JP5567292B2 - Active energy ray-curable release agent composition, coating film forming method using the same, release liner - Google Patents

Description

  The present invention relates to an active energy ray-curable release agent composition, a coating film forming method using the same, and a release liner, and has excellent peeling force, residual adhesion rate, coating film appearance, solvent resistance, and abrasion resistance, and is used as a raw material. The present invention relates to an active energy ray-curable release agent composition that can be applied to a pressure-sensitive adhesive tape for use in electronic materials or the like, and a release liner used for pressure-sensitive adhesive sheets, and a release liner using the same.

  Adhesive tapes and adhesive sheets are used in various industries because of their good handleability and good adhesive properties. Also in the field of electronic equipment, many adhesive tapes and adhesive sheets are used for bonding various members. Various release agents are coated on the release liner of the pressure-sensitive adhesive tape and pressure-sensitive adhesive sheet in order to impart a desired release force.

  The performance required for the release agent used for these includes not only stable release force but also many other performances. For example, the appearance of the coating film is important in order to obtain a residual adhesion rate after using a release agent and a smoother surface. Furthermore, it is necessary to have solvent resistance when a solvent-based pressure-sensitive adhesive is coated on a release sheet and dried by heat, and wear resistance that does not impair the peel force even after the surface is rubbed and worn.

  Conventional release agents are roughly classified into two types, thermoplastic and thermosetting resins. Since thermoplastic resins are not reactively cured after coating, they have low solvent resistance and heat resistance after film formation. On the other hand, although thermosetting resins are excellent in solvent resistance, heat resistance, etc., they are premised on heat-curing after coating, and therefore have a drawback that they cannot be used on substrates that are thin and weak against heat. In addition, one of the main resins of thermosetting resins is one in which an alkyd resin is cured with a crosslinking agent such as melamine (see Patent Document 1 and Patent Document 2).

JP 2008-156498 A JP 2008-156499 A

Although alkyd resin cured with a cross-linking agent such as melamine has high performance, in addition to the fact that it is thermosetting as described above, it contains some unreacted formaldehyde used as a raw material as an impurity. This is also being reviewed from the perspective of this. For this reason, there has long been a demand for a release agent that does not involve heat and that does not contain environmental pollutants. Also, in the case of pressure-sensitive adhesive sheets used for electronic materials, etc., if the silicone that is the release component moves from the release liner to the pressure-sensitive adhesive sheet side, this silicone will cause a failure of the electrical and electronic equipment. The non-migratory nature of the silicone is also an important performance. Silicone is highly suitable as a release component and is widely used. However, a release agent composition that exhibits release properties without using silicone is most desirable.
The present invention is a release liner used for pressure-sensitive adhesive tapes or pressure-sensitive adhesive sheets for use in electronic materials, etc., which has good peel strength, residual adhesion rate, coating film appearance, solvent resistance, and wear resistance, and does not use silicone as a raw material. The present invention provides an active energy ray-curable release agent composition applicable to the present invention, a coating film forming method using the same and a release liner.

As a result of intensive investigations taking into account the above-mentioned object, the inventors have an average of three or more (meth) acryloyl groups in one molecule, and the concentration thereof is 8 equivalents or more per kg (meta). An acrylate (A), an organic isocyanate (B) having at least two isocyanate groups in one molecule, one selected from those having 8 to 22 carbon atoms, or two or more higher alcohols (C) A silicone-free UV-curable release agent with good release force, residual adhesion rate, coating film appearance, solvent resistance, and abrasion resistance, if necessary by adding a photopolymerization initiator to the resin obtained by reaction. It was found that a composition was obtained.
In the present invention, [1] hydroxyl group-containing (meth) acrylate (A) having three or more (meth) acryloyl groups on average in one molecule and having a concentration of 8 equivalents or more per 1 kg, in one molecule One molecule selected from organic isocyanate (B) having at least two or more isocyanate groups, one selected from those having 8 to 22 carbon atoms, or two or more higher alcohols (C), (meth) acryloyl groups It consists of (meth) acrylate (D) which does not contain a hydroxyl group having 3 or more on average and its concentration is 8 equivalents or more per kilogram, and (B) and (C) can be reacted. An active energy ray-curable release agent composition for a release liner obtained by further reacting a mixture of ((A) + (D)) with the reaction product ((B) + (C)), Reaction product ((B) + ( C)) and the mixture ((A) + (D)) are ((B) + (C)) / ((A) + (B) + (C) + (D) ) in mass ratio. = Active energy ray-curable release agent composition for release liner adjusted to be 0.01 to 0.5.
The present invention also provides [2] the active energy ray-curable release agent according to the above [1], wherein the hydroxyl group-containing (meth) acrylate (A) has a structure represented by the general formula (1) or the general formula (2). It is a composition.

（一般式（１）、（２）中、Ｘ^１〜Ｘ^１０は、それぞれ独立に（メタ）アクリロイル基又は水酸基を表し、Ｘ^１〜Ｘ^６のうち少なくとも３個以上５個以下は、（メタ）アクリロイル基を示し、Ｘ^７〜Ｘ^１０のうち３個は、（メタ）アクリロイル基を示す。）

(In the general formulas (1) and (2), X ^{1 to} X ¹⁰ each independently represent a (meth) acryloyl group or a hydroxyl group, and at least 3 to 5 of X ^{1 to} X ⁶ are (meta ) Represents an acryloyl group, and three of X ^{7 to} X ¹⁰ represent a (meth) acryloyl group.

The present invention also provides [3] the active energy ray-curable release agent composition according to the above [1] or [2], wherein the organic isocyanate (B) is an isocyanurate of hexamethylene diisocyanate.
In the present invention, [4] the total isocyanate group content of the organic isocyanate (B) is obtained by subtracting the total hydroxyl group content of the higher alcohol (C) from the total isocyanate group content of the organic isocyanate (B). The active energy ray-curable release agent composition according to any one of [1] to [3], which is adjusted to be smaller than the amount of hydroxyl group.
In addition, the present invention provides [5] the active energy ray-curable release agent composition according to any one of [1] to [4] described above as a base material to have a thickness of 0.05 to 10 μm in solid content. It is a coating film forming method of coating, irradiating with active energy rays and curing.
Moreover, this invention is a peeling liner obtained by the coating-film formation method as described in [6] said [5].

  According to the present invention, it is possible to obtain an active energy ray-curable release agent composition and a release liner that have good peeling force, residual adhesion rate, coating film appearance, solvent resistance, and abrasion resistance and do not use silicone as a raw material. I can do it.

  In the present invention, the hydroxyl group-containing (meth) acrylate (A) having at least three (meth) acryloyl groups on average in one molecule and having a concentration of 8 equivalents or more per 1 kg, at least two in one molecule. The organic isocyanate (B) having one or more isocyanate groups, one kind selected from those having 8 to 22 carbon atoms, or two or more kinds of higher alcohols (C), and having a mass ratio of ((B) + ( C)) / ((A) + (B) + (C)) = related to an active energy ray-curable release agent composition for a release liner adjusted to be 0.01 to 0.5.

  The hydroxyl group-containing (meth) acrylate (A) constituting the active energy ray-curable release agent composition of the present invention has three or more (preferably five or more) average (meth) acryloyl groups in one molecule. In addition, the concentration should be 8 equivalents or more (preferably 10 equivalents) or more per kilogram. The reason is to have sufficient curability. In the active energy ray-curable release agent composition, the contained (meth) acryloyl group undergoes a radical reaction and is cured by polymerization. However, it is generally known that radicals are trapped by oxygen molecules and deactivated, so that they are inhibited from curing in the presence of oxygen, and that the effect becomes more pronounced as the film becomes thinner. The active energy ray-curable release agent composition of the present invention is 0.05 to 10 μm in order to obtain a cost problem and a smoother surface when an active energy ray-curable release agent composition layer is provided on a substrate. Often coated with a thin film. The active energy ray-curable composition that exhibits sufficient curability in such a situation is limited. If it does not have sufficient curability, curing failure tends to occur even when active energy rays are irradiated. As a result, even if the appearance is cured, the residual adhesion rate, wear resistance, solvent resistance, etc. are deteriorated, and the peeling force tends to be heavy. If the (meth) acrylate (A) has three or more (meth) acryloyl groups in one molecule and the concentration is 8 equivalents or more per 1 kg, sufficient curability can be obtained even in the above-described thin film. Have In addition, (meth) acrylate means an acrylate, a methacrylate, and mixtures thereof.

  In order to obtain better curability, it is desirable to use a hydroxyl group-containing acrylate that does not contain a methacryloyl group and that has only an acryloyl group and a hydroxyl group as a functional group. Among them, dipentaerythritol monoacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate having the structure shown in the above general formulas (1) and (2), One or a mixture of two or more selected from pentaerythritol monoacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate, and the concentration of acryloyl groups contained in the molecule is three or more on average, and its concentration Is preferably adjusted to 8 equivalents or more per kg.

  Moreover, according to a use condition, the acrylate which does not contain a hydroxyl group but contains only an acryloyl group, such as dipentaerythritol hexaacrylate and pentaerythritol tetraacrylate, can also be used together.

  The organic isocyanate (B) constituting the active energy ray-curable release agent composition of the present invention is not particularly limited as long as it has at least two isocyanate groups in one molecule. Typical examples include tolylene diisocyanate, hydrogenated tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, lysine diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, Furthermore, biuret type polyisocyanate compounds obtained by reacting these various diisocyanate compounds with water, or adduct type polyisocyanate compounds obtained by reacting various diisocyanate compounds with polyhydric alcohols such as trimethylolpropane, or various compounds. And the like and known ones such as a multimer obtained by isocyanurate formation. In particular, when isocyanurate of hexamethylene diisocyanate is used for the organic isocyanate (B), the residual adhesion rate is good and the peeling tends to be lightest, which is desirable.

Since the higher alcohol (C) constituting the active energy ray-curable release agent composition of the present invention is reacted with the hydroxyl group-containing (meth) acrylate (A) via the organic isocyanate (B), at least in one molecule. It must have one or more hydroxyl groups. Moreover, in order to express favorable peeling force, it is calculated | required that the carbon number is 8-22. Others are not particularly limited, but a saturated higher alcohol having 18 or more carbon atoms and a straight chain is preferable because the peeling force is particularly light. Unsaturated higher alcohols and branched types can also be used, but when this is used, the peel strength tends to be heavier than that using linear saturated higher alcohols, but the active energy Since the crystallinity of the linear curable release agent composition is lowered, the transparency is higher and a smooth coating film is easily obtained, which is desirable from the viewpoint of coating film appearance.
Examples of linear higher alcohols include octyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetanol, cetostearyl alcohol, stearyl alcohol, and behenyl alcohol, and examples of linear unsaturated higher alcohols include oleyl. Examples of branched higher alcohols include alcohols such as 2-hexyldecanol, 2-octyldodecanol, and 2-decyltetradodecanol.

  As the higher alcohol (C) having 8 to 22 carbon atoms having a hydroxyl group, a commercially available product can be used. For example, as a linear saturated higher alcohol, Conol 10WS, Conol 1098, Conol 1275, Conol 20F, Conol 20P, Conol 1495, Conol 1670, Conol 1695, Conol 30CK, Conol 30OC, Conol 30RC, Conol 30F, Conol 30S, Conol 30SS, Conol 30T, Conol 2265, Conol 2280 (trade name, manufactured by Shin Nippon Chemical Co., Ltd.), Calcoal 0898 , Calcoal 0880, Calcoal 1098, Calcoal 2098, Calcoal 4098, Calcoal 6098, Calcoal 8098, Calcoal 200GD, Calcoal 2475, Calcoal 2474, Calcoal 2 73, Calcoal 2463, Calcoal 2455, Calcoal 2450, Calcoal 4250, Calcoal 6870, Calcoal 6850, Calcoal 8688, Calcoal 8665, Calcoal 220-80 (trade name, manufactured by Kao Corporation), linear unsaturated higher alcohol, Rica Call 60B, Rica Call 70B, Rica Call 75BJ, Rica Call 85BJ, Rica Call 90B, Rica Call 90BR, Rica Call 90BHR, Rica Call 110BJ, Angkor Call 50A, Angkor Call 60AN, Angkor Cole 70AN, Angkor Cole 80AN, Angkor Cole 85AN, Angkor Cole 90NR, Angersol 90NHR (trade name, manufactured by Shin Nippon Rika Co., Ltd.) Ecole 160BR, NJ Coal 200A, NJ Coal 240A (trade name, manufactured by Shin Nippon Chemical Co., Ltd.) and the like.

  The ratio of the mass ratio of the hydroxyl group-containing (meth) acrylate (A), organic isocyanate (B), and higher alcohol (C) is ((B) + (C)) / ((A) + (B) + (C) ) = In the range of 0.01 to 0.5. When smaller than this, it becomes difficult to obtain a stable peeling force. On the other hand, if it is too large, the content of hydroxyl group-containing (meth) acrylate will be low, so the solvent resistance and residual adhesive rate will deteriorate, and if linear saturated higher alcohol is used, active energy ray curing The crystallinity of the release agent composition becomes high, and the coating surface tends to be whitened or smooth when coated. If it is in the range, a stable peeling force is expressed, and an active energy ray-curable release agent composition having good solvent resistance, residual adhesion rate, and coating film appearance can be obtained.

  Further, the value obtained by subtracting the total hydroxyl group content of the higher alcohol (C) from the total isocyanate group amount of the organic isocyanate (B) is smaller than the total hydroxyl group content of the hydroxyl group-containing (meth) acrylate (A). If adjusted, the amount of the higher alcohol (C) remaining without reacting with the hydroxyl group-containing (meth) acrylate (A) can be reduced. That is, it is desirable because the amount of the long-chain alkyl group-containing compound having no active energy ray curing ability is reduced, and as a result, the residual adhesion rate and the solvent resistance are likely to be improved. For this reason, it is preferable to react (B) and (C) first and then react (A) as shown in the Examples.

  Examples of the active energy rays used in the present invention include known and conventional ones such as electron beams, α rays, β rays, γ rays, infrared rays, visible rays, and ultraviolet rays. Among them, studies on electron beams and ultraviolet rays are relatively advanced. In particular, ultraviolet rays are desirable because they have the advantage that the irradiation device can be obtained at low cost.

  When the active energy ray-curable release agent composition of the present invention is cured with active energy rays, it is not necessary to mix a photopolymerization initiator if the above-mentioned electron beam is used. Need to be mixed. Examples of photopolymerization initiators that can be used include 2,2-dimethoxy-1,2-diphenylethane-1-one, benzophenone, and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2. -Methyl-1-propan-1-one, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] ethyl ester, oxy-phenyl-acetic acid 2- [2-hydroxy- Ethoxy] -ethyl ester, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-dimethylamino-2- (4-methylbenzyl)-(4-1-morpholine -4-yl-phenyl) -butan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxa Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 1,2-octanedione, 1- [ 4- (phenylthio)-, 2- (o-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o- Acetyloxime), 2-chlorothioxanthone, 2,4-diethylthioxanthone, benzophenone, [4- (methylphenylthio) phenyl] phenylmethanone, ethyl anthraquinone, etc., one kind or a mixture of two or more kinds are used. I can do it. 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-hydroxy -1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinopropan-1-one is preferred, especially 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methylpropane-1 -On is particularly desirable. The blending amount is preferably adjusted to 5 to 15% by mass with respect to the total mass of (A), (B), and (C) from the viewpoints of curability, cost, and the like.

  In order to enhance the effect of the photopolymerization initiator, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylamino-benzoic acid ethyl ester, N-methyldiethanolamine, bisethylaminobenzophenone, ethyl-4-dimethylaminobenzoate, Initiating aids such as 2-ethylhexyl-4-dimethylaminobenzoate can also be used.

  The active energy ray-curable release agent composition of the present invention is usually an organic solvent solution for convenience of use, but the organic solvent has good solubility with each component and has no reactivity. If it exists, a conventionally well-known thing can be used. For example, toluene, xylene, methanol, ethanol, isobutanol, n-butanol, methyl ethyl ketone, hexane, heptane and the like can be used alone or in a mixture of two or more, and the amount used is 1 to 60% by mass of the resin solid content. It is desirable to be in the range.

  The active energy ray-curable release agent composition of the present invention is peeled off by coating (coating) a substrate, heating in the case of a solvent system, volatilizing the solvent, and then irradiating and curing the active energy ray. A layer can be formed. The heating temperature is 50 to 100 ° C. although it depends on the film thickness and the diluent solvent.

  When the active energy ray-curable release agent composition of the present invention is applied to a substrate to produce a release liner, the release agent layer is preferably 0.05 to 10 μm. Within this range, a release liner having a smooth coated surface and a stable release force can be produced at a relatively low cost.

  Specific examples of the substrate for the release liner include film substrates such as polyethylene film, polypropylene film, polyethylene terephthalate film and polyethylene naphthalate film, and fine paper, medium paper, art paper, cast coated paper, and Examples thereof include paper base materials such as coated paper.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Further, “parts” and “%” shown in the examples represent mass and mass% unless otherwise specified.

[Example 1]
In a flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube, Coronate HX (trade name, manufactured by Nippon Polyurethane Co., Ltd., trade name Hexamethylene) as an organic isocyanate (B) having at least two isocyanate groups in one molecule 570 parts of diisocyanate isocyanurate), 405 parts of Conol 30SS (trade name, Stearyl Alcohol, manufactured by Shin Nippon Chemical Co., Ltd.) as higher alcohol (C) having 8 to 22 carbon atoms, and 975 parts of toluene were heated to 85 ° C. For 7 hours to obtain a reaction product having a resin solid content of 50%. In a separate flask having the same equipment, KAYARAD DPHA (Nippon Kayaku Co., Ltd., general formula (1), mixture of pentaacrylate and hexaacrylate ) as a mixture of (A) and (D) 990 parts, 20 parts ((B) + (C) = 10 parts) of the reaction product obtained above and 990 parts of toluene were added, the temperature was raised to 85 ° C. and the mixture was allowed to react for 7 hours, and the result of IR measurement was isocyanate. After confirming the disappearance of the group and lowering the temperature in the system to 30 ° C., 100 parts of Irgacure 184 (Ciba Japan Co., Ltd. photopolymerization initiator, 1-hydroxy-cyclohexyl-phenyl-ketone) was added and mixed. Then, an active energy ray-curable release agent composition A was obtained.

[Example 2]
In a flask equipped with the same equipment as in Example 1, 570 parts of Coronate HX (manufactured by Nippon Polyurethane Co., Ltd.) as an organic isocyanate (B) having at least two isocyanate groups in one molecule, high grade having 8 to 22 carbon atoms As alcohol (C), 405 parts of Conol 30SS (manufactured by Nippon Nippon Chemical Co., Ltd.) and 975 parts of toluene were charged, heated to 85 ° C. and incubated for 7 hours to obtain a reaction product having a resin solid content of 50%. . In a separate flask having the same equipment, 950 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a mixture of (A) and (D) and 100 parts of the reaction product obtained earlier ((B) + ( C) = 50 parts), 950 parts of toluene were charged, heated to 85 ° C., kept for 7 hours and reacted to confirm that the isocyanate group had disappeared as a result of IR measurement, and the system temperature was lowered to 30 ° C. Then, 100 parts of Irgacure 184 (manufactured by Ciba Japan Co., Ltd.) was charged and mixed to obtain an active energy ray-curable release agent composition B.

[Example 3]
In a flask equipped with the same equipment as in Example 1, 570 parts of Coronate HX (manufactured by Nippon Polyurethane Co., Ltd.) as an organic isocyanate (B) having at least two isocyanate groups in one molecule, high grade having 8 to 22 carbon atoms As alcohol (C), 405 parts of Conol 30SS (manufactured by Nippon Nippon Chemical Co., Ltd.) and 975 parts of toluene were charged, heated to 85 ° C. and incubated for 7 hours to obtain a reaction product having a resin solid content of 50%. . In another flask having the same equipment, 900 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a mixture of (A) and (D) and 200 parts of the reaction product obtained earlier ((B) + ( C) = 100 parts), charged with 900 parts of toluene, heated to 85 ° C., kept for 7 hours, reacted to confirm that the isocyanate group disappeared as a result of IR measurement, and lowered the system temperature to 30 ° C. Then, 100 parts of Irgacure 184 (manufactured by Ciba Japan Co., Ltd.) was charged and mixed to obtain an active energy ray-curable release agent composition C.

[Example 4]
In a flask equipped with the same equipment as in Example 1, 570 parts of Coronate HX (manufactured by Nippon Polyurethane Co., Ltd.) as an organic isocyanate (B) having at least two isocyanate groups in one molecule, high grade having 8 to 22 carbon atoms As alcohol (C), 405 parts of Conol 30SS (manufactured by Nippon Nippon Chemical Co., Ltd.) and 975 parts of toluene were charged, heated to 85 ° C. and incubated for 7 hours to obtain a reaction product having a resin solid content of 50%. . In another flask having the same equipment, 850 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a mixture of (A) and (D) and 300 parts of the reaction product obtained earlier ((B) + ( C) = 150 parts), charged with 850 parts of toluene, heated to 85 ° C., kept for 7 hours, reacted to confirm that the isocyanate group disappeared as a result of IR measurement, and lowered the system temperature to 30 ° C. Then, 100 parts of Irgacure 184 (manufactured by Ciba Japan Co., Ltd.) was charged and mixed to obtain an active energy ray-curable release agent composition D.

[Example 5]
In a flask equipped with the same equipment as in Example 1, 570 parts of Coronate HX (manufactured by Nippon Polyurethane Co., Ltd.) as an organic isocyanate (B) having at least two isocyanate groups in one molecule, high grade having 8 to 22 carbon atoms As alcohol (C), 405 parts of Conol 30SS (manufactured by Nippon Nippon Chemical Co., Ltd.) and 975 parts of toluene were charged, heated to 85 ° C. and incubated for 7 hours to obtain a reaction product having a resin solid content of 50%. . In a separate flask having the same equipment, 500 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a mixture of (A) and (D) and 1000 parts of the reaction product obtained earlier ((B) + ( C) = 500 parts), charged with 500 parts of toluene, heated to 85 ° C., kept for 7 hours, reacted to confirm that the isocyanate group disappeared as a result of IR measurement, and lowered the system temperature to 30 ° C. Then, 100 parts of Irgacure 184 (manufactured by Ciba Japan Co., Ltd.) was charged and mixed to obtain an active energy ray-curable release agent composition E.

[Example 6]
In a flask equipped with the same equipment as in Example 1, 222 parts of isophorone diisocyanate as organic isocyanate (B) having at least two isocyanate groups in one molecule, and Conol 30SS as higher alcohol (C) having 8 to 22 carbon atoms 270 parts (manufactured by Shin Nippon Chemical Co., Ltd.) and 492 parts of toluene were charged, the temperature was raised to 85 ° C., and the reaction was carried out for 7 hours to obtain a reaction product having a resin solid content of 50%. In another flask having the same equipment, 850 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a mixture of (A) and (D) and 300 parts of the reaction product obtained earlier ((B) + ( C) = 150 parts), charged with 850 parts of toluene, heated to 85 ° C., kept for 7 hours, reacted to confirm that the isocyanate group disappeared as a result of IR measurement, and lowered the system temperature to 30 ° C. Then, 100 parts of Irgacure 184 (manufactured by Ciba Japan Co., Ltd.) was charged and mixed to obtain an active energy ray-curable release agent composition F.

[Example 7]
In a flask equipped with the same equipment as in Example 1, 168 parts of hexamethylene diisocyanate as organic isocyanate (B) having at least two isocyanate groups in one molecule, and conol as higher alcohol (C) having 8 to 22 carbon atoms 270 parts of 30SS (manufactured by Nippon Shin-Rika Co., Ltd.) and 438 parts of toluene were charged, heated to 85 ° C. and incubated for 7 hours to obtain a reaction product having a resin solid content of 50%. In another flask having the same equipment, 850 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a mixture of (A) and (D) and 300 parts of the reaction product obtained earlier ((B) + ( C) = 150 parts), charged with 850 parts of toluene, heated to 85 ° C., kept for 7 hours, reacted to confirm that the isocyanate group disappeared as a result of IR measurement, and lowered the system temperature to 30 ° C. Then, 100 parts of Irgacure 184 (manufactured by Ciba Japan Co., Ltd.) was charged and mixed to obtain an active energy ray-curable release agent composition G.

[Example 8]
In a flask equipped with the same equipment as in Example 1, 570 parts of Coronate HX (manufactured by Nippon Polyurethane Co., Ltd.) as an organic isocyanate (B) having at least two isocyanate groups in one molecule, high grade having 8 to 22 carbon atoms As alcohol (C), 171 parts of Calcoal 0898 (trade name: Octyl Alcohol, manufactured by Kao Corporation) and 741 parts of toluene were charged, heated to 85 ° C. and allowed to react for 7 hours to obtain a reaction product having a resin solid content of 50%. Obtained. In another flask having the same equipment, 850 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a mixture of (A) and (D) and 300 parts of the reaction product obtained earlier ((B) + ( C) = 150 parts), charged with 850 parts of toluene, heated to 85 ° C., kept for 7 hours, reacted to confirm that the isocyanate group disappeared as a result of IR measurement, and lowered the system temperature to 30 ° C. Then, 100 parts of Irgacure 184 (manufactured by Ciba Japan Co., Ltd.) was charged and mixed to obtain an active energy ray-curable release agent composition H.

[Example 9]
In a flask equipped with the same equipment as in Example 1, 570 parts of Coronate HX (manufactured by Nippon Polyurethane Co., Ltd.) as an organic isocyanate (B) having at least two isocyanate groups in one molecule, high grade having 8 to 22 carbon atoms 279 parts of Calcoal 2098 (Lauryl alcohol manufactured by Kao Corporation) and 849 parts of toluene were added as alcohol (C), and the mixture was heated to 85 ° C. and kept for 7 hours to obtain a reaction product having a resin solid content of 50%. . In another flask having the same equipment, 850 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a mixture of (A) and (D) and 300 parts of the reaction product obtained earlier ((B) + ( C) = 150 parts), charged with 850 parts of toluene, heated to 85 ° C., kept for 7 hours, reacted to confirm that the isocyanate group disappeared as a result of IR measurement, and lowered the system temperature to 30 ° C. Then, 100 parts of Irgacure 184 (manufactured by Ciba Japan Co., Ltd.) was charged and mixed to obtain an active energy ray-curable release agent composition I.

[Example 10]
In a flask equipped with the same equipment as in Example 1, 570 parts of Coronate HX (manufactured by Nippon Polyurethane Co., Ltd.) as an organic isocyanate (B) having at least two isocyanate groups in one molecule, high grade having 8 to 22 carbon atoms As alcohol (C), 489 parts of Conol 2280 (manufactured by Shin Nippon Rika Co., Ltd., 80-85% behenyl alcohol) and 1059 parts of toluene were charged, heated to 85 ° C. and incubated for 7 hours to react, and the resin solid content 50% of the reaction was obtained. In another flask having the same equipment, 850 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a mixture of (A) and (D) and 300 parts of the reaction product obtained earlier ((B) + ( C) = 150 parts), charged with 850 parts of toluene, heated to 85 ° C., kept for 7 hours, reacted to confirm that the isocyanate group disappeared as a result of IR measurement, and lowered the system temperature to 30 ° C. Then, 100 parts of Irgacure 184 (manufactured by Ciba Japan Co., Ltd.) was charged and mixed to obtain an active energy ray-curable release agent composition J.

[Example 11]
In a flask equipped with the same equipment as in Example 1, 570 parts of Coronate HX (manufactured by Nippon Polyurethane Co., Ltd.) as an organic isocyanate (B) having at least two isocyanate groups in one molecule, high grade having 8 to 22 carbon atoms As alcohol (C), 467 parts of NJECOAL 200A (2-octyldodecanol manufactured by Shin Nippon Chemical Co., Ltd.) and 1037 parts of toluene were charged, heated to 85 ° C. and kept for 7 hours to react, and the resin solid content was 50%. A reaction product was obtained. In another flask having the same equipment, 850 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a mixture of (A) and (D) and 300 parts of the reaction product obtained earlier ((B) + ( C) = 150 parts), charged with 850 parts of toluene, heated to 85 ° C., kept for 7 hours, reacted to confirm that the isocyanate group disappeared as a result of IR measurement, and lowered the system temperature to 30 ° C. Then, 100 parts of Irgacure 184 (manufactured by Ciba Japan Co., Ltd.) was charged and mixed to obtain an active energy ray-curable release agent composition K.

[Example 12]
In a flask equipped with the same equipment as in Example 1, 570 parts of Coronate HX (manufactured by Nippon Polyurethane Co., Ltd.) as an organic isocyanate (B) having at least two isocyanate groups in one molecule, high grade having 8 to 22 carbon atoms As alcohol (C), 400 parts of Ricacol 90B (Oleyl alcohol manufactured by Shin Nippon Rika Co., Ltd.) and 970 parts of toluene are charged, heated to 85 ° C. and kept for 7 hours to react, and a reaction product having a resin solid content of 50% is obtained. Obtained. In another flask having the same equipment, 850 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a mixture of (A) and (D) and 300 parts of the reaction product obtained earlier ((B) + ( C) = 150 parts), charged with 850 parts of toluene, heated to 85 ° C., kept for 7 hours, reacted to confirm that the isocyanate group disappeared as a result of IR measurement, and lowered the system temperature to 30 ° C. Then, 100 parts of Irgacure 184 (manufactured by Ciba Japan Co., Ltd.) was charged and mixed to obtain an active energy ray-curable release agent composition L.

[Example 13]
In a flask equipped with the same equipment as in Example 1, 570 parts of Coronate HX (manufactured by Nippon Polyurethane Co., Ltd.) as an organic isocyanate (B) having at least two isocyanate groups in one molecule, high grade having 8 to 22 carbon atoms As alcohol (C), 405 parts of Conol 30SS (manufactured by Nippon Nippon Chemical Co., Ltd.) and 975 parts of toluene were charged, heated to 85 ° C. and incubated for 7 hours to obtain a reaction product having a resin solid content of 50%. . In another flask with the same equipment, as a mixture of (A) and (D), KAYARAD PET-30 (trade name, manufactured by Nippon Kayaku Co., Ltd., having the structure represented by the general formula (2), triacrylate and tetra Acrylate mixture), 300 parts ((B) + (C) = 150 parts) of the reaction product obtained earlier, and 850 parts of toluene, heated to 85 ° C. and kept for 7 hours to react. As a result of IR measurement, it was confirmed that the isocyanate group had disappeared, the temperature inside the system was lowered to 30 ° C., and then 100 parts of Irgacure 184 (manufactured by Ciba Japan Co., Ltd.) was charged and mixed, and an active energy ray-curable release agent composition Product M was obtained.

[Comparative Example 1]
100 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), 100 parts of toluene, and 10 parts of Irgacure 184 (manufactured by Ciba Japan Co., Ltd.) were mixed to obtain an active energy ray-curable release agent composition N.

[Comparative Example 2]
In a flask equipped with the same equipment as in Example 1, 570 parts of Coronate HX (manufactured by Nippon Polyurethane Co., Ltd.) as an organic isocyanate (B) having at least two isocyanate groups in one molecule, high grade having 8 to 22 carbon atoms As alcohol (C), 405 parts of Conol 30SS (manufactured by Nippon Nippon Chemical Co., Ltd.) and 975 parts of toluene were charged, heated to 85 ° C. and incubated for 7 hours to obtain a reaction product having a resin solid content of 50%. . In a separate flask having the same equipment, 995 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a mixture of (A) and (D) and 10 parts of the reaction product obtained previously ((B) + ( C) = 5 parts), charged with 995 parts of toluene, heated to 85 ° C., kept for 7 hours, reacted to confirm that the isocyanate group disappeared as a result of IR measurement, and lowered the system temperature to 30 ° C. Then, 100 parts of Irgacure 184 (manufactured by Ciba Japan Co., Ltd.) was charged and mixed to obtain an active energy ray-curable release agent composition O.

[Comparative Example 3]
In a flask equipped with the same equipment as in Example 1, 570 parts of Coronate HX (manufactured by Nippon Polyurethane Co., Ltd.) as an organic isocyanate (B) having at least two isocyanate groups in one molecule, high grade having 8 to 22 carbon atoms As alcohol (C), 405 parts of Conol 30SS (manufactured by Nippon Nippon Chemical Co., Ltd.) and 975 parts of toluene were charged, heated to 85 ° C. and incubated for 7 hours to obtain a reaction product having a resin solid content of 50%. . In another flask having the same equipment, 400 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a mixture of (A) and (D) and 1200 parts of the reaction product obtained earlier ((B) + ( C) = 600 parts), charged with 400 parts of toluene, heated to 85 ° C., kept for 7 hours, reacted to confirm that the isocyanate group disappeared as a result of IR measurement, and lowered the system temperature to 30 ° C. Then, 100 parts of Irgacure 184 (manufactured by Ciba Japan Co., Ltd.) was charged and mixed to obtain an active energy ray-curable release agent composition P.

[Comparative Example 4]
In a flask equipped with the same equipment as in Example 1, 570 parts of Coronate HX (manufactured by Nippon Polyurethane Co., Ltd.) as organic isocyanate (B) having at least two isocyanate groups in one molecule, 111 parts of butyl alcohol, and 681 of toluene The reaction product was obtained by heating up to 85 ° C. and incubating for 7 hours. In another flask having the same equipment, 850 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), 300 parts of the reaction product obtained earlier and 850 parts of toluene were charged, and the temperature was raised to 85 ° C. for 7 hours. It was kept warm and reacted, and it was confirmed that the isocyanate group had disappeared as a result of IR measurement. After the temperature in the system was lowered to 30 ° C., 100 parts of Irgacure 184 (manufactured by Ciba Japan Co., Ltd.) was added and mixed, and active energy rays A curable release agent composition Q was obtained.

[Comparative Example 5]
In a flask having the same equipment as in Example 1, 570 parts of Coronate HX (manufactured by Nippon Polyurethane Co., Ltd.) as an organic isocyanate (B) having at least two isocyanate groups in one molecule, Conol 30SS (Shin Nippon Rika Co., Ltd.) 405 parts by company) and 975 parts of toluene were charged, the temperature was raised to 85 ° C., and the reaction was continued for 7 hours to obtain a reaction product. In a separate flask having the same equipment, 850 parts of 2-hydroxyethyl acrylate, 300 parts of the reaction product obtained earlier and 850 parts of toluene were charged, and the temperature was raised to 85 ° C. and kept for 7 hours to react. As a result of IR measurement, it was confirmed that the isocyanate group had disappeared, the temperature inside the system was lowered to 30 ° C., and then 100 parts of Irgacure 184 (manufactured by Ciba Japan Co., Ltd.) was charged and mixed, and an active energy ray-curable release agent composition Product R was obtained.

[Comparative Example 6]
In a flask having the same equipment as in Example 1, 570 parts of Coronate HX (manufactured by Nippon Polyurethane Co., Ltd.) as an organic isocyanate (B) having at least two isocyanate groups in one molecule, Conol 30SS (Shin Nippon Rika Co., Ltd.) 405 parts by company) and 975 parts of toluene were charged, the temperature was raised to 85 ° C., and the reaction was continued for 7 hours to obtain a reaction product. In another flask having the same equipment, 850 parts of epoxy ester 3000A (manufactured by Kyoeisha Chemical Co., Ltd., acrylic acid adduct of bisphenol A diglycidyl ether), 300 parts of the reaction product obtained earlier, and 850 parts of methyl ethyl ketone. Charge, heat up to 85 ° C., incubate for 7 hours, react to confirm that the isocyanate group has disappeared as a result of IR measurement, lower the temperature inside the system to 30 ° C., and then use Irgacure 184 (manufactured by Ciba Japan Co., Ltd.). A release agent composition S was obtained by charging 100 parts and mixing.

[Comparative Example 7]
Paratoluenesulfonic acid was added to a non-silicon type alkyd-based thermosetting release resin Resus Fine 303 (manufactured by Hitachi Chemical Polymer Co., Ltd.) at 5% based on the solid content to obtain a release agent composition T.

  The performance evaluation was performed according to the following method.

An untreated polyethylene terephthalate (hereinafter abbreviated as “PET”) film having a thickness of 100 μm was used as a base material for the release film for evaluation, and each test resin was coated to a solid content thickness of 0.15 μm. The active energy ray-curable release agent compositions A to S volatilize the solvent at 70 ° C. for 30 seconds after coating, and 100 mJ / cm ² of ultraviolet rays using an ultraviolet irradiation device (one high-pressure mercury lamp 80 W / cm). Was irradiated and cured to obtain a release film for evaluation (release liner). The release agent composition T, after coating, volatilizes the solvent at 150 ° C. for 1 minute and heat cures to obtain a release film for evaluation.

1) Peeling force: Polyester adhesive tape (Nitto 31B, product name manufactured by Nitto Denko Corporation) was reciprocally pressed with a 2 kg roller on the treated surface of the produced release film, and cut to a width of 20 mm. The film was pulled at 180 ° at a speed of 300 mm / min, and the peeling force was measured.

2) Residual adhesion rate: The tape test piece subjected to the measurement in 1) was reciprocally pressed to a stainless steel plate with a 2 kg roller, pulled at 180 ° at a speed of 300 mm / min, and the peeling force W (N / 20 mm) was measured. did. On the other hand, a polyester adhesive tape without the above-described processing adhered to a stainless steel plate, which measures the force W ₀ (N / 20 mm width) required to peel from the stainless steel plate under the same conditions as above, W for the W ₀ The ratio (W / W ₀ ) (percentage) was determined as the residual adhesion rate.

3) Coating film appearance: After coating and curing the test resin on the substrate, the coating film appearance was visually observed.
“◎”: No problem “○”: Slight whitening (crystallization)
“△”: Whitening, slight roughness “×”: Roughness, bumpy

4) Solvent resistance: Gauze impregnated with methyl ethyl ketone rubs the surface of the produced release film with a load of 1.0 kgf and the gauze reciprocates until the release layer is affected by the solvent and melts or peels off from the substrate. The number of times was measured.

5) Abrasion resistance: The coating film surface of the evaluation release film was strongly rubbed with gauze three times, the peeling force was measured in the same manner as in 1) above, and the peeling force / rubbing film surface was rubbed with gauze. The change in peel force was measured with no peel force. As a result, the case where the peel force change was within ± 10% was evaluated as “◯”, and the case where the peel force change exceeded ± 10% was evaluated as “X”.

Table 1 shows the number of acryloyl groups in one molecule in the component (A) used in the active energy ray-curable release composition A to S prepared above, the equivalent per 1 kg, and the organic isocyanate of component (B). The mass ratio of the component (B) + (C) to the total number of carbon atoms of the component (C) and (A), (B), (C) , (D) is shown collectively. Table 2 summarizes the performance evaluation results of each example and comparative example.

As shown in Tables 1 and 2, Comparative Example 5 in which (meth) acryloyl groups of component (A) are not contained in an average of three or more in one molecule, and (meth) acryloyl groups are averaged in one molecule. In Comparative Example 6, which does not contain three or more and the concentration is less than 8 equivalents per 1 kg, the residual adhesion rate, solvent resistance, and wear resistance are all poor. Moreover, the comparative example 4 from which the carbon number of (C) component remove | deviates from the range of 8-22 is too large as peeling force, and is unsuitable as a peeling liner. In the case of Comparative Examples 1, 2, and 3 where the mass ratio of the component (B) + (C) is outside the range of 0.01 to 0.50, the mass ratio as in Comparative Examples 1 and 2 is less than 0.01. Is not sufficient as a release liner because the peel force is too large, and if the mass ratio is more than 0.50 as in Comparative Example 3, the peel force becomes small, but the mass ratio of the hydroxyl group-containing acrylate becomes small. Solvent resistance and wear resistance are deteriorated, and as a result, the residual adhesion rate is also deteriorated. Furthermore, since the crystallinity of the active energy ray-curable release agent composition is also increased, the coating film is easily whitened and the appearance of the coating film is also deteriorated.
On the other hand, in Examples 1-13 which adjust the number and density | concentration of the (meth) acryloyl group of (A) component, and satisfy | fill the mass ratio of (B) + (C) component, and carbon number of (C) component. Depending on the composition, the peel force can be changed from 100 to 6800 mN / 20 mm, and since the residual adhesive rate is high, there is little influence on the adhesive by the release agent, and it is excellent in solvent resistance and abrasion resistance. Suitable as a composition for a liner, the silicone-free active energy ray-curable release agent composition of the present invention has an excellent release force equivalent to the alkyd-based thermosetting release agent composition of Comparative Example 7, It can be seen that it has a residual adhesion rate, coating film appearance, solvent resistance, and abrasion resistance.

Claims (6)

Hydroxyl group-containing (meth) acrylate (A) having three or more (meth) acryloyl groups on average in a molecule and having a concentration of 8 equivalents or more per 1 kg, at least two or more isocyanates in one molecule Organic isocyanate (B) having a group, one kind selected from those having 8 to 22 carbon atoms, or two or more kinds of higher alcohols (C), and (meth) acryloyl groups on average in three molecules The reaction product ((B) obtained by reacting (B) and (C) comprising ( meth) acrylate (D) not containing a hydroxyl group and having a concentration of 8 equivalents or more per kg. + (C)) and an active energy ray-curable release agent composition for a release liner obtained by further reacting the mixture of ((A) + (D)) with the reactant ((B) + (C)) and the mixture Reaction with the product ((A) + (D)) is ((B) + (C)) / ((A) + (B) + (C) + (D) ) = 0.01- An active energy ray-curable release agent composition for a release liner that has been adjusted to 0.5. The active energy ray-curable release agent composition according to claim 1, wherein the hydroxyl group-containing (meth) acrylate (A) has a structure represented by the general formula (1) or the general formula (2).

(In the general formulas (1) and (2), X ^{1 to} X ¹⁰ each independently represent a (meth) acryloyl group or a hydroxyl group, and at least 3 to 5 of X ^{1 to} X ⁶ are (meta ) Represents an acryloyl group, and three of X ^{7 to} X ¹⁰ represent a (meth) acryloyl group. The active energy ray-curable release agent composition according to claim 1 or 2, wherein the organic isocyanate (B) is an isocyanurate of hexamethylene diisocyanate. The value obtained by subtracting the total hydroxyl group content of the higher alcohol (C) from the total isocyanate group amount of the organic isocyanate (B) is adjusted to be smaller than the total hydroxyl group content of the hydroxyl group-containing (meth) acrylate (A). The active energy ray-curable release agent composition according to any one of claims 1 to 3. The active energy ray-curable release agent composition according to any one of claims 1 to 4 is applied to a substrate so as to have a film thickness of 0.05 to 10 μm in solid content, and irradiated with active energy rays to be cured. A method for forming a coating film. A release liner obtained by the coating film forming method according to claim 5.