JP2017066319A - Releasability adding component, active energy ray curable release agent composition and coated film formation method, release liner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a release liner having light release force and small in release force change before and after conducting a heating treatment with a state contacting with an adhesive.SOLUTION: There is provided a releasability adding component by reacting (meth)acrylate having one or more (meth)acryloyl group and a hydroxyl group as average respectively in a molecule (A), at least one or more kind of organic isocyanate (B) selected from one having 2 isocyanate groups in a molecule and average molecular weight of 300 or less (B) and higher alcohol having 8 to 22 carbon atoms (C) with adjusting mol number of the higher alcohol (C)/mol number of the organic isocyanate (B)=0.1 to 2. There is provided an active energy ray curable release agent composition obtained by mixing the releasability adding component (α) and any active energy ray curable film making component (β) so that content of the higher alcohol (C) is 0.5 to 10% based on total sum of mass of (α) and (β).SELECTED DRAWING: None

Description

  The present invention relates to an active energy ray-curable release agent composition applicable to a release liner used for an adhesive tape or an adhesive sheet for use in electronic materials, a coating film forming method, a release liner using the same, and an active energy ray curable property It is related with the peelability provision component applied to a release agent composition.

  Adhesive tapes and adhesive sheets are used in various industries because of their good handleability and good adhesive properties. 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.

  As performance required for the release agent used in these, not only stable release force but also many other properties can be mentioned. 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 peeling force even after the surface is rubbed and worn.

  Conventional release agents are roughly classified into two types, thermoplastic and thermosetting. Since thermoplastic release agents do not react and cure after coating, they have low solvent resistance and heat resistance after film formation. On the other hand, although a thermosetting release agent is excellent in solvent resistance and heat resistance, it needs to be cured by heating after coating, and has a problem that it cannot be used for a heat-sensitive substrate.

  One of the main resins used for a thermosetting release agent is one that cures an alkyd resin with a crosslinking agent such as melamine (see Patent Document 1 and Patent Document 2). Although the alkyd resin cured with a crosslinking agent such as melamine has high performance, in addition to being a thermosetting resin as described above, a part of formaldehyde used as a raw material is included as an unreacted material. Since formaldehyde is a substance of concern, its use is being suppressed from the viewpoint of environmental problems. For this reason, there has long been a demand for a release agent that does not involve heat and does not contain environmentally hazardous substances.

  In addition, in the case of pressure-sensitive adhesive sheets used for electronic material applications, etc., if the silicone that is the release component moves from the release liner to the pressure-sensitive adhesive sheet side, the transferred silicone will cause failure of electrical and electronic equipment. The non-migration of silicone to the side is also an important issue.

  Thus, 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 desired.

  In addition, as a release agent composition which does not use silicone, does not contain formaldehyde, and cures with active energy rays, it is disclosed in Patent Document 3, for example.

  The present inventors proceeded with the study of the release agent composition, and the technology disclosed in Patent Document 4 was disclosed as an active energy ray-curable release agent composition that does not use silicone as a raw material with a small increase in release force after heat treatment. developed.

JP 2008-156498 A JP 2008-156499 A Japanese Patent No. 5567292 JP 2010-100117 A

  The usage environment of the separator provided with the release layer is often a process in which an adhesive or an adhesive, other moldings, or the like is applied or molded on the release layer, and heat treatment is performed, followed by peeling. The release agent composition described in Patent Document 4 is less changeable than the release agent composition described in Patent Document 3 in the release force after the release layer is molded and subjected to heat treatment, and has good performance. As shown, the peeling force after the heat treatment in the state of contact with the pressure-sensitive adhesive or the adhesive is still largely changed, and it is necessary to study improvement from the viewpoint of heat resistance.

In view of the above problems, the present invention provides:
(1) (Meth) acrylate (A) having one or more (meth) acryloyl groups and hydroxyl groups in one molecule on average, two isocyanate groups in one molecule, and an average molecular weight of 300 or less A peelability-imparting component (α) obtained by reacting at least one organic isocyanate (B) selected from those with a higher alcohol (C) having 12 to 22 carbon atoms, the higher alcohol It provides the peelability-imparting component adjusted and reacted so that the number of moles of (C) / the number of moles of organic isocyanate (B) = 0.1-2.
(2) An active energy ray-curable release agent composition comprising the peelability-imparting component (α) and the active energy ray-curable film-forming component (β) according to (1), The present invention provides an active energy ray-curable release agent composition in which the film component (β) has a structure represented by the general formula (1) or the general formula (2).

（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個以上は、（メタ）アクリロイル基を示し、Ｘ^７〜Ｘ^１０のうち少なくとも３個以上は、（メタ）アクリロイル基を示す。）
（３） 剥離性付与成分中に含まれる高級アルコール（Ｃ）の含有量が、剥離性付与成分（α）と活性エネルギー線硬化性造膜成分（β）の質量総和に対し質量比で０．５〜１０％である（２）に記載の活性エネルギー線硬化性剥離剤組成物を提供するものである。
（４） （メタ）アクリレート（Ａ）が、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、および一般式（３）に示す構造を有する（メタ）アクリレートのいずれかである、（２）または（３）に記載の活性エネルギー線硬化性剥離剤組成物を提供するものである。

(In the general formulas (1) and (2), X ^{1 to} X ¹⁰ each independently represents a (meth) acryloyl group or a hydroxyl group, and at least three of X ^{1 to} X ⁶ are (meth) acryloyl groups. And at least three of X ^{7 to} X ¹⁰ represent a (meth) acryloyl group.)
(3) The content of the higher alcohol (C) contained in the peelability-imparting component is 0.00 by mass ratio with respect to the total mass of the peelability-imparting component (α) and the active energy ray-curable film-forming component (β). The active energy ray-curable release agent composition according to (2), which is 5 to 10%, is provided.
(4) (Meth) acrylate (A) is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and general The active energy ray-curable release agent composition according to (2) or (3), which is any of (meth) acrylates having a structure represented by formula (3).

（一般式（３）中、Ｘ^１１は（メタ）アクリロイル基を表す。 ｋ、ｌはそれぞれ独立して２、３、４のいずれかの整数を示し、ｍ、ｎはそれぞれ独立して０〜３０の整数を表す。）
（５） （２）〜（４）のいずれかに記載の活性エネルギー線硬化性剥離剤組成物を基材に樹脂固形分で０．０５〜１０μｍの膜厚となるよう塗工し、活性エネルギー線を照射し、硬化させる塗膜形成方法である。
（６） （２）〜（４）に記載の活性エネルギー線硬化性剥離剤組成物により得られる剥離ライナーを提供するものである。

(In General Formula (3), X ¹¹ represents a (meth) acryloyl group. K and l each independently represent an integer of 2, 3, or 4, and m and n each independently represents 0 to 0. Represents an integer of 30.)
(5) The active energy ray-curable release agent composition according to any one of (2) to (4) is applied to a base material so as to have a film thickness of 0.05 to 10 μm in terms of resin solids, and active energy This is a method for forming a coating film by irradiating and curing a wire.
(6) A release liner obtained from the active energy ray-curable release agent composition according to (2) to (4) is provided.

  According to the present invention, it is possible to provide an active energy ray-curable release agent composition and a release liner which have a small change in peeling force before and after being subjected to heat treatment in a state of being in contact with the adhesive and the adhesive and do not use silicone as a raw material.

  The active energy ray-curable release agent composition of the present invention comprises (meth) acrylate (A) having at least one (meth) acryloyl group and one hydroxyl group in one molecule, and two isocyanates in one molecule. Releasability obtained by reacting at least one organic isocyanate (B) having a group and an average molecular weight of 300 or less with a higher alcohol (C) having 12 to 22 carbon atoms It is an imparting component (α), which is a peelable imparting component that is adjusted and reacted so that the number of moles of higher alcohol (C) / number of moles of organic isocyanate (B) = 0.1-2.

  The (meth) acrylate (A) used for the peelability-imparting component (α) of the present invention is for urethane reaction with the (meth) acryloyl group, which is an active energy ray-curable functional group, and the organic isocyanate (B). One having at least one hydroxyl group per molecule on average. By reacting the hydroxyl group with the organic isocyanate (B), a (meth) acryloyl group can be incorporated into the peelability-imparting component to impart an active energy ray curing ability. When it does not contain a hydroxyl group and has only a (meth) acryloyl group, it is not incorporated into the skeleton of the peelability-imparting component and acts as an active energy ray-curable film-forming component. In this case, since the active energy ray-curing ability is not imparted to the peelability-imparting component, it does not react with the active energy ray-curable film-forming component, so there is a risk of performance degradation such as solvent resistance and abrasion resistance, Since the reaction product of the organic isocyanate (B) and the higher alcohol (C) has a high melting point of about 100 ° C., a release agent having high heat resistance, which is an object of the present invention, can be provided. On the other hand, when it does not contain a (meth) acryloyl group, it acts as a plasticizer component and may cause a decrease in heat resistance.

  The organic isocyanate (B) used in the active energy ray-curable release agent composition of the present invention has two isocyanate groups in one molecule and has an average molecular weight of 300 or less. Similar to (meth) acrylate (A), the more complex the structure of the peelability-imparting component (α), the better the compatibility with other resins and the lowering of the melting point of the peelability-imparting component. It becomes a factor of sex decline. In particular, the tendency of the organic isocyanate (B) that directly reacts with the higher alcohol (C) is more remarkable. If higher heat resistance is desired, at least one selected from hexamethylene diisocyanate or diphenylmethane diisocyanate is preferred.

  The average molecular weight of the organic isocyanate (B) of the present invention is 300 or less, preferably 168 to 264. Specifically, hexamethylene diisocyanate, lysine diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, and tolidine diisocyanate are suitable. Among these, hexamethylene diisocyanate (molecular weight 168) and diphenylmethane diisocyanate (molecular weight 250) are particularly preferred in view of cost and good handleability.

  Since the higher alcohol (C) having 8 to 22 carbon atoms used in the active energy ray-curable release agent composition of the present invention is reacted with the organic isocyanate (B), at least one hydroxyl group is contained in one molecule. have. If the carbon number is 8-22, good peeling force can be expressed. The higher alcohol (C) is a saturated higher alcohol, especially having 18 or more carbon atoms, and a straight-chain alcohol has a lighter (smaller) release force and a user-friendly release agent composition that is delighted by customers. Unsaturated higher alcohols and branched higher alcohols can also be used, but when these are used, the peel force is heavier (larger) than that using linear saturated higher alcohols. Since the crystallinity of the active energy ray-curable release agent composition is lowered, a smooth coating film having high transparency can be obtained. When importance is attached to the appearance of the coating film, an unsaturated or branched type higher alcohol is used. That is, it is a preferable aspect to select a higher alcohol according to the use of the release agent composition.

  Examples of linear higher alcohols include octyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetanol, cetostearyl alcohol, stearyl alcohol, behenyl alcohol, and oleyl as linear unsaturated higher alcohols. Examples of branched higher alcohols include alcohols such as 2-hexyldecanol, 2-octyldodecanol, and 2-decyltetradodecanol.

  Commercially available products can be used as the higher alcohol (C) having 8 to 22 carbon atoms suitable for the present invention. 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 2473, Calcoal 2463, Calcoal 2455, Calcoal 2450, Calcoal 4 50, Calcoal 6870, Calcoal 6850, Calcoal 8688, Calcoal 8665, Calcoal 80-80 (trade name of Kao Corporation), linear unsaturated higher alcohols include Ricacol 60B, Ricacol 70B, Ricacol 75BJ, Ricacol 85BJ, Rica Call 90B, Rica Call 90BR, Rica Call 90BHR, Rica Call 110BJ, Angkor Cole 50A, Angers Cole 60AN, Angers Cole 70AN, Angers Cole 80AN, Angers Cole 85AN, Angers Cole 90AN, Angers Cole 90NR, Angers Cole 90NHR Product names), NJ Coal 160BR, NJ Coal 200A, NJ Coal 240A (New Japan) Of trade names Co., Ltd.) and the like.

  When (meth) acrylate (A), organic isocyanate (B), and higher alcohol (C) are reacted, the number of moles of higher alcohol (C) / number of moles of organic isocyanate (B) = 0.1-2. When adjusted to, stable peeling force and heat resistance can be obtained. If the higher alcohol (C) is 0.1 or more, a stable peeling force can be obtained and heat resistance is also good. On the other hand, when the number of moles of the higher alcohol (C) / number of moles of the organic isocyanate (B) exceeds 2, the excess remains without reacting with the organic isocyanate (B). The reactant may reduce heat resistance.

  Next, the present invention is an active energy ray-curable release agent composition comprising an active energy ray-curable peelability-imparting component (α) and an active energy ray-curable film-forming component (β), which comprises an active energy ray The curable film-forming component (β) is an active energy ray-curable release agent composition having a structure represented by the general formula (1) or the general formula (2).

（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個以上は、（メタ）アクリロイル基を示し、Ｘ^７〜Ｘ^１０のうち少なくとも３個以上は、（メタ）アクリロイル基を示す。）
本発明の活性エネルギー線硬化性剥離剤組成物に使用される活性エネルギー線造膜成分（β）は、活性エネルギー線硬化性の官能基を有していれば、他は特に制限はない。酸素阻害の影響を受け難い数μｍ以上の厚膜、ないしは硬化成膜させた後、変形させる用途である程度の柔軟性が必要となる場合は、活性エネルギー線硬化性官能基等量が低い活性エネルギー線硬化性樹脂を用い、逆に酸素阻害を受け易い薄膜または塗工成膜から使用されるまでほぼ平面で取り扱われる大きな変形を伴わない用途では、上記一般式（１）または一般式（２）に代表される良好な硬化性を持つ高硬度の材料が好ましい。

(In the general formulas (1) and (2), X ^{1 to} X ¹⁰ each independently represents a (meth) acryloyl group or a hydroxyl group, and at least three of X ^{1 to} X ⁶ are (meth) acryloyl groups. And at least three of X ^{7 to} X ¹⁰ represent a (meth) acryloyl group.)
The active energy ray film-forming component (β) used in the active energy ray-curable release agent composition of the present invention is not particularly limited as long as it has an active energy ray-curable functional group. Active energy ray-curable functional group with low equivalent energy when thick flexibility of several μm or more that is difficult to be affected by oxygen inhibition, or when a certain degree of flexibility is required for deformation after film formation For applications that use a linear curable resin and are not subject to large deformations that are handled almost flatly until it is used from a thin film or coating film that is susceptible to oxygen inhibition, the above general formula (1) or general formula (2) A high-hardness material having good curability represented by

  If higher (good) curability is desired, it is desirable to use an acrylate that does not contain a methacryloyl group. Among them, dipentaerythritol monoacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol monoacrylate, pentaerythritol diacrylate, penta It is a mixture of two or more selected from erythritol triacrylate and pentaerythritol pentaacrylate, and contains acryloyl groups on average three or more per molecule and the concentration is adjusted to 8 equivalents or more per kg. Things are desirable.

  In particular, as the active energy ray-curable film-forming component (β), one or two selected from dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate More than species are preferred.

  Generally, the (meth) acrylate (A) and the active energy ray-curable film-increasing component (β) used in the active energy ray-curable release agent composition of the present invention are each one type or two or more types ( It consists of a meth) acrylate compound. Therefore, the hydroxyl group-containing (meth) acrylate (A) and the active energy ray-curable film-forming component (β) are each a mixture or a single substance. Examples of the hydroxyl group-containing (meth) acrylate (A) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Glycerin mono (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid, 2-methacryloyloxyethyl-2-hydroxy Examples thereof include propyl phthalate, 2- (meth) acryloyloxyethyl-acid phosphate, and epoxy (meth) acrylate obtained by addition reaction of (meth) acrylic acid to the epoxy group of the epoxy resin. It is. Furthermore, when it is desired to adjust the peeling force, epoxy acrylate such as 2-hydroxy-3-phenoxypropyl (meth) acrylate, (meth) acrylic acid adduct of bisphenol A to glycidyl ether, and the following general formula (3) Those having an aromatic ring, ethylene oxide, propylene oxide, or butylene oxide skeleton in the structure, such as (meth) acrylate having a structure, are preferred.

  However, if light peeling force or better heat resistance is desired, among the above hydroxyl group-containing (meth) acrylates, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meta) ) Acrylate and 4-hydroxybutyl (meth) acrylate are more preferred. The peelability-imparting component develops peelability and heat resistance by being oriented at the release layer interface when the release layer is formed. The more complicated the structure of the peelability-imparting component is, the better the compatibility with other organic resins and the lowering of the melting point, so that the peel force becomes unstable and the heat resistance may be lowered.

  In the active energy ray-curable release agent composition of the present invention, the content of the higher alcohol (C) contained in the peelability-imparting component (α) is such that the peelability-imparting component (α) and the active energy ray-curable film-forming composition. The mass ratio is 0.5 to 10% with respect to the total mass of the component (β). Preferably it is 1 to 5%, particularly preferably 1.5 to 2%. If the content of the higher alcohol (C) is 0.5% or more, a stable peeling force can be obtained. On the other hand, even if it exceeds 10%, the tendency to increase the peel strength including heat resistance cannot be confirmed (because the performance is saturated), which is not only effective, but also increases the content of higher alcohol (C), so that the active energy The content of the wire curable film-forming component (β) is decreased, which may affect the curing characteristics, which is not preferable.

  Next, in the curable release agent composition of the present invention, (meth) acrylate (A) is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4 -An active energy ray-curable release agent composition which is either hydroxybutyl (meth) acrylate or (meth) acrylate having a structure represented by the general formula (3).

（一般式（３）中、Ｘ^１１は（メタ）アクリロイル基を表す。ｋ、ｌはそれぞれ独立して２、３、４の何れかの整数を示し、ｍ、ｎはそれぞれ独立して０〜３０の整数を表す。）

(In General Formula (3), X ¹¹ represents a (meth) acryloyl group. K and l each independently represent an integer of 2, 3, or 4, and m and n each independently represents 0 to 0. Represents an integer of 30.)

  Examples of the active energy ray in the present invention include known and commonly used ones such as electron beam, α ray, β ray, γ ray, infrared ray, visible ray, and ultraviolet ray. Among them, research on electron beams and ultraviolet rays is relatively advanced, and in particular, ultraviolet rays 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 electron beam is used. In addition, when making it harden | cure with an ultraviolet-ray, it is necessary to mix a photoinitiator with an active energy ray hardening release agent composition.

  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 or a mixture of two or more known ones may be used. Can do. In particular, 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-one is particularly desirable. Further, the blending amount of the photopolymerization initiator is desirably 3 to 15% by mass with respect to the resin solid content of the active energy ray-curable release agent composition from the viewpoints of curability and cost.

  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 an active energy ray-curable release agent composition. It is desirable that the resin solid content is in the range of 1 to 60% by mass.

  The active energy ray-curable release agent composition of the present invention is applied to a substrate by coating (coating), in the case of a solvent system, heating to volatilize the solvent and then irradiating the active energy ray to cure. A film (release agent layer) can be formed. The heating temperature is generally 50 to 100 ° C. although it depends on the film thickness and the diluent solvent. The coating film (release agent layer) can be used as a release liner, and is applied so as to have a film thickness of 0.05 to 10 μm in terms of resin solid content when applied to a substrate. Furthermore, the film thickness is preferably 0.1 to 3 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 coat. Paper base materials, such as paper, are mentioned.

  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 indicate parts by mass and mass% unless otherwise specified.

[Production Example 1]
In a flask equipped with a stirrer and a thermometer, 2,204 parts of BHEA (trade name, 2-hydroxyethyl acrylate, manufactured by Nippon Shokubai Co., Ltd.) as a hydroxyl group-containing (meth) acrylate, and Millionate MT as an organic isocyanate (B) 5,000 parts (trade name, diphenylmethane diisocyanate manufactured by Nippon Polyurethane Co., Ltd.) and 270 parts of Conol 30SS (trade name, Stearyl Alcohol manufactured by Shin Nippon Chemical Co., Ltd.) as higher alcohol (C) were added and the temperature was raised to 100 ° C. The mixture was warmed and allowed to react for 7 hours, and as a result of IR measurement, it was confirmed that the isocyanate group had disappeared. The number of moles of higher alcohol (C) / number of moles of organic isocyanate (B) was 0.05.

[Production Example 2]
In a flask having the same equipment as in Production Example 1, as hydroxyl-containing (meth) acrylate, BHEA (trade name, 2-hydroxyethyl acrylate, manufactured by Nippon Shokubai Co., Ltd.), 1044 parts, as organic isocyanate (B) 2,500 parts of Millionate MT (trade name, manufactured by Nippon Polyurethane Co., Ltd., diphenylmethane diisocyanate) and 270 parts of Konol 30SS (trade name, manufactured by Shin Nippon Chemical Co., Ltd., stearyl alcohol) as higher alcohol (C) were charged at 100 ° C. The mixture was heated up to 7 hours and reacted for 7 hours, and as a result of IR measurement, it was confirmed that the isocyanate group had disappeared. The number of moles of higher alcohol (C) / number of moles of organic isocyanate (B) was 0.1.

[Production Example 3]
In a flask having the same equipment as in Production Example 1, 580 parts of BHEA (trade name, 2-hydroxyethyl acrylate, manufactured by Nippon Shokubai Co., Ltd.) as hydroxyl-containing (meth) acrylate, and HDI (organic isocyanate (B) as HDI ( 504 parts of Nippon Polyurethane Co., Ltd. trade name, hexamethylene diisocyanate) and 270 parts of Conol 30SS (trade name, Stearyl Alcohol made by Nippon Chemical Co., Ltd.) as higher alcohol (C) are charged and heated to 100 ° C. The mixture was kept warm for 7 hours to react, and as a result of IR measurement, it was confirmed that the isocyanate group had disappeared. The number of moles of higher alcohol (C) / number of moles of organic isocyanate (B) = 0.33.

[Production Example 4]
In a flask equipped with the same equipment as in Production Example 1, 250 parts of Millionate MT (trade name, diphenylmethane diisocyanate manufactured by Nippon Polyurethane Co., Ltd.) is used as the organic isocyanate (B), and Conol 30SS (New Nippon Rika Co., Ltd.) as the higher alcohol (C). 540 parts of product name (stearyl alcohol, manufactured by Co., Ltd.), heated up to 100 ° C. and kept for 7 hours to react, and confirmed that the isocyanate group disappeared as a result of IR measurement. Obtained. The number of moles of higher alcohol (C) / number of moles of organic isocyanate (B) = 2.

[Production Example 5]
In a flask equipped with the same equipment as in Production Example 1, 250 parts of Millionate MT (trade name, diphenylmethane diisocyanate manufactured by Nippon Polyurethane Co., Ltd.) is used as the organic isocyanate (B), and Conol 30SS (New Nippon Rika Co., Ltd.) as the higher alcohol (C). 810 parts of a product name (stearyl alcohol, manufactured by Co., Ltd.), heated to 100 ° C. and incubated for 7 hours to be reacted. As a result of IR measurement, it was confirmed that the isocyanate group had disappeared. Obtained. The number of moles of higher alcohol (C) / number of moles of organic isocyanate (B) was 3.

[Production Example 6]
In a flask equipped with the same equipment as in Production Example 1, 580 parts of BHEA (trade name, 2-hydroxyethyl acrylate, manufactured by Nippon Shokubai Co., Ltd.) as the hydroxyl group-containing (meth) acrylate, and Sumijoule as the organic isocyanate (B) Charged 1,008 parts of N3400 (trade name made by Sumika Bayer Urethane Co., Ltd., uretdione of hexamethylene diisocyanate), and 270 parts of Conol 30SS (trade name, Nippon Steel Chemical Co., Ltd., stearyl alcohol) as higher alcohol (C) The temperature was raised to 100 ° C. and kept for 7 hours to react, and as a result of IR measurement, it was confirmed that the isocyanate group had disappeared. The number of moles of higher alcohol (C) / number of moles of organic isocyanate (B) = 0.33.

[Production Example 7]
In a flask equipped with the same equipment as in Production Example 1, 232 parts BHEA (trade name, 2-hydroxyethyl acrylate, manufactured by Nippon Shokubai Co., Ltd.) as a hydroxyl group-containing (meth) acrylate, and Sumijoule as organic isocyanate (B) 504 parts of N3300 (trade name, manufactured by Sumika Bayer Urethane Co., Ltd., isocyanurate of hexamethylene diisocyanate), and 270 parts of Conol 30SS (trade name, manufactured by Shin Nippon Chemical Co., Ltd., stearyl alcohol) as higher alcohol (C) Then, the temperature was raised to 100 ° C., and the reaction was carried out by keeping the temperature for 7 hours. As a result of IR measurement, it was confirmed that the isocyanate group had disappeared. The number of moles of higher alcohol (C) / number of moles of organic isocyanate (B) = 1.

[Example 1]
In a flask equipped with the same equipment as in Production Example 1, 212 parts of the peelability-imparting component 2 obtained in Production Example 2 and KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as the active energy ray-curable film-forming component (β) Product name, 788 parts of a mixture of pentaacrylate and hexaacrylate having the structure shown in the general formula (1)), Irgacure 184 (a photopolymerization initiator manufactured by BASF Japan Ltd., 1-hydroxy-cyclohexyl-phenyl-ketone) 100 parts was charged and heated to 100 ° C. and mixed for 1 hour to obtain an active energy ray-curable release agent composition A. The content of the higher alcohol (C) contained in the active energy ray-curable release agent was 1.5%.

[Example 2]
In a flask equipped with the same equipment as in Production Example 1, 25 parts of the peelability-imparting component 3 obtained in Production Example 3 and NK Economer A-PG5054E (Shin Nakamura Kagaku) as the active energy ray-curable film-forming component (β) 975 parts of trade name, polyglycerin polyethylene glycol polyacrylate), 100 parts of Irgacure 184 (BASF Japan photopolymerization initiator, 1-hydroxy-cyclohexyl-phenyl-ketone) was charged to 100 ° C. After heating, the mixture was mixed for 1 hour to obtain an active energy ray-curable release agent composition B. The content of the higher alcohol (C) contained in the active energy ray-curable release agent was 0.5%.

[Example 3]
In a flask having the same equipment as in Production Example 1, 75 parts of the peelability-imparting component 3 obtained in Production Example 3 and KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as the active energy ray-curable film-forming component (β) 925 parts of a product name, a mixture of pentaacrylate and hexaacrylate having the structure shown in the general formula (1)), Irgacure 184 (a photopolymerization initiator manufactured by BASF Japan Ltd., 1-hydroxy-cyclohexyl-phenyl-ketone) 100 parts was charged and heated to 100 ° C. and mixed for 1 hour to obtain an active energy ray-curable release agent composition C. The content of the higher alcohol (C) contained in the active energy ray-curable release agent was 1.5%.

[Example 4]
In a flask equipped with the same equipment as in Production Example 1, 501 parts of the peelability-imparting component 3 obtained in Production Example 3 was used as an active energy ray-curable film-forming component (β). 499 parts of trade name, polyester urethane acrylate), Irgacure 184 (BASF Japan Ltd. photopolymerization initiator, 1-hydroxy-cyclohexyl-phenyl-ketone) was charged in 100 parts, and the temperature was raised to 100 ° C. for 1 hour. The active energy ray-curable release agent composition D was obtained by mixing. The content of the higher alcohol (C) contained in the active energy ray-curable release agent was 10%.

[Example 5]
In a flask having the same equipment as in Production Example 1, 22 parts of the peelability-imparting component 4 obtained in Production Example 4, and KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as the active energy ray-curable film-forming component (β) 978 parts of a product name, a mixture of pentaacrylate and hexaacrylate having the structure shown in the general formula (1)), Irgacure 184 (a photopolymerization initiator manufactured by BASF Japan Ltd., 1-hydroxy-cyclohexyl-phenyl-ketone) 100 parts were charged and heated to 100 ° C. and mixed for 1 hour to obtain an active energy ray-curable release agent composition E. The content of the higher alcohol (C) contained in the active energy ray-curable release agent was 1.5%.

[Example 6]
In a flask equipped with the same equipment as in Production Example 1, 750 parts of the peelability-imparting component 3 obtained in Production Example 3 and KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as the active energy ray-curable film-forming component (β) , 250 parts of a mixture of pentaacrylate and hexaacrylate having the structure shown in the general formula (1)), Irgacure 184 (a photopolymerization initiator manufactured by BASF Japan Ltd., 1-hydroxy-cyclohexyl-phenyl-ketone) 100 parts was charged and heated to 100 ° C. and mixed for 1 hour to obtain an active energy ray-curable release agent composition F. The content of the higher alcohol (C) contained in the active energy ray-curable release agent was 15%.

[Comparative Example 1]
In a flask having the same equipment as in Production Example 1, 22 parts of the peelability-imparting component 4 obtained in Production Example 4, and KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as the active energy ray-curable film-forming component (β) 978 parts of a product name, a mixture of pentaacrylate and hexaacrylate having the structure shown in the general formula (1)), Irgacure 184 (a photopolymerization initiator manufactured by BASF Japan Ltd., 1-hydroxy-cyclohexyl-phenyl-ketone) 100 parts was charged and heated to 100 ° C. and mixed for 1 hour to obtain an active energy ray-curable release agent composition G. The content of the higher alcohol (C) contained in the active energy ray-curable release agent was 1.5%.

[Comparative Example 2]
In a flask having the same equipment as in Production Example 1, 20 parts of the peelability-imparting component 5 obtained in Production Example 5, and KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as the active energy ray-curable film-forming component (β) 980 parts, a mixture of pentaacrylate and hexaacrylate having the structure shown in the general formula (1), Irgacure 184 (a photopolymerization initiator manufactured by BASF Japan Ltd., 1-hydroxy-cyclohexyl-phenyl-ketone) 100 parts was charged and heated to 100 ° C. and mixed for 1 hour to obtain an active energy ray-curable release agent composition H. The content of the higher alcohol (C) contained in the active energy ray-curable release agent was 1.5%.

[Comparative Example 3]
In a flask having the same equipment as in Production Example 1, 138 parts of the peelability-imparting component 6 obtained in Production Example 6 and KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as the active energy ray-curable film-forming component (β) , 862 parts Irgacure 184 (a photopolymerization initiator manufactured by BASF Japan Ltd., 1-hydroxy-cyclohexyl-phenyl-ketone) 100 parts was charged and heated to 100 ° C. and mixed for 1 hour to obtain an active energy ray-curable release agent composition I. The content of higher alcohol (C) contained in the active energy ray-curable release agent was 2%.

[Comparative Example 4]
In a flask equipped with the same equipment as in Production Example 1, 75 parts of the peelability-imparting component 7 obtained in Production Example 7 and KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as the active energy ray-curable film-forming component (β) 925 parts of a product name, a mixture of pentaacrylate and hexaacrylate having the structure shown in the general formula (1)), Irgacure 184 (a photopolymerization initiator manufactured by BASF Japan Ltd., 1-hydroxy-cyclohexyl-phenyl-ketone) 100 parts was charged and heated to 100 ° C. and mixed for 1 hour to obtain an active energy ray-curable release agent composition J. The content of higher alcohol (C) contained in the active energy ray-curable release agent was 2%.

[Comparative Example 5]
To a flask equipped with the same equipment as in Production Example 1, 1,000 parts of KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., a mixture of pentaacrylate and hexaacrylate having a structure represented by the general formula (1)), Irgacure 184 (a photopolymerization initiator manufactured by BASF Japan Ltd., 1-hydroxy-cyclohexyl-phenyl-ketone) was charged with 100 parts, heated to 100 ° C., mixed for 1 hour, and active energy ray-curable release agent composition. K was obtained.

[Creation of release film for evaluation]
A release film for evaluation was produced by the following method.

Each test resin (active energy ray curable release) adjusted to an arbitrary concentration with a solvent was used as an untreated polyethylene terephthalate (hereinafter abbreviated as PET) film having a thickness of 100 μm as a base material for the release film for evaluation. After the film formation, the agent compositions A to K) were coated so that the dry film thickness was 0.30 μm. Next, the film was dried by heating at a temperature of 80 ° C. for 1 minute, and cured by irradiating with 200 mJ / cm ² of ultraviolet rays using an ultraviolet irradiation device (one high-pressure mercury lamp 80 W / cm) to obtain a release film (release liner) for evaluation. It was.

[Peeling force]
The peeling force was measured by the following method.

  Using the prepared release films for evaluation and polyester adhesive tapes (Nitto 31B, trade name of Nitto Denko Corporation), three types of peel forces were measured according to the following conditions. In all the peel strength evaluations, the pressure-sensitive adhesive tape was reciprocally pressed with a 2 kg roller, pulled at 180 ° at a test width of 25 mm and a speed of 300 mm / min, and the peel strength was measured.

Peeling force (1): Measured after pressure-sensitive adhesive tape is pressure-bonded to release film and left at room temperature for 30 minutes Peeling force (2): Pressure-sensitive adhesive tape is pressure-bonded to release film cured at 70 ° C. for 20 hours and then left at room temperature for 30 minutes Measured after peeling strength (3): measured after pressure-sensitive adhesive tape is applied to the release film and then cured at 70 ° C. for 20 hours

  The molecular weight of the component (B) in the release components 1 to 7 used in the active energy ray-curable release agent compositions A to K prepared in Table 1, (B) the components (B) and (C) used for the production The (C) component content with respect to the total mass ratio of (α) and (β), the material name of the (β) component, and the performance evaluation results of each example and comparative example are collectively shown.

* (Β) Abbreviation of material name DPHA: Trade name KAYARAD DPHA (dipentaerythritol penta / hexaacrylate)
5054E: Product name NK Economer 5054E (polyglycerin polyethylene glycol polyacrylate)
TL2300: Product name Teslac 2300 (polyester urethane acrylate)

  As shown in Table 1, Comparative Example 1 and Comparative Example 2 in which the (C) / (B) mol ratio is outside the scope of the present invention, and Comparative Example 3 in which the molecular weight of the component (B) is outside the scope of the present invention, In Comparative Example 4, although peeling force (1) and (2) exhibit light peeling force as compared with Comparative Example 5 which does not include the peelability-imparting component (α), peeling after heating in a state where the adhesive tape is bonded In the evaluation of the peeling force (3), the heavy peeling changes greatly, and the heat resistance is not sufficient.

  On the other hand, each sample of Examples 1-6 whose (B) component molecular weight, (C) / (B) mol ratio, and (C) component content are within the scope of the present invention is an active energy ray-curable film-increasing component. Regardless of the type of (β), all of the peel forces (1) to (3) exhibit a light peel force. When the group of the example and the group of the comparative example are compared in the peel force (3), the difference is clear. Note that the sample of Example 6 in which the content of the higher alcohol (C) is 15% is different from the sample of Example 4 in which the content of the higher alcohol (C) is 10%, and the peeling force (1) (2) (3 ) Are equivalent, and even when the content of the higher alcohol (C) exceeds 10%, it is understood that there is no change in these characteristics.

  From these results, the active energy ray-curable release agent composition of the present invention has a light release force and good heat resistance in a state where the adhesive is in contact with it. It turns out that it is more suitable as a composition for release liners including a liner.

Claims (6)

From (meth) acrylate (A) having one or more (meth) acryloyl groups and one hydroxyl group in one molecule on average, having two isocyanate groups in one molecule, and having an average molecular weight of 300 or less A peelability-imparting component (α) obtained by reacting at least one selected organic isocyanate (B) with a higher alcohol (C) having 8 to 22 carbon atoms,
A peelability-imparting component prepared and reacted so that the number of moles of higher alcohol (C) / number of moles of organic isocyanate (B) = 0.1-2.   The content of the higher alcohol (C) contained in the peelability-imparting component is 0.5 to 0.5 by mass ratio with respect to the total mass of the peelability-imparting component (α) and the active energy ray-curable film-forming component (β). The active energy ray-curable release agent composition according to claim 1, which is 10%. An active energy ray-curable release agent composition comprising the peelability-imparting component (α) according to claim 1 and an active energy ray-curable film-forming component (β), wherein the active energy ray-curable film-forming component ( An active energy ray-curable release agent composition in which β) has a structure represented by general formula (1) or general formula (2).

(In the general formulas (1) and (2), X ^{1 to} X ¹⁰ each independently represents a (meth) acryloyl group or a hydroxyl group, and at least three of X ^{1 to} X ⁶ are (meth) acryloyl groups. And at least three of X ^{7 to} X ¹⁰ represent a (meth) acryloyl group.) (Meth) acrylate (A) is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and general formula (3) The active energy ray-curable release agent composition according to claim 2, which is any one of (meth) acrylates having a structure represented by:

(In General Formula (3), X ¹¹ represents a (meth) acryloyl group. K and l each independently represent an integer of 2, 3, or 4, and m and n each independently represents 0 to 0. Represents an integer of 30.)   The active energy ray-curable release agent composition according to any one of claims 2 to 4 is applied to a substrate so as to have a film thickness of 0.05 to 10 μm in resin solids, and irradiated with active energy rays. A method for forming a coating film to be cured.   A release liner obtained by the active energy ray-curable release agent composition according to claim 2.