KR102264801B1 - Thermosetting release coating agent, release film and method for producing the release film - Google Patents

Abstract

(Problem) To provide a novel thermosetting release coating agent that can form a cured coating film that is excellent in releasability (separability from a mold) and has little bleed-out problem on a plastic film at a relatively low temperature and in a short time .
(Solution Means) (A) a polyol having at least three hydroxyl groups in the molecule and having a molecular weight of 80 to 5000 and a hydroxyl value of 30 to 2000 mgKOH/g, or (A1) having at least three hydroxyl groups in the molecule and having a molecular weight (A2) a polyol having 200 to 5000 and a hydroxyl value of 30 to 840 mgKOH/g, and (A2) a polyol having at least three hydroxyl groups in the molecule and having a molecular weight of 80 to 200 and a hydroxyl value of 841 to 2000 mgKOH/g, and ( B) It is a thermosetting release coating agent containing hydroxyl-containing silicone and (C) polyisocyanate.

Description

Thermosetting release coating agent, release film, manufacturing method of release film {THERMOSETTING RELEASE COATING AGENT, RELEASE FILM AND METHOD FOR PRODUCING THE RELEASE FILM}

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.

BACKGROUND ART Plastic films such as polyethylene terephthalate are used in various industrial fields because of their excellent performance such as transparency, dimensional stability, mechanical properties, and chemical resistance.

Specifically, for example, use as a base film for optical film products, such as a prism sheet of an LCD member, a light-diffusion sheet, a reflecting plate, an anti-reflection plate, a touch panel, an explosion-proof film, a PPD filter, is mentioned.

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

As a release agent used for a release film, a silicone resin is known.

Patent Document 1 proposes a method of laminating a compounding solution comprising an acrylic resin, a melamine resin, and a silicone resin. Moreover, as described in patent document 2, an acid catalyst may be used together for the purpose of improving sclerosis|hardenability of a melamine resin.

Japanese Patent Laid-Open No. 11-170440 Japanese Patent Laid-Open No. 2002-19037

However, silicone resins often bleed out the surface of the coating film, migrate to an adherend such as an adhesive or a resin sheet laminated on the coating film, and its properties are impaired. there is a problem. Moreover, the compounding liquid used in the method of laminating|stacking the compounding liquid which consists of an acrylic resin, a melamine resin, and a silicone resin has a problem that the temperature required for hardening is 190 degreeC, and the thermal damage to a base material is large. Moreover, when an acid catalyst is used together, the aging stability (pot life) of a coating agent deteriorates, and there also exists a problem that it causes a thickening and causes the fall of workability|operativity.

According to the present invention, a cured coating film having excellent releasability (separability from a mold) and less problem of bleed-out on a plastic film can be formed at a low temperature and in a shorter time than in the prior art, An object is to provide a novel thermosetting release coating agent.

MEANS TO SOLVE THE PROBLEM This inventor discovered that the said subject could be solved with the thermosetting mold release coating agent containing a predetermined polyol, predetermined silicone resin, and polyisocyanate, as a result of examining. 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 1A)

(A) a polyol having at least three hydroxyl groups in the molecule and having a molecular weight of 80 to 5000 and a hydroxyl value of 30 to 2000 mgKOH/g;

or

(A1) a polyol having at least three hydroxyl groups in the molecule and having 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 and having a molecular weight of 80 to 200 and a hydroxyl value of 841 to 2000 mgKOH/g;

and

(B) hydroxyl group-containing silicone;

(C) polyisocyanate

A thermosetting release coating comprising a.

(Item 1B)

(A) a polyol having at least three hydroxyl groups in the molecule and having a molecular weight of 80 to 5000 and a hydroxyl value of 30 to 2000 mgKOH/g;

(B) hydroxyl group-containing silicone;

(C) polyisocyanate

A thermosetting release coating comprising a.

(Item 1C)

(A1) a polyol having at least three hydroxyl groups in the molecule and having 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 and having a molecular weight of 80 to 200 and a hydroxyl value of 841 to 2000 mgKOH/g;

(B) hydroxyl group-containing silicone;

(C) polyisocyanate

A thermosetting release coating comprising a.

(Item 2)

(A) The thermosetting release coating agent of the said item whose molecular weight is 200-5000, and the polyol of component has a hydroxyl value of 30-840 mgKOH/g.

(Item 3)

(A) The thermosetting release coating agent according to any one of the above items, wherein the component contains a ring-opening polymerization polyester polyol (a-1) and/or a polycondensation polyester polyol (a-2).

(Item 4)

(B) The thermosetting release coating agent according to any one of the above items, wherein the component contains at least one selected from the group consisting of an acrylic polymer moiety, a polyester moiety, a polyether moiety, and a carbinol moiety.

(Item 5)

(D) The thermosetting release coating agent of any one of the above items further comprising a curing catalyst.

(Item 6)

(E) The thermosetting release coating agent of any one of the above items further comprising an organic solvent.

(Item 7)

A release film comprising the cured film of the thermosetting release coating agent of any one of the above items and a plastic film as components.

(Item 8)

The release film of the above item, wherein the plastic film is a polyethylene terephthalate film.

(Item 9)

A method for producing a release film, characterized in that the thermosetting release coating agent according to any one of the above items is applied to at least one side of a plastic film and subjected to heat treatment.

(Item 10)

The method for producing the release film of the above item, wherein the plastic film is a polyethylene terephthalate film.

In the present disclosure, it is intended that the above-described one or more features may be provided in a further combination in addition to the specified combination. New embodiments and advantages other than the above will be recognized by those skilled in the art by reading and understanding the following detailed description as necessary.

The thermosetting release coating agent of this invention is excellent in aging stability (pot life). In addition, since a cured film having good releasability (separability from a mold) and solvent resistance is formed at a relatively low temperature and in a short time, productivity is high. In addition, in the coating agent, since the silicone transferability from the cured film 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 has a cured film having good releasability (separability from a mold) and solvent resistance, and furthermore, a material containing a lot of organic solvent, such as a cast solution for a resin sheet or an inorganic slurry, etc. can be applied to

The release film according to the present invention is useful as a release film for manufacturing processes such as resin sheets, synthetic leather, decorative plates, carbon fiber prepregs, and ceramic electronic parts. It is also preferable as a release film for transfer printing-related products, and a release film (separator) for protecting adhesive layers such as polarizing plates and retardation plates.

Throughout this specification, expressions in the singular also include concepts in the plural, unless specifically stated otherwise. In addition, the terms used in this specification are used with the meaning normally used in the said field|area unless otherwise indicated. Accordingly, unless otherwise defined, 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 inconsistency, the present specification (including definitions) shall control.

(Description of preferred embodiment)

Preferred embodiments 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 is not limited to the following description. Therefore, it is apparent that those skilled in the art can make appropriate changes within the scope of the present invention in consideration of the description in the present specification. In addition, the following embodiment of this invention can be used individually or can also be used combining them.

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

Component (A) is a polyol having at least three hydroxyl groups in the molecule, having a molecular weight of about 80 to 5000 and a hydroxyl value of about 30 to 2000 mgKOH/g, and various known ones can be used without particular limitation. In this specification, "molecular weight" is food or number average molecular weight. When the structure of a compound can be expressed uniquely with a specific chemical formula, such as trimethylolpropane, the molecular weight is food. On the other hand, when the structure of the compound cannot be uniquely expressed by a specific chemical formula, such as a ring-opening polymerization polyester polyol or a polycondensation type polyester polyol, the molecular weight is a number average molecular weight. The upper limit of the normal molecular weight is about 5000, 4500, 4000, 3500, 3000, 2500, 2000, 1500, 1000, 900, 800, 700, 600, 500, 400, 300, 200, 150, 134, 100, and the normal molecular weight The lower limit of 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 values of the upper and lower limits 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 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, 400 mgKOH/g, 350 mgKOH/g, 340 mgKOH/g, 300mgKOH/g, 200mgKOH/g, 100mgKOH/g, 90mgKOH/g, 85mgKOH/g, 84mgKOH/g, 80mgKOH/g, 70mgKOH/g, 60mgKOH/g, 56mgKOH/g, 50mgKOH/g, about 40mgKOH/g, The lower limit of normal hydroxyl value 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.

The range of the hydroxyl value can be set by appropriately selecting from the values of the upper and lower limits described above. From the viewpoint of coexistence of solvent resistance and peelability of the cured coating film, preferably, the molecular weight is about 90 to 2000 and the hydroxyl value is about 80 to 1900 mgKOH/g.

(A) As a non-limiting specific example of a component, For example, ring-opening polymerization polyester polyol (a-1) (hereinafter, (a-1) component) and/or polycondensation type polyester polyol (a-2) (hereinafter , (a-2) component) is mentioned.

(a-1) As for a component, the polylactone triol and/or polylactone tetraol etc. which are specifically, a reaction product of various well-known lactone, a triol, and/or tetraol are mentioned. However, it is not intended to be limited to this. Examples of the lactone include β-propiolactone, γ-butyrolactone, δ-valerolactone, β-methyl-δ-valerolactone and ε-caprolactone, and two or more types are used in combination. can do. Examples of the triol include glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, and the like, and examples of the tetraol include pentaerythritol. , two or more types may be used in combination. (a-1) As a commercial item of a component, it is Fracel 303, the same L320ALA, the same 305, the same 308, the same 309, the same 312, the same, for example. (the said) 320, the same 410, etc. are mentioned (all are Daicel Corporation products).

(a-2) Component is specifically, a reaction product with various well-known low molecular weight diol, low molecular weight dicarboxylic acid, and a triol. Although it is not limited to this as an example of (a-2) component, Polyester polyol, polyester tetraol, polyester triol, etc. are mentioned. Examples of the low molecular weight diol 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. are mentioned, 2 or more types can be used together. As said low molecular weight dicarboxylic acid, for example, 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 corresponding ones Anhydride etc. are mentioned, 2 or more types can be used together. The triol is the same as described above. (a-2) As a commercial item of a component, For example, Kuraray Polyol F-510, F-1010, F-2010, F-3010 (all (all) KURARAY CO., LTD.) etc. are mentioned.

(a-1) When using a component and (a-2) component together, those mass ratio is although it does not specifically limit, Usually, the upper limit of 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, 65/35 , 70/30, 75/25, 80/20, 85/15, 90/10, 95/5. In addition, 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 values of the upper and lower limits described above. The range of the preferable mass ratio is about 1/99 to 99/1.

(A) Polyols (henceforth (a-3) component) other than both of (a-1) component and (a-2) component are also mentioned to (A) component. Specific examples thereof include polyether triol, polyether tetraol, polycarbonate triol, castor oil polyol, and alkyl polyol. As used herein, the term "alkyl polyol" refers to a compound containing only an alkyl group, an alkylene group and a hydroxyl group in the compound, and a compound containing three or more hydroxyl groups in the compound. Although not limited to these as an example of "alkyl polyol", trimethylolpropane, glycerol, pentaerythritol, etc. are mentioned. (a-3) As a commercial item of a component, For example, Adeka polyether (ADEKA POLYETHER) G-300, G-400, G-700, AMF-302, AMF-502, AMF-702, BMD-54, GM -30 (all manufactured by ADEKA CORPORATION), HS 6G-160, HS CM-025P, HS MC-075P (all manufactured by Hokoku Corporation), trimethylolpropane (Mitsubishi Oil) Gas Chemical Co., Ltd. (MITSUBISHI GAS CHEMICAL COMPANY, INC.), Glycerin (product of SAKAMOTO YAKUHIN KOGYO CO., LTD), Pentaritto (Koe Chemical Co., Ltd. (KOEI CHEMICAL) CO., LTD.) products) and the like. As (A) component, (a-1) component and (a-2) component are not included, and as long as the requirements of (A) component are satisfied, even if component (a-3) is used alone, desired thermosetting release coating agent can provide Moreover, when using (a-3) component together with (a-1) component and/or (a-2) component, the ratio of (a-3) component to (A) component is not specifically limited, Usually less than 50 mass%, for example, less than 45 mass%, less than 40 mass%, less than 35 mass%, less than 34 mass%, less than 30 mass%, less than 25 mass%, less than 20 mass%, less than 15 mass%; It is less than 10 mass % and less than 5 mass %.

Further, as component (A), a polyol (A1) having at least three hydroxyl groups in the molecule, having a molecular weight of 200 to 5000 and a hydroxyl value of 30 to 840 mgKOH/g, and having at least three hydroxyl groups in the molecule and having a molecular weight The polyol (A2) of 80 to 200 and a hydroxyl value of 841 to 2000 mgKOH/g may be included, respectively.

(B) As long as it is a so-called hydroxyl-containing organic modified silicone, various well-known things can be used without restriction|limiting in particular as component. Examples of the modified site include at least one selected from the group consisting of an acrylic polymer moiety, a polyester moiety, a polyether moiety, and a carbinol moiety. The acrylic polymer moiety may be, for example, a (co)polymer of acrylic acid ester and/or methacrylic acid ester. In addition, the said modified site|part should just flow in any one of the one terminal, both terminals, and a side chain of a silicone chain.

As a commercial item of the component (B) whose said modified site|part is an acrylic polymer, For example, KX-028-G (manufactured by T&K TOP), BK-K-PSA (manufactured by BICK) (BYK Japan KL) (BYK LK) 3700, for example. , SYMAC US-270 (product of TOAGOSEI CO., LTD.), etc. are mentioned, and 2 or more types can be used together.

As a commercial item of the component (B) whose said modified site|part is polyester, and the commercial item of the (B) component whose said modified site|part is polyether, For example, BK-370, BK-375, BAB-377, BKMA37 - Japan Co., Ltd. product), X-22-4952, KF-6123 (Shin-Etsu Chemical Co., Ltd. product) etc. are mentioned, 2 or more types can be used together have.

As a commercial item of (B) component whose said modified site|part is carbinol, X-22-4039, X-22-4015, X-22-4952, X-22-4272, X-22-170BX, X-, for example. 22-170DX, KF-6000, KF-6001, KF-6002, KF-6003, KF-6123, X-22-176F (manufactured by Shin-Etsu Chemical Co., Ltd.), Silaplane FM Silaplane FM-4421, silaplane FM-4425, silaplane FM-0411, silaplane FM-0421, silaplane FM-0421, silaplane Note) product), etc. are mentioned, and 2 or more types can be used together.

(C) As a component, For example, aromatic diisocyanate, such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; Aliphatic diisocyanate, such as hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, and lysine diisocyanate; Diisocyanates, such as alicyclic diisocyanates, such as dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1, 4- cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, and the said diisocyanate Triisocyanate, such as an isocyanurate body, an adduct body, and a biuret body, is mentioned. Moreover, so-called polymeric isocyanate, such as polymethylene polyphenyl polyisocyanate, for example, can also be used. These can use 2 or more types together.

(A) Although the usage-amount of component and (C)component is not specifically limited, The upper limit of molar ratio (NcO/OOH) of the isocyanate group of (C)component group and the hydroxyl group of (A)component is 3, 2.5, 2, 1.5 , 1, 0.5, 0.4, 0.3. Moreover, the lower limit of molar ratio (NcO/OH) of the isocyanate group of (C)component and the hydroxyl group of (A)component is 2.5, 2, 1.5, 1, 0.5, 0.4, 0.3, 0.2. Moreover, the range of the molar ratio (NcO/OH) of the isocyanate group of (C)component group and the hydroxyl group of (A)component can be appropriately selected from the value of the upper limit and a lower limit of the said description, and can be set. The range of the preferable molar ratio (NcO/OH) of the isocyanate group of component (C) and the hydroxyl group of (A) component is the molar ratio of the isocyanate group of (C)component and the hydroxyl group of (A)component normally from a viewpoint of solvent resistance especially (C) NTCO/OH) should be about 0.2 to 3.

Although the usage-amount of (B)component is not specifically limited, either, The upper limit of the usage-amount of (B)component is normally 10 mass % in conversion of solid content with respect to the total mass (solid content conversion) of (A) component and (C)component, 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 usage-amount of (B)component is normally 9 mass %, 8 mass %, 7 mass %, 6 mass %, 5 in solid content conversion with respect to the total mass (solid content conversion) of (A) component and (C)component They are mass %, 4 mass %, 3 mass %, 2 mass %, 1 mass %, 0.8 mass %, 0.5 mass %, 0.2 mass %, and 0.1 mass %. Moreover, the usage-amount range of (B) component can be suitably selected from the value of the upper limit and a lower limit of the said description, and can be set. The preferable example of the usage-amount range of (B) component is 0.1-10 mass with respect to the total mass (solid content conversion) of normally (A) component and (C)component from a viewpoint of solvent resistance and mold release property (separability with respect to a metal mold|die) normally (solid content conversion) % (in terms of solid content), the range may be sufficient.

In the coating agent of this invention, you may contain various well-known (D) hardening catalyst (henceforth (D) component) as needed. (D) As a component, 1, 4- diazabicyclo (2,2,2) octane (DABOC), 1,8-diazabicyclo (5,4,0) undecene-7 (DBF), tertiary amine compounds such as 1,5-diazabicyclo(4,3,0)nonene-5(DBM); dibutyl tin dichloride, dibutyl tin oxide, dibutyl tin dibromide, dibutyl tin dimaleate, dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin sulfide, tributyl tin sulfide, tributyl tin oxide , tributyl tin acetate, triethyl tin ethoxide, tributyl tin ethoxide, dioctyl tin oxide, dioctyl tin dilaurate, dioctyltin diversatate, tributyl tin chloride, tributyl tin trichlor tin-based compounds such as loacetate and tin 2-ethylhexanoate; titanium compounds such as dibutyl titanium dichloride, tetrabutyl titanate and butoxytitanium trichloride; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate; iron-based compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt-based compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; Bismuth compounds, such as bismuth 2-ethylhexanoate and bismuth naphthenate, etc. are mentioned, 2 or more types can be used together. Among these, the said tin-type compound and/or the said iron-type compound are preferable from a hardenable viewpoint. Moreover, the said iron-type compound is preferable also from a viewpoint of the pot life of a coating agent.

(D) When component is used, the usage-amount is not specifically limited, Although the upper limit of the usage-amount of (D)component is normally 10 mass % with respect to the total mass (solid content conversion) of (A) component and (C)component, 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 usage-amount of (D)component is normally 9 mass %, 8 mass %, 7 mass %, 6 mass %, 5 mass % with respect to the total mass (solid content conversion) of (A) component and (C)component, 4 mass %, 3 mass %, 2 mass %, 1 mass %, 0.5 mass %, 0.1 mass %, 0.01 mass %. Moreover, the usage-amount range of (D)component can be suitably selected from the value of the upper limit and a lower limit of the said description, and can be set. A preferable example of the usage-amount range of (D)component is 0.01-10 mass % with respect to the total mass (solid content conversion) of (A) component and (C)component normally from viewpoints, such as pot life and reaction hardening rate of a coating agent (solid content conversion) What is necessary is just to be in the range used as about solid content conversion).

The coating agent of this invention may contain various well-known (E) organic solvents (henceforth (E) component) as needed. Specifically, for example, methyl ethyl ketone, methyl isobutyl ketone, acetone, acetyl acetone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, dimethyl glycol, toluene, xylene, isopropyl alcohol, ethanol, butanol, etc. These can be mentioned, and 2 or more types can be used together. Among these, it is preferable that a ketone-type organic solvent is contained from a viewpoint of the pot life of the coating agent of this invention, and it is preferable that acetylacetone is contained also in a ketone-type organic solvent.

When (E) component is used, the usage-amount is not specifically limited, Usually, As for the upper limit of the usage-amount of (E) component, the solid content concentration of the coating agent of this invention is 50 mass %, 45 mass %, 40 mass % in conversion of solid content. , 35 mass %, 30 mass %, 25 mass %, 21 mass %, 20 mass %, 15 mass %, 10 mass %, is used so as to be 5 mass %, and the lower limit of the usage-amount of (E) component is the limit of this invention Solid content concentration of coating agent 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 21 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 1 mass in conversion of solid content % is used. Moreover, the usage-amount range of (E) component can be suitably selected from the value of the upper limit and a lower limit of the said description, and can be set. Preferably (E) component is used so that solid content concentration of the coating agent of this invention may become 1-50 mass %.

In the coating agent of this invention, you may contain various well-known (F) diol (henceforth (F) component) as needed. Specifically, polycaprolactonediol, polyesterdiol (except polycaprolactonediol), polyetherdiol, polycarbonate diol, etc. are mentioned, for example. (F) As a commercial item of a component, Kurare polyol P-510, P-1010, P-1020, P-2010 (all are Kuraray Co., Ltd. products), for example as a commercial item of component , Fraxel 205, Dong 208, Dong 210, Dong 212 (all manufactured by Daicel Co., Ltd.), Adeca polyether P-400, BP-11 (all manufactured by Adeka Co., Ltd.) ), Kurare Polyol C-590, C-1090, C-2090 (all manufactured by Kuraray Co., Ltd.), Duranol T-5650J, T-5652 (All of them are manufactured by ASAHI KASEI CHEMICALS CORPORATION), Fraxel DC210 (product of Daicel), NIPPOLAN 981, 980R (Tosoh Corporation) ) products), ethylene glycol, diethylene glycol, 14GG (all products of Mitsubishi Chemical Corporation), CHD-D (products of Nagase & CO., LTD.), etc. can be heard

When (F) component is used, the usage-amount is not specifically limited, Usually, although the upper limit of the usage-amount of (F) component is 50 mass % with respect to the total mass (solid content conversion) of (A) component and (F) component, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, and the lower limit of the usage-amount of (F) component is (A) 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass % with respect to the total mass (solid content conversion) of a component and (F)component , is 1% by mass. Moreover, the usage-amount range of (F) component can be suitably selected from the value of the upper limit and a lower limit of the said description, and can be set. Preferably (F) component is used so that it may become 1 mass % - 50 mass %.

The coating agent of this invention is (A) component, (B) component, and (C)component, and one or more components chosen from the group which consists of (D)component, (E)component, and (F)component as needed. is mixed with The mixing means and mixing order are not particularly limited.

In the coating agent of the present invention, if necessary, binder resins (acrylic resins, urethane resins, polyester resins, epoxy resins, alkyd resins, etc.) other than component (A), fine particles, anti-slip agents (anti-slip agents), preservatives, Rust preventives, pH regulators, antioxidants, pigments, dyes, lubricants, leveling agents, antifoaming agents and the like may be included.

The release film according to the present invention is an article comprising, as components, a cured film made of the thermosetting release coating agent of the present invention and a plastic film, and is obtained by applying the coating agent of the present invention to at least one side of a plastic film and heat-treating it.

Examples of the plastic film include a polycarbonate film, a polymethyl methacrylate film, a polystyrene film, a polyethylene terephthalate film, a polyimide film, a polyolefin film, a nylon film, an epoxy resin film, a melamine resin film, and a triacetyl cellulose resin film. , ABS resin film, ABS resin film, norbornene resin film, etc. are mentioned. The plastic film may be one that has been subjected to surface treatment (corona discharge, etc.). In addition, the said plastic film should just be one in which a layer (for example, an easy-to-adhesive layer) other than the coating agent composition of this invention was formed in the single side|surface or both surfaces. As said plastic film, the point of performance, such as transparency, dimensional stability, mechanical property, and chemical-resistance, a polyethylene terephthalate film is preferable. Moreover, the thickness of the said plastic film is not specifically limited, Usually, it is good if it is about 10-100 micrometers.

The application 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 also is not particularly limited, usually the mass after drying may be in a range that 0.1~10g / m ^2, preferably about 0.2~5g / m ^2.

The heating condition is also not particularly limited, and is usually about 30 seconds to 2 minutes at 90 to 130 degrees, and the coating agent of the present invention has relatively good fast curing at a relatively low temperature. Therefore, the coating agent of this invention is suitable for the plastic film which is easy to deform|transform by heat.

Moreover, you may add a curing treatment to the release film which concerns on this invention as needed. Although the conditions are not specifically limited, It is about 1 to 24 hours at 20-50 degrees. By doing in this way, the solvent resistance of a cured film becomes more favorable.

As mentioned above, preferable embodiment for making this invention understand easily was shown and demonstrated. The present invention will be described below based on examples, but the above description and the following examples are provided for purposes of illustration only, and not for the purpose of limiting the present invention. Accordingly, the scope of the present invention is not limited to the embodiment specifically described herein nor to the Examples, but is limited only by the claims.

[Example]

Hereinafter, the present invention will be described in detail through Examples and Comparative Examples, but it is not intended to limit the scope of the present invention by them. The present invention is not construed as being limited thereto, and examples obtained by appropriately combining the technical means disclosed in the respective examples are also included in the scope of the present invention. In addition, in each Example and comparative example, part or % is a mass basis.

Moreover, a hydroxyl value can be measured by the method based on JISK0070. The number average molecular weight can be measured by a polystyrene calibration curve using gel permeation chromatography (GPC).

<Preparation of thermosetting release coating agent>

Example 1

(A) Kurare Polyol F-510 (manufactured by Kuraray Co., Ltd.; it is composed of 3-methyl-1,5-pentanediol, adipic acid and trimethylolpropane, as a component, has a number average molecular weight of 500 and a hydroxyl value of 340 mgKOH/g 10.00 parts of polyester polyol), 0.22 parts of BK-377 (Bikchemy Japan Co., Ltd. product; polyether-modified hydroxyl group-containing silicone) (solid content concentration 100%) as component (B), 0.22 parts, and coronate as component (C) (CORONATE) HX (manufactured by Tosoh Corporation; isocyanurate form of hexamethylene diisocyanate) (solid content concentration 100%) of 11.86 parts, (D) component dioctyl tin dilaurate (solid content concentration 100% or less, 0.02 parts of DLC) and 83.14 parts of a mixed solvent (hereinafter, MEK/MIBK mixed solvent) in which the mass ratio of methyl ethyl ketone and methyl isobutyl ketone is 1:1 as component (E) was used. By mixing the above components well, a thermosetting release coating agent having a solid content concentration of 21% was prepared.

Example 2

(A) 10.00 parts of Kurare Polyol F-510 as component, (B) 0.87 parts of BK-370 (Bikchemy Japan Co., Ltd.; polyester-modified hydroxyl group-containing silicone) (solid content concentration of 25%) as component (B) As (C)component, 82.48 parts of MEK/MIBK mixed solvents were used as 11.86 parts of coronate HX and (D)component, 0.02 part of DOTLTL as (D)component, and (E) component. By mixing the above components well, a thermosetting release coating agent having a solid content concentration of 21% was prepared.

Example 3

(A) 10.00 parts of Kurarepolyol F-510 as component, and (B) 0.87 parts of BK-SIA LLA3700 (Bikchemi Japan Co., Ltd.; silicone-modified hydroxyl group-containing acrylic polymer) (solids content: 25%) as component (B) As (C)component, 82.48 parts of MEK/MIBK mixed solvents were used as 11.86 parts of coronate HX and (D)component, 0.02 part of DOTLTL as (D)component, and (E) component. By mixing the above components well, a thermosetting release coating agent having a solid content concentration of 21% was prepared.

Example 4

(A) 10.00 parts of Kurarepolyol F-510 as a component, 0.26 parts of BK-377 as (B) component, (C) As a component, Takenate D-110N (Mitsui Chemicals, Inc.) product: 21.91 parts of xylylene diisocyanate adduct) (solid content concentration of 75%), 0.03 parts of DLC as component (D), and 95.06 parts of MEK/MIBK mixed solvent as component (E). By mixing the above components well, a thermosetting release coating agent having a solid content concentration of 21% was prepared.

Example 5

(A) 10.00 parts of Kurarepolyol F-510 as a component, 0.27 parts of BK-377 as (B) component, Takenate D-120N (Mitsui Chemicals Co., Ltd. product; hydrogenated xylylenedi as (C)component) 22.91 parts of an isocyanate adduct) (solid content concentration of 75%), 0.03 parts of DOTLTL as (D) component, and 97.65 parts of MEK/MIBK mixed solvent as (E) component were used. By mixing the above components well, a thermosetting release coating agent having a solid content concentration of 21% was prepared.

Example 6

(A) 10.00 parts of Kurarepolyol F-510 as component, (B) 0.18 part of BK-377 as component, (C) MILLIONATE MMG-200 (manufactured by Tosoh Corporation; Polyme) as component Lycdiphenylmethane diisocyanate (MDI)) (solid content concentration of 100%) was used in 8.13 parts, (D) as component 0.02 parts of DOTLD, (E) as component, 68.95 parts of MEK/MIBK mixed solvent was used. By mixing the above components well, a thermosetting release coating agent having a solid content concentration of 21% was prepared.

Example 7

(A) 10.00 parts of Fraxel 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), (B) 0.29 parts of BK-377 as component, (C) ) 19.02 parts of coronate H as a component, 0.03 parts of DLC as (D)component, and 110.39 parts of MEK/MIBK mixed solvent as (E)component were used. By mixing the above components well, a thermosetting release coating agent having a solid content concentration of 21% was prepared.

Example 8

(A) 10.00 parts of Fraxel L320ALA (manufactured by Daicel Co., Ltd.; polycaprolactone triol having a number average molecular weight of 2000 and a hydroxyl value of 84 mgKOH/g) as component (A), (B) 0.13 parts of BK-377 as component, (C) ) As a component, 2.96 parts of coronate HX, 0.01 part of DLC as (D)component, and 49.29 parts of MEK/MIBK mixed solvents were used as (E)component. By mixing the above components well, a thermosetting release coating agent having a solid content concentration of 21% was prepared.

Example 9

(A) 10.00 parts of Adeca polyether AMA-302 (product of ADA Co., Ltd.; polyether triol having a number average molecular weight of 3000 and a hydroxyl value of 56 mgKOH/g) as component (A), and 0.12 parts of BK-377 as component (B) , 45.54 parts of MEK/MIBK mixed solvent were used as 1.97 parts of coronate H as (C)component, 0.01 part of DOTLTL as (D)component, and (E) component as (E)component. By mixing the above components well, a thermosetting release coating agent having a solid content concentration of 21% was prepared.

Example 10

(A) 10.00 parts of kurarepolyol F-510 as a component, 0.26 parts of BK-377 as (B) component, 21.91 parts of Takenate D-110N as (C)component, (E) MEK/MIBK mixing as a component 94.96 parts of solvent were used. By mixing the above components well, a thermosetting release coating agent having a solid content concentration of 21% was prepared.

Example 11

As component (A), it is 10.00 parts of kurarepolyol F-510, (B) component is BK-377 as 0.22 part, (C) component is 11.86 parts of coronate HX, (D) component is tris (2,4-) 0.02 parts of pentanedionato) iron (III) (solid content concentration of 100% or less, TDP) and 83.14 parts of MEK/MIBK mixed solvent as (E) component were used. By mixing the above components well, a thermosetting release coating agent having a solid content concentration of 21% was prepared.

Example 12

(A) 10.00 parts of Kurarepolyol F-510 as a component, 0.26 parts of BK-377 as (B) component, 21.91 parts of Takenate D-110N as (C)component, 0.03 parts of TLD as (D)component , 95.06 parts of MEK/MIBK mixed solvent were used as component (E). By mixing the above components well, a thermosetting release coating agent having a solid content concentration of 21% was prepared.

Example 13

(A) 10.00 parts of Fraxel 303 as a component, 0.36 parts of BK-377 as (B) component, 35.15 parts of Takenate D-110N as (C) component, 0.04 parts of TDP as (D) component, (E) As a component, 129.52 parts of MEK/MIBK mixed solvent was used. By mixing the above components well, a thermosetting release coating agent having a solid content concentration of 21% was prepared.

Example 14

(A) 10.00 parts of Fraxel 303 as a component, (B) 1.16 parts of BK-SIA LLA 3700 as a component, and SilaPlain FMD-D-modified silicon 11 (JN Concentration: 100% Carbinol Co., Ltd.) product of 0.07 parts; , (C) 35.15 parts of Takenate D-110N as component, 0.04 parts of TDP as (D) component, 128.65 parts of MEK/MIBK mixed solvent as (E) component were used. By mixing the above components well, a thermosetting release coating agent having a solid content concentration of 21% was prepared.

Example 15

(A) 10.00 parts of Kurarepolyol F-510 as component, (B) 0.85 parts of BQ-SIA LLA3700 as component, 0.05 parts of Silaplane MD-LD-A11 as 21.91 parts, (C) Takenate part as component (C) , 0.03 parts of TPD as component (D), and 94.43 parts of MEK/MIBK mixed solvent as component (E) were used. By mixing the above components well, a thermosetting release coating agent having a solid content concentration of 21% was prepared.

Example 16

(A) 10.00 parts of trimethylolpropane (manufactured by Mitsubishi Gas Chemicals Co., Ltd.; alkyltriol having a molecular weight of 134 and a hydroxyl value of 1250 mgKOH/g) as component (B), 2.28 parts of BM-SIPL3700 and Sila Plain L3700 as component (B) -DA11 was 0.14 parts, (C) component 81.66 parts Takenate D-110N, (D) component TDP 0.07 part, (E) component, 248.84 parts of MEK/MIBK mixed solvent were used. By mixing the above components well, a thermosetting release coating agent having a solid content concentration of 21% was prepared.

Example 17

(A) 10.00 parts of Fraxel 303 and 5.00 parts of trimethylolpropane as a component, (B) 2.30 parts of BK-SIA LLA 3700 as a component and 0.14 parts of silaplaneate D-D-A110 11 as a component, 0.07 parts of TPD as 75.99 parts of (D) component, and 253.07 parts of MEK/MIBK mixed solvents as (E) component were used. By mixing the above components well, a thermosetting release coating agent having a solid content concentration of 21% was prepared.

Example 18

(A) 10.00 parts of Fraxel 303 and 5.00 parts of trimethylolpropane as a component, (B) 2.30 parts of BK-SIA LLA 3700 as a component and 0.14 parts of silaplaneate D-D-A110 11 as a component, 75.99 parts of, 0.07 parts of TDP as component (D), 3.60 parts of acetylacetone and 249.47 parts of MEK/MIBK mixed solvent as component (E) were used. By mixing the above components well, a thermosetting release coating agent having a solid content concentration of 21% was prepared.

Comparative Example 1

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

Comparative Example 2

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

(A)
(B)
(C)
(D) NCO _(C)
O _(A)
(B)%
(D)% Example 1 Kurare Polyol F-510
BK-377 Coronate HX DDLC 1.0 1.0 0.1 Example 2 Kurare Polyol F-510
BK-370 Coronate HX DDLC 1.0 1.0 0.1 Example 3 Kurare Polyol F-510 BSQ-SIOL3700 Coronate HX DDLC 1.0 1.0 0.1 Example 4 Kurare Polyol F-510
BK-377 Takenate D-110N DDLC 1.0 1.0 0.1 Example 5 Kurare Polyol F-510
BK-377 Takenate D-120N DDLC 1.0 1.0 0.1 Example 6 Kurare Polyol F-510
BK-377 Milionate MMR-200 DDLC 1.0 1.0 0.1 Example 7 Fraxel 303 BK-377 Coronate HX DDLC 1.0 1.0 0.1 Example 8 Fraxel L320A L
BK-377 Coronate HX DDLC 1.0 1.0 0.1
Example 9 Adecapolyether AM-302
BK-377
Coronate HX
DDLC
1.0
1.0
0.1 Example 10 Kurare Polyol F-510
BK-377 Takenate D-110N
- 1.0 1.0 0 Example 11 Kurare Polyol F-510
BK-377 Coronate HX TPD 1.0 1.0 0.1 Example 12 Kurare Polyol F-510
BK-377 Takenate D-110N TPD 1.0 1.0 0.1 Example 13
Fraxel 303
BK-377 Takenate D-110N TPD 1.0 1.0 0.1
Example 14
Fraxel 303 BMASK-SIOL3700
Silaplane FM-DA11
Takenate D-110N
TPD
1.0
0.8
0.2
0.1
Example 15
Kurare Polyol F-510 BMASK-SIOL3700
Silaplane FM-DA11
Takenate D-110N
TPD
1.0
0.8
0.2
0.1
Example 16
trimethylolpropane BMASK-SIOL3700
Silaplane FM-DA11
Takenate D-110N
TPD
1.0
0.8
0.2
0.1
Example 17 Fraxel 303
trimethylolpropane BMASK-SIOL3700
Silaplane FM-DA11
Takenate D-110N
TPD
1.0
0.8
0.2
0.1
Example 18 Fraxel 303
trimethylolpropane BMASK-SIOL3700
Silaplane FM-DA11
Takenate D-110N
TPD
1.0
0.8
0.2
0.1
Comparative Example 1 Kurare Polyol P-1010
BK-377
Coronate HX
DDLC
1.0
1.0
0.1
Comparative Example 2 Kurare Polyol F-510
radish
Coronate HX
DDLC
1.0
-
0.1

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

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

<Production of 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 was 1 μm, and dried at 120 degrees for 1 minute. A release film having a cured film formed therein was prepared. For Example 10, a release film having a cured film made of the coating agent was prepared by drying at 120 degrees for 10 minutes, and for the coating agent of other Examples and Comparative Examples, a release film was prepared in the same manner as in Example 1.

<Solvent resistance of cured film>

After the release film according to Example 1 was left at 23°C overnight, the cured film was rubbed with a cotton swab impregnated with methyl ethyl ketone, and the cured film did not dissolve even after 100 rounds. Meanwhile, when the release film according to Example 9 was evaluated in the same manner, the base film was exposed at the 80th time. Solvent resistance was evaluated in the same manner with respect to the release film according to the other examples, but the cured film did not dissolve even after 100 reciprocations. On the other hand, when the release film according to Comparative Example 1 was evaluated in the same manner, the base film was exposed in the second time. On the other hand, for the film according to Comparative Example 2, the cured film did not dissolve even after 100 reciprocations. The results are shown in Table 2.

<Evaluation of releasability (separability to mold)>

After leaving the release film according to Example 1 to stand overnight, a polyester adhesive tape (Nitto Denko Corporation 31B tape: 20 mm width) was bonded to the surface of the cured film while being compressed with a 2 kg roller, It was left at 23 degrees for 1 hour. Then, using a Tensilon universal testing machine (product name RTC-1250A, Orientec Co., Ltd.), pull the adhesive tape horizontally at an angle of 180 degrees (0.3 m/mｉｎ), and the force required for peeling (N /20mm) was measured. In addition, the peeling force was measured in the same manner for the release films of other Examples and Comparative Examples. When the release film according to Comparative Example 1 was evaluated, measurement was not possible because the cured film was agglomerated and destroyed. The results are shown in Table 2.

solvent resistance
(number of round trips) peel force
(N/20mm) Example 1 >100 1.7 Example 2 >100 4.3 Example 3 >100 3.0 Example 4 >100 0.5 Example 5 >100 3.1 Example 6 >100 1.3 Example 7 >100 1.5 Example 8 >100 1.9 Example 9 80 6.0 Example 10 >100 0.8 Example 11 >100 1.4 Example 12 >100 0.5 Example 13 >100 0.4 Example 14 >100 0.1 Example 15 >100 0.1 Example 16 >100 0.1 Example 17 >100 0.1 Example 18 >100 0.1 Comparative Example 1 2 not measurable Comparative Example 2 >100 13

This application claims priority to Japanese Patent Application No. 2016-90241 (filed on April 28, 2016) and Japanese Patent Application No. 2016-157084 (filed on August 10, 2016), the entire contents of which are specific As described herein, the contents of which are incorporated herein by reference.

Claims (10)

(A) a polyol having at least three hydroxyl groups in the molecule and having a molecular weight of 80 to 5000 and a hydroxyl value of 30 to 2000 mgKOH/g;
(B) hydroxyl group-containing silicone;
(C) polyisocyanate;
(E) organic solvent in an amount such that the solid content concentration of the coating agent is 1 to 50 mass % in terms of solid content
A thermosetting release coating agent for a plastic film comprising a.
According to claim 1,
(A) The thermosetting release coating agent for plastic films whose molecular weight is 200-5000, and the polyol of component has a hydroxyl value of 30-840 mgKOH/g.
(A1) a polyol having at least three hydroxyl groups in the molecule and having 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 and having a molecular weight of 80 to 200 and a hydroxyl value of 841 to 2000 mgKOH/g;
(B) hydroxyl-containing silicone;
(C) polyisocyanate;
(E) organic solvent in an amount such that the solid content concentration of the coating agent is 1-50 mass % in terms of solid
A thermosetting release coating agent for a plastic film comprising a.
4. The method according to any one of claims 1 to 3,
(A) The thermosetting release coating agent for plastic films in which a component contains a ring-opening polymerization type polyester polyol (a-1) and/or a polycondensation type polyester polyol (a-2).
4. The method according to any one of claims 1 to 3,
(B) The thermosetting release coating agent for plastic films in which a component contains at least 1 sort(s) chosen from the group which consists of an acrylic polymer part, a polyester part, a polyether part, and a carbinol part.
4. The method according to any one of claims 1 to 3,
(D) Thermosetting release coating agent for plastic film further comprising a curing catalyst.
A release film comprising as components a cured film of the thermosetting release coating agent for a plastic film of any one of claims 1 to 3 and a plastic film.
8. The method of claim 7,
A release film in which the plastic film is a polyethylene terephthalate film.
A method for producing a release film, characterized in that the thermosetting release coating agent for a plastic film according to any one of claims 1 to 3 is applied to at least one side of the plastic film and subjected to heat treatment.
10. The method of claim 9,
A method for producing a release film in which the plastic film is a polyethylene terephthalate film.