH / g, (B) a hydroxyl group-containing silicone, and (C) A thermosetting release coating agent containing a polyisocyanate. [Selection diagram] None

Description

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

  Plastic films such as polyethylene terephthalate have excellent properties such as transparency, dimensional stability, mechanical properties, and chemical resistance, and are therefore used in various industrial fields. Specific examples include use as a base film for optical film products such as prism sheets for LCD members, light diffusion sheets, reflectors, antireflection plates, touch panels, explosion-proof films, and PDP filters.

  In addition, the plastic film is often used as a base film for a release film, and is also used as a separator for various adhesive sheets and protective films for touch panels. Moreover, a release film is used also in the manufacturing process of a ceramic electronic component or a resin sheet.

  A silicone resin is known as a release agent used for the release film.

  Patent Document 1 proposes a method of laminating a mixture liquid composed of an acrylic resin, a melamine resin, and a silicone resin. Moreover, as described in Patent Document 2, an acid catalyst may be used in combination for the purpose of improving the curability of the melamine resin.

JP-A-11-170440 JP 2002-19037 A

  However, the silicone resin often bleeds out to the surface of the coating film and moves to an adherend such as a pressure-sensitive adhesive or a resin sheet laminated on the coating film. Moreover, the compounding liquid used in the method of laminating the compounding liquid composed of an acrylic resin, a melamine resin and a silicone resin has a problem that the temperature necessary for curing is 190 ° C. and the heat damage to the substrate is large. Further, when an acid catalyst is used in combination, there is also a problem that the stability with time (pot life) of the coating agent is deteriorated to increase the viscosity and to decrease the workability.

  The present invention provides a novel thermosetting release coating agent that can form a cured coating film on a plastic film that has excellent releasability and less bleed-out problems at a lower temperature and in a shorter time than conventional ones. The task is to do.

  As a result of studies, the present inventor has found that the above-described problem can be solved by a thermosetting release coating agent containing a predetermined polyol, a predetermined silicone resin, and a polyisocyanate. That is, the present invention relates to the following thermosetting release coating agent and a method for producing a release film.

The present disclosure provides the following items.
(Item 1)
(A) a polyol having at least three hydroxyl groups in the molecule, a molecular weight of 80 to 5000, and a hydroxyl value of 30 to 2000 mgKOH / g;
(B) a hydroxyl group-containing silicone;
(C) a polyisocyanate;
A thermosetting release coating agent comprising:
(Item 2)
(A) The thermosetting release coating agent of the said item whose polyol of a component is 200-5000 molecular weight and whose hydroxyl value is 30-840 mgKOH / g.
(Item 3)
(A1) a polyol having at least three hydroxyl groups in the molecule, a molecular weight of 200 to 5000, and a hydroxyl value of 30 to 840 mgKOH / g;
(A2) a polyol having at least three hydroxyl groups in the molecule, a molecular weight of 80 to 200, and a hydroxyl value of 841 to 2000 mgKOH / g;
(B) a hydroxyl group-containing silicone;
(C) a polyisocyanate;
A thermosetting release coating agent comprising:
(Item 4)
The thermosetting release coating agent according to any one of the above items, wherein the component (A) comprises a ring-opening polymerization type polyester polyol (a-1) and / or a polycondensation type polyester polyol (a-2). .
(Item 5)
(B) The thermosetting release coating agent according to any one of the above items, wherein the component comprises at least one selected from the group consisting of an acrylic polymer moiety, a polyester moiety, a polyether moiety, and a carbinol moiety.
(Item 6)
The thermosetting release coating agent according to any one of the above items, further comprising (D) a curing catalyst.
(Item 7)
The thermosetting release coating agent according to any one of the above items, further comprising (E) an organic solvent.
(Item 8)
A release film comprising a cured film of a thermosetting release coating agent according to any one of the above items and a plastic film as constituent elements.
(Item 9)
The release film as described above, wherein the plastic film is a polyethylene terephthalate film.
(Item 10)
A method for producing a release film, wherein the thermosetting release coating agent according to any one of the above items is applied to at least one surface of a plastic film, followed by heat treatment.
(Item 11)
The method for producing a release film according to the above item, wherein the plastic film is a polyethylene terephthalate film.

  In this disclosure, it is contemplated that one or more of the above-described features may be provided in further combinations in addition to the express combinations. Additional embodiments and advantages other than those described above will be recognized by those of ordinary skill in the art upon reading and understanding the following detailed description as necessary.

  The thermosetting release coating agent of the present invention is excellent in aging stability (pot life). In addition, since a cured film having good releasability and solvent resistance is formed at a relatively low temperature in a short time, productivity is high. Moreover, since the silicone transfer property from the cured film of the coating agent to the adherend is small, it is particularly useful as a release agent for various release films.

  The release film according to the present invention is provided with a cured film having good release properties and solvent resistance, and a material containing a large amount of an organic solvent, such as a cast solution for resin sheets and an inorganic slurry, is coated thereon. can do.

  The release film according to the present invention is useful as a release film for production processes of resin sheets, synthetic leather, decorative boards, carbon fiber prepregs, ceramic electronic components and the like. Further, it is also suitable as a release film for transfer printing related products, a release film (separator) for protecting an adhesive layer such as a polarizing plate or a retardation plate.

  Throughout this specification, the singular forms also include the plural concept unless specifically stated otherwise. Moreover, the term used in this specification is used by the meaning normally used in the said field unless there is particular mention. Thus, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

(Description of Preferred Embodiment)
Hereinafter, preferred embodiments of the present invention will be described. 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 is obvious that those skilled in the art can make appropriate modifications within the scope of the present invention with reference to the description in the present specification. Also, the following embodiments of the present invention may be used alone or in combination.

  The thermosetting release coating agent (hereinafter referred to as coating agent) of the present invention comprises a predetermined (A) polyol (hereinafter referred to as (A) component), (B) hydroxyl group-containing silicone (hereinafter referred to as (B) component), (C) It is a composition containing polyisocyanate (henceforth (C) component).

  The component (A) is a polyol having at least three hydroxyl groups in the molecule, a molecular weight of about 80 to 5,000, and a hydroxyl value of about 30 to 2,000 mg KOH / g. Can be used without restrictions. In the present specification, “molecular weight” is a formula weight or a number average molecular weight. When the structure of a compound can be uniquely expressed by a specific chemical formula such as trimethylolpropane, the molecular weight is a formula weight. On the other hand, when the structure of a compound cannot be expressed uniquely with a specific chemical formula, such as a ring-opening polymerization type polyester polyol or a polycondensation type polyester polyol, the molecular weight is a number average molecular weight. Usually, the upper limit of molecular weight is about 5000, 4500, 4000, 3500, 3000, 2500, 2000, 1500, 1000, 900, 800, 700, 600, 500, 400, 300, 200, 150, 134, 100, The lower limit of the molecular weight is about 4500, 4000, 3500, 3000, 2500, 2000, 1500, 1000, 900, 800, 700, 600, 500, 400, 300, 200, 150, 134, 100, 90, 80. The molecular weight range can be set by appropriately selecting from the upper limit and lower limit values described above. The upper limit of the hydroxyl value is usually 2000 mgKOH / g, 1900 mgKOH / g, 1800 mgKOH / g, 1700 mgKOH / g, 1600 mgKOH / g, 1500 mgKOH / g, 1400 mgKOH / g, 1300 mgKOH / g, 1250 mgKOH / g, 1200 mgKOH / g, 1100 mgKOH / g. g, 1000 mg KOH / g, 900 mg KOH / g, 800 mg KOH / g, 700 mg KOH / g, 600 mg KOH / g, 550 mg KOH / g, 540 mg KOH / g, 500 mg KOH / g, 400 mg KOH / g, 350 mg KOH / g, 340 mg KOH / g, 300 mg KOH / g, 200 mg KOH / g, 100 mg KOH / g, 90 mg KOH / g, 85 mg KOH / g, 84 mg KOH / g, 70 m KOH / g, 60 mgKOH / g, 56 mgKOH / g, 50 mgKOH / g, about 40 mgKOH / g, and usually the lower limit of the hydroxyl value is 1900 mgKOH / g, 1800 mgKOH / g, 1700 mgKOH / g, 1600 mgKOH / g, 1500 mgKOH / g, 1400 mgKOH / g, 1300 mgKOH / g, 1250 mgKOH / g, 1200 mgKOH / g, 1100 mgKOH / g, 1000 mgKOH / g, 900 mgKOH / g, 800 mgKOH / g, 700 mgKOH / g, 600 mgKOH / g, 550 mgKOH / g, 540 mgKOH / g, 500 mgKOH / g g, 400 mgKOH / g, 350 mgKOH / g, 340 mgKOH / g, 300 mgKOH / g, 200 mgKOH / g, 100 mgK H / g, a 90mgKOH / g, 85mgKOH / g, 84mgKOH / g, 70mgKOH / g, 60mgKOH / g, 56mgKOH / g, 50mgKOH / g, 40mgKOH / g, 30mgKOH / g approximately. The range of the hydroxyl value can be set by appropriately selecting from the upper limit and lower limit values described above. From the viewpoint of achieving both solvent resistance and peelability of the cured film, the molecular weight is preferably about 90 to 2000, and the hydroxyl value is about 80 to 1900 mgKOH / g.

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

  Specific examples of the component (a-1) include polycaprolactone triol and / or polycaprolactone tetraol, which are reaction products of various known caprolactones with triols and / or tetraols. However, it is not intended to be limited to this. Examples of the caprolactone include β-propiolactone, γ-butyrolactone, δ-valerolactone, β-methyl-δ-valerolactone, and ε-caprolactone, and two or more of them can be used in combination. Examples of the triol include glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanepolyol, 1,2,4-butanepolyol, and the tetraol includes pentaerythritol. More than one species can be used in combination. Examples of commercially available (a-1) component include Plaxel 303, L320AL, 305, 308, 309, 312, 320, and 410 (all manufactured by Daicel Corporation).

  Specifically, the component (a-2) is a reaction product with various known low-molecular diols, low-molecular dicarboxylic acids, and triols. Examples of the component (a-2) include, but are not limited to, polyester polyol, polyester tetraol, and polyester triol. Examples of the low molecular diol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl 1,3-propanediol, 1,3-butanediol, , 4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol and the like, and two or more kinds 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 suberin. Examples thereof include acids and anhydrides of the corresponding ones, and two or more kinds can be used in combination. The triol is the same as described above. (A-2) As a commercial item of a component, Kuraray polyol F-510, the same F-1010, the same F-2010, the same F-3010 (all made by Kuraray Co., Ltd.) etc. are mentioned, for example.

  When the component (a-1) and the component (a-2) are used in combination, their mass ratio is not particularly limited, but 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, They are 65/35, 70/30, 75/25, 80/20, 85/15, 90/10, and 95/5. 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 and lower limit values described above. A preferable range of the mass ratio is about 1/99 to 99/1.

  Examples of the component (A) include polyols other than both the component (a-1) and the component (a-2) (hereinafter referred to as the component (a-3)). Specific examples include polyether triol, polyether tetraol, polycarbonate triol, castor oil polyol, alkyl polyol, and the like. In the present specification, the “alkyl polyol” refers to a compound containing only an alkyl group, an alkylene group and a hydroxyl group in the compound and containing three or more hydroxyl groups in the compound. Examples of “alkyl polyol” include, but are not limited to, trimethylolpropane, glycerin, pentaerythritol and the like. As a commercial item of (a-3) component, for example, ADEKA polyether G-300, G-400, G-700, AM-302, AM-502, AM-702, BM-54, GM-30 (all (Manufactured by Adeka Corporation), HS 6G-160, HS CM-025P, HS CM-075P (all manufactured by Toyokuni Oil Co., Ltd.), trimethylolpropane (manufactured by Mitsubishi Gas Chemical Co., Ltd.), glycerin (Sakamoto Pharmaceutical Co., Ltd.) Co., Ltd.), Penalit (manufactured by Guangei Chemical Industry Co., Ltd.) and the like. As the component (A), the component (a-1) and the component (a-2) are not included, and the desired thermosetting is possible even if the component (a-3) is used alone as long as the requirements of the component (A) are satisfied. It is possible to provide an adhesive release coating agent. When the component (a-3) is used in combination with the component (a-1) and / or the component (a-2), the ratio of the component (a-3) to the component (A) is not particularly limited. Less than 50%, for example, less than 45%, less than 40%, less than 35%, less than 34%, less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, 10% % And less than 5% by mass.

  As the component (A), a polyol (A1) having at least three hydroxyl groups in the molecule, a molecular weight of 200 to 5000, and a hydroxyl value of 30 to 840 mgKOH / g, and a hydroxyl group in the molecule And a polyol (A2) having a molecular weight of 80 to 200 and a hydroxyl value of 841 to 2000 mgKOH / g.

  As the component (B), various known materials can be used without particular limitation as long as they are so-called hydroxyl group-containing organically modified silicones. Examples of the modified site include at least one selected from the group consisting of an acrylic polymer site, a polyester site, a polyether site, and a carbinol site. The acrylic polymer moiety can be, for example, a (co) polymer of acrylic ester and / or methacrylic ester. In addition, the modified site only needs to be introduced into one end, both ends, or the side chain of the silicone chain.

  Examples of commercially available products of the component (B) in which the modified site is an acrylic polymer include, for example, ZX-028-G (manufactured by T & K TOKA), BYK-SILCLEAN 3700 (manufactured by Big Chemie Japan), and Cymac. US-270 (manufactured by Toagosei Co., Ltd.) and the like can be mentioned, and two or more kinds can be used in combination.

  Examples of the commercially available product of the component (B) in which the modified site is polyester and the commercial product of the component (B) in which the modified site is a polyether include BYK-370, BYK-375, BYK-377, BYK- SILCLEAN 3720 (manufactured by Big Chemie Japan Co., Ltd.), X-22-4952, KF-6123 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be mentioned, and two or more can be used in combination.

  Examples of the commercially available component (B) in which the modified site is carbinol 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 Corporation), etc. Two or more types can be used in combination.

  Examples of the component (C) include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate; dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1 , 4-cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate and other diisocyanates such as alicyclic diisocyanates, and isocyanurates, adducts and biurets of the diisocyanates. Also, so-called polymeric isocyanate such as polymethylene polyphenyl polyisocyanate can be used. Two or more of these can be used in combination.

  Although the usage-amount of (A) component and (C) component is not specifically limited, The upper limit of the molar ratio (NCO / OH) of the hydroxyl group of (A) component and the isocyanate group of (C) component is 3, 2.5, 2, 1.5, 1, 0.5, 0.4, and 0.3. The lower limit of the molar ratio (NCO / OH) of the hydroxyl group of component (A) to the isocyanate group of component (C) is 2.5, 2, 1.5, 1, 0.5, 0.4, 0.3. 0.2. The range of the molar ratio (NCO / OH) of the hydroxyl group of component (A) to the isocyanate group of component (C) can be appropriately selected and set from the upper limit and lower limit values described above. The range of the molar ratio (NCO / OH) of the hydroxyl group of component (A) to the isocyanate group of component (C) is usually from the viewpoint of solvent resistance, and usually the hydroxyl group of component (A) and the isocyanate group of component (C). The molar ratio (NCO / OH) may be about 0.2 to 3.

  The amount of the component (B) used is not particularly limited, but the upper limit of the amount of the component (B) is usually converted to a solid content relative to the total mass (converted to a solid content) of the component (A) and the component (C). 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%. The lower limit of the amount of component (B) used is usually 9% by mass, 8% by mass, and 7% by mass in terms of solid content with respect to the total mass (in terms of solid content) of component (A) and component (C). 6 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, 0.8 mass%, 0.5 mass%, 0.2 mass%, and 0.1 mass%. . In addition, the usage-amount range of (B) component can be suitably selected and set from the value of the said upper limit and minimum. (B) From the viewpoint of solvent resistance and releasability, a preferred example of the amount of component used is usually 0.1 to the total mass (in terms of solid content) of component (A) and component (C). It may be in a range that is about 10% by mass (in terms of solid content).

  The coating agent of the present invention may contain various known (D) curing catalysts (hereinafter referred to as (D) component) as necessary. Examples of the component (D) include 1,4-diazabicyclo (2,2,2) octane (DABCO), 1,8-diazabicyclo (5,4,0) undecene-7 (DBU), 1,5-diazabicyclo. Tertiary amine compounds such as (4, 3, 0) nonene-5 (DBN); dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide , Tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, dioctyltin dilaurate, dioctyltin diversate, tributyltin chloride, tributyltin trichloroacetate, 2-ethy Tin compounds such as tin hexanoate; titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, lead naphthenate Iron compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; bismuth compounds such as bismuth 2-ethylhexanoate and bismuth naphthenate, etc. 2 or more types can be used in combination. Among these, the tin compound and / or the iron compound are preferable from the viewpoint of curability. Moreover, the said iron type compound is preferable also from a viewpoint of the pot life of a coating agent.

  When the component (D) is used, the amount used is not particularly limited, but the upper limit of the amount used of the component (D) is usually the total mass (converted to solid content) of the component (A) and the component (C). On the other hand, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0% .1% by mass. The lower limit of the amount of component (D) used is usually 9% by mass, 8% by mass, 7% by mass, and 6% by mass with respect to the total mass (in terms of solid content) of component (A) and component (C). 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1% by mass, 0.5% by mass, 0.1% by mass, and 0.01% by mass. In addition, the usage-amount range of (D) component can be suitably selected and set from the value of the said upper limit and minimum. A preferable example of the amount range of the component (D) is usually 0 with respect to the total mass (in terms of solid content) of the component (A) and the component (C) from the viewpoint of the pot life of the coating agent and the reaction curing rate. It may be within a range of about 0.01 to 10% by mass (solid content conversion).

  The coating agent of the present invention may contain various known (E) organic solvents (hereinafter referred to as (E) components) as necessary. Specific examples include methyl ethyl ketone, methyl isobutyl ketone, acetone, acetylacetone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, dimethyl glycol, toluene, xylene, isopropyl alcohol, ethanol, butanol, etc. Can be used together. Among these, from the viewpoint of the pot life of the coating agent of the present invention, a ketone-based organic solvent is preferably included, and among the ketone-based organic solvents, acetylacetone is preferably included.

  When the component (E) is used, the amount used is not particularly limited. Usually, the upper limit of the amount used of the component (E) is that the solid content concentration of the coating agent of the present invention is 50% by mass in terms of solid content, 45 It is used to the extent of 40% by 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, 5% by mass, The lower limit of the amount used is that the solid content concentration of the coating agent of the present invention is 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 21 mass%, 20 mass%, 15 mass% in terms of solid content. It is used to the extent of 10% by mass, 5% by mass, and 1% by mass. In addition, the usage-amount range of (E) component can be suitably selected and set from the value of the said upper limit and minimum. Preferably (E) component is used so that the solid content concentration of the coating agent of this invention may be 1-50 mass%.

  The coating agent of the present invention may contain various known (F) diols (hereinafter referred to as (F) component) as necessary. Specific examples include polycaprolactone diol, polyester diol (excluding polycaprolactone diol), polyether diol, and polycarbonate diol. Examples of commercially available products of component (F) include Kuraray polyol P-510, P-1010, P-1020, P-2010 (all manufactured by Kuraray Co., Ltd.), Plaxel 205, 208, 210, 212 (all manufactured by Daicel Corporation) Adeka Polyether P-400, BPX-11 (all manufactured by Adeka Corporation), Kuraray Polyol C-590, C-1090, C-2090 (all Kuraray Co., Ltd.) ), Duranol T-5650J, T-5562 (all manufactured by Asahi Kasei Chemicals Corporation), Plaxel CD210 (manufactured by Daicel Corporation), Nipponran 981, 980R (manufactured by Tosoh Corporation), ethylene glycol, diethylene glycol 14BG (all Mitsubishi Chemical Corporation, CHDM-D (Nagase Sangyo Co., Ltd.)).

  When the component (F) is used, the amount used is not particularly limited. Usually, the upper limit of the amount used of the component (F) is the total mass (in terms of solid content) of the component (A) and the component (F). On the other hand, it is 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, and (F) component The minimum of the usage-amount is 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass% with respect to the total mass (solid content conversion) of (A) component and (F) component. 15% by mass, 10% by mass, 5% by mass, and 1% by mass. In addition, the usage-amount range of (F) component can be suitably selected and set from the value of the said upper limit and minimum. Preferably (F) component is used so that it may become 1 mass%-50 mass%.

  The coating agent of the present invention is selected from the group consisting of (A) component, (B) component and (C) component, and (D) component, (E) component and (F) component as required 1 It is a mixture of two or more components. The mixing means and the mixing order are not particularly limited.

  In the coating agent of the present invention, if necessary, a binder resin other than the component (A) (acrylic resin, urethane resin, polyester resin, epoxy resin, alkyd resin, etc.), fine particles, anti-slip agent, antiseptic agent, rust inhibitor, A pH adjuster, antioxidant, pigment, dye, lubricant, leveling agent, antifoaming agent and the like may be included.

  The release film according to the present invention is an article comprising a cured film made of the thermosetting release coating agent of the present invention and a plastic film as components, and the coating agent of the present invention is applied to at least one surface of the plastic film. Obtained by heat treatment.

  Examples of the plastic film include polycarbonate film, polymethyl methacrylate film, polystyrene film, polyethylene terephthalate film, polyimide film, polyolefin film, nylon film, epoxy resin film, melamine resin film, triacetyl cellulose resin film, ABS resin film, An AS resin film, a norbornene-based resin film, and the like can be given. The plastic film may be subjected to surface treatment (corona discharge or the like). The plastic film may be provided with a layer (for example, an easy adhesion layer) other than the coating agent composition of the present invention on one side or both sides. The plastic film is preferably a polyethylene terephthalate film in terms of performance such as transparency, dimensional stability, mechanical properties, and chemical resistance. In addition, the thickness of this plastic film is not specifically limited, Usually, what is necessary is just about 10-100 micrometers.

The 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 not particularly limited as long as the mass after drying is usually about 0.1 to 10 g / m ² , preferably 0.2 to 5 g / m ² .

  The heating conditions are not particularly limited, and are usually about 90 seconds to 130 ° C. for about 30 seconds to 2 minutes, and the coating agent of the present invention has relatively good fast curability at a relatively low temperature. Therefore, the coating agent of the present invention is suitable for a plastic film that is easily deformed by heat.

  Moreover, you may attach | subject the release film which concerns on this invention to curing treatment as needed. The conditions are not particularly limited, but are about 20 to 50 ° C. for about 1 to 24 hours. By doing so, the solvent resistance of the cured film becomes better.

  The present invention has been described with reference to the preferred embodiments for easy understanding. The present invention will be described below based on examples, but the above description and the following examples are provided only for the purpose of illustration and are not provided for the purpose of limiting the present invention. Accordingly, the scope of the present invention is not limited to the embodiments or examples specifically described in the present specification, but is limited only by the scope of the claims.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail through an Example and a comparative example, it does not intend limiting the scope of the present invention by them. The present invention is not construed as being limited thereto, and examples obtained by appropriately combining technical means disclosed in each example are also included in the scope of the present invention. Moreover, in each Example and a comparative example, a part or% is a mass reference | standard.

  The hydroxyl value can be measured by a method according to JIS K0070. The number average molecular weight can be measured with a polystyrene calibration curve using gel permeation chromatography (GPC).

<Preparation of thermosetting release coating agent>
Example 1
(A) Kuraray polyol F-510 (manufactured by Kuraray Co., Ltd.) as a component; polyester having a number average molecular weight of 500 and a hydroxyl value of 340 mgKOH / g, comprising 3-methyl-1,5-pentanediol, adipic acid and trimethylolpropane (Polyol) as 10.00 parts, (B) component as BYK-377 (manufactured by BYK Japan KK; polyether-modified hydroxyl group-containing silicone) (solid content concentration: 100%) as 0.22 parts, as (C) component Coronate HX (manufactured by Tosoh Corp .; isocyanurate of hexamethylene diisocyanate) (solid content concentration 100%) is 11.86 parts, and (D) component is dioctyltin dilaurate (solid content concentration 100% or less, DOTDL) is 0. .02 parts, methyl ethyl ketone and methyl isobutyl keto as component (E) 83.14 parts of a mixed solvent (hereinafter, MEK / MIBK mixed solvent) having a mass ratio of 1 to 1 was used. A thermosetting release coating agent having a solid concentration of 21% was prepared by thoroughly mixing the above components.

Example 2
As component (A), Kuraray polyol F-510 is 10.00 parts, and as component (B), BYK-370 (manufactured by Big Chemie Japan Co., Ltd .; polyester-modified hydroxyl group-containing silicone) (solid content concentration 25%) is 0.87. In addition, 11.86 parts of Coronate HX was used as the component (C), 0.02 parts of DOTDL were used as the component (D), and 82.48 parts of MEK / MIBK mixed solvent were used as the component (E). A thermosetting release coating agent having a solid concentration of 21% was prepared by thoroughly mixing the above components.

Example 3
As component (A), Kuraray polyol F-510 (10.00 parts) and as component (B) BYK-SILCLEAN 3700 (produced by Big Chemie Japan Co., Ltd .; silicone-modified hydroxyl group-containing acrylic polymer) (solid content concentration 25%) 87 parts, 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) were used. A thermosetting release coating agent having a solid concentration of 21% was prepared by thoroughly mixing the above components.

Example 4
(A) Kuraray polyol F-510 as component 10.00 parts, (B) component BYK-377 0.26 parts, (C) component Takenate D-110N (Mitsui Chemicals, Inc .; xylylene diisocyanate) The adduct body (solid content concentration: 75%) was used at 21.91 parts, DOTDL as 0.03 parts as component (D), and 95.06 parts of MEK / MIBK mixed solvent as component (E). A thermosetting release coating agent having a solid concentration of 21% was prepared by thoroughly mixing the above components.

Example 5
(A) 10.00 parts of Kuraray polyol F-510 as component, 0.27 parts of BYK-377 as component (B), Takenate D-120N (manufactured by Mitsui Chemicals, Inc .; hydrogenated xylori as component (C) (Adduct body of diisocyanate) (solid content concentration 75%) was 22.91 parts, DOTDL was 0.03 part as (D) component, and 97.65 parts of MEK / MIBK mixed solvent was used as (E) component. A thermosetting release coating agent having a solid concentration of 21% was prepared by thoroughly mixing the above components.

Example 6
(A) 10.00 parts of Kuraray polyol F-510 as component, 0.18 parts of BYK-377 as (B) component, Millionate MR-200 (manufactured by Tosoh Corporation) as component (C); polymeric diphenylmethane diisocyanate ( MDI)) (solid content concentration 100%) was used in 8.13 parts, DOTDL as 0.02 parts as component (D), and 68.95 parts of MEK / MIBK mixed solvent as component (E). A thermosetting release coating agent having a solid concentration of 21% was prepared by thoroughly mixing the above components.

Example 7
As component (A), Plaxel 303 (manufactured by Daicel Corporation; polycaprolactone triol having a number average molecular weight of 300 and a hydroxyl value of 540 mgKOH / g) is 10.00 parts, and as component (B) is 0.29 parts of BYK-377. As component (C), 19.02 parts of coronate HX, 0.03 part of DOTDL as component (D), and 110.39 parts of MEK / MIBK mixed solvent as component (E) were used. A thermosetting release coating agent having a solid concentration of 21% was prepared by thoroughly mixing the above components.

Example 8
As component (A), Plaxel L320AL (manufactured by Daicel Corporation; polycaprolactone triol having a number average molecular weight of 2000 and a hydroxyl value of 84 mgKOH / g) is 10.00 parts, and as component (B) is 0.13 parts of BYK-377. As component (C), 2.96 parts of coronate HX, 0.01 part of DOTDL as component (D), and 49.29 parts of MEK / MIBK mixed solvent as component (E) were used. A thermosetting release coating agent having a solid concentration of 21% was prepared by thoroughly mixing the above components.

Example 9
As component (A), ADEKA polyether AM-302 (manufactured by ADEKA Corporation; polyether triol having a number average molecular weight of 3000 and a hydroxyl value of 56 mgKOH / g) is 10.00 parts, and as component (B), BYK-377 is 0. .12 parts, 1.97 parts of Coronate HX as component (C), 0.01 parts of DOTDL as component (D), and 45.54 parts of MEK / MIBK mixed solvent as component (E) were used. A thermosetting release coating agent having a solid concentration of 21% was prepared by thoroughly mixing the above components.

Example 10
As component (A) Kuraray polyol F-510 10.00 parts, (B) component BYK-377 0.26 parts, (C) component Takenate D-110N 21.91 parts, (E) component 94.96 parts of MEK / MIBK mixed solvent was used. A thermosetting release coating agent having a solid concentration of 21% was prepared by thoroughly mixing the above components.

Example 11
(A) Component Kuraray polyol F-510 10.00 parts, (B) Component BYK-377 0.22 parts, (C) Component Coronate HX 11.86 parts, (D) Component Tris ( 2,2-Pentandionato) iron (III) (solid content concentration of 100% or less, TPDI) was used in 0.02 part, and (E) component was used in MEK / MIBK mixed solvent 83.14 parts. A thermosetting release coating agent having a solid concentration of 21% was prepared by thoroughly mixing the above components.

Example 12
(A) Plaxel 303 as component (10.00 parts), (B) component as BYK-377 (0.26 parts), (C) ingredient as Takenate D-110N as 21.91 parts, (D) ingredient as TPDI as 0 0.03 part, and 95.06 parts of MEK / MIBK mixed solvent was used as the component (E). A thermosetting release coating agent having a solid concentration of 21% was prepared by thoroughly mixing the above components.

Example 13
(A) Plaxel 303 as component (10.00 parts), (B) component as BYK-377 (0.36 parts), (C) component Takenate D-110N as 35.15 parts, (D) component as TPDI as 0 .04 parts, and 129.52 parts of MEK / MIBK mixed solvent as component (E) were used. A thermosetting release coating agent having a solid concentration of 21% was prepared by thoroughly mixing the above components.

Example 14
(A) 10.00 parts of Plaxel 303 as component, 1.16 parts of BYK-SILCLEAN3700 as component (B) and Silaplane FM-DA11 (manufactured by JNC Corporation; carbinol-modified silicone) (solid content concentration 100% 0.07 parts), 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) did. A thermosetting release coating agent having a solid concentration of 21% was prepared by thoroughly mixing the above components.

Example 15
(A) 10.00 parts of Kuraray polyol F-510 as component, 0.85 parts of BYK-SILCLEAN3700 and 0.05 parts of silaplane FM-DA11 as component (B), Takenate D-110N as component (C) 21.91 parts, 0.03 parts of TPDI as component (D), and 94.43 parts of MEK / MIBK mixed solvent as component (E). A thermosetting release coating agent having a solid concentration of 21% was prepared by thoroughly mixing the above components.

Example 16
As component (A), trimethylolpropane (manufactured by Mitsubishi Gas Chemical Co., Inc .; alkyltriol having a molecular weight of 134 and a hydroxyl value of 1250 mgKOH / g) is 10.00 parts, and as component (B), 2.28 parts of BYK-SILCLEAN3700 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 MEK / MIBK mixed solvent as component (E) .84 parts were used. A thermosetting release coating agent having a solid concentration of 21% was prepared by thoroughly mixing the above components.

Example 17
As component (A), 10.00 parts of Plaxel 303 and 5.00 parts of trimethylolpropane, as component (B), 2.30 parts of BYK-SILCLEAN3700 and 0.14 parts of Silaplane FM-DA11, (C) As components, 75.99 parts of Takenate D-110N, 0.07 parts of TPDI as component (D), and 253.07 parts of MEK / MIBK mixed solvent as component (E) were used. A thermosetting release coating agent having a solid concentration of 21% was prepared by thoroughly mixing the above components.

Example 18
As component (A), 10.00 parts of Plaxel 303 and 5.00 parts of trimethylolpropane, as component (B), 2.30 parts of BYK-SILCLEAN3700 and 0.14 parts of Silaplane FM-DA11, (C) As components, 75.99 parts of Takenate D-110N, 0.07 parts of TPDI as component (D), 3.60 parts of acetylacetone and 249.47 parts of MEK / MIBK mixed solvent as component (E) were used. A thermosetting release coating agent having a solid concentration of 21% was prepared by thoroughly mixing the above components.

Comparative Example 1
As component (A), Kuraray polyol P-1010 (manufactured by Kuraray Co., Ltd .; polyester diol having a number average molecular weight of 1000 and a hydroxyl value of 112 mgKOH / g consisting of 3-methyl-1,5-pentanediol and adipic acid)) 10.00 parts, 0.14 parts of BYK-377 as component (B), 3.95 parts of coronate HX as component (C), 0.01 part of DOTDL as component (D), MEK as component (E) /53.04 parts of MIBK mixed solvent was used. A thermosetting release coating agent having a solid concentration of 21% was prepared by thoroughly mixing the above components.

Comparative Example 2
A thermosetting release coating agent was prepared in the same manner as in Example 1 except that BYK-377 was not used.

(B)%:% by mass of component (B) relative to the total mass of component (A) and component (C)
(D)%:% by mass of component (D) with respect to the total mass of component (A) and component (C)

<Production of release film>
By coating the coating agent of Example 1 on a commercially available polyethylene terephthalate film (trade name Lumirror T60, 50 μm thickness) so that the coating thickness after drying is 1 μm, and drying at 120 ° C. for 1 minute, A release film having a cured film made of the coating agent was prepared. About Example 10, the release film provided with the cured film which consists of this coating agent by making it dry at 120 degreeC for 10 minute (s) was produced, and it is the same as that of Example 1 about the coating agent of another Example and a comparative example. Thus, a release film was prepared.

<Solvent resistance of cured film>
After leaving the release film according to Example 1 at 23 ° C. overnight, the cured film was rubbed with a cotton swab impregnated with methyl ethyl ketone. As a result, the cured film did not dissolve even after 100 reciprocations. On the other hand, when the release film according to Example 9 was similarly evaluated, the base film was exposed at the 80th time. The solvent resistance of the release films according to other examples was similarly evaluated, but the cured film did not dissolve even after exceeding 100 reciprocations. On the other hand, when the release film according to Comparative Example 1 was similarly evaluated, the base film was exposed at the second time. On the other hand, with respect to the film according to Comparative Example 2, the cured film did not dissolve even after exceeding 100 reciprocations. The results are shown in Table 2.

<Evaluation of releasability>
The mold release film according to Example 1 was allowed to stand overnight, and then a polyester adhesive tape (31B tape manufactured by Nitto Denko Co., Ltd .: 20 mm width) was bonded to the surface of the cured film while being pressure-bonded with a 2 kg roller. And left for 1 hour. Next, using the Tensilon universal testing machine (product name RTC-1250A, manufactured by Orientec Co., Ltd.), the adhesive tape was pulled horizontally at an angle of 180 ° (0.3 m / min), and the force required for peeling ( N / 20 mm). Moreover, the peeling force was similarly measured about the release film of the other Example and the comparative example. When the release film according to Comparative Example 1 was evaluated, the cured film was agglomerated and destroyed, and measurement was not possible. The results are shown in Table 2.

  This application claims priority to Japanese Patent Application No. 2006-90241 (filed on Apr. 28, 2016) and Japanese Patent Application No. 2006-157084 (filed on Aug. 10, 2016). The contents should be incorporated by reference as if the entire contents were specifically described herein.

Claims (11)

(A) a polyol having at least three hydroxyl groups in the molecule, a molecular weight of 80 to 5000, and a hydroxyl value of 30 to 2000 mgKOH / g;
(B) a hydroxyl group-containing silicone;
(C) a polyisocyanate;
A thermosetting release coating agent comprising: The thermosetting release coating agent according to claim 1, wherein the polyol as the component (A) has a molecular weight of 200 to 5,000 and a hydroxyl value of 30 to 840 mgKOH / g. (A1) a polyol having at least three hydroxyl groups in the molecule, a molecular weight of 200 to 5000, and a hydroxyl value of 30 to 840 mgKOH / g;
(A2) a polyol having at least three hydroxyl groups in the molecule, a molecular weight of 80 to 200, and a hydroxyl value of 841 to 2000 mgKOH / g;
(B) a hydroxyl group-containing silicone;
(C) a polyisocyanate;
A thermosetting release coating agent comprising: The thermosetting release according to any one of claims 1 to 3, wherein the component (A) comprises a ring-opening polymerization type polyester polyol (a-1) and / or a polycondensation type polyester polyol (a-2). Mold coating agent. The thermosetting release coating agent according to any one of claims 1 to 4, wherein the component (B) contains at least one selected from the group consisting of an acrylic polymer moiety, a polyester moiety, a polyether moiety, and a carbinol moiety. The thermosetting release coating agent according to any one of claims 1 to 5, further comprising (D) a curing catalyst. The thermosetting release coating agent according to any one of claims 1 to 6, further comprising (E) an organic solvent. A release film comprising the cured film of the thermosetting release coating agent according to any one of claims 1 to 7 and a plastic film as constituent elements. The release film according to claim 8, wherein the plastic film is a polyethylene terephthalate film. A method for producing a release film, comprising applying the thermosetting release coating agent according to any one of claims 1 to 7 to at least one surface of a plastic film, followed by heat treatment. The method for producing a release film according to claim 10, wherein the plastic film is a polyethylene terephthalate film.