JP2019108456A - Active energy ray-curable release agent composition, release agent for carrier, and coating film formation method and release liner formation method each using the same release agent - Google Patents

Abstract

To provide an active energy ray-curable release agent composition that has both good appearance of a coated surface and a light peel force and is suitable for a carrier in a manufacturing process for the manufacture of high-definition electronic components, and the like, to provide a release agent for a carrier and to provide a coating film formation method and a release liner formation method each using the release agent.SOLUTION: The active energy ray-curable release agent composition for a release liner includes a reaction product of (A) a hydroxyl group-containing (meth)acrylate having three or more (meth)acryloyl groups on average in one molecule and having the concentration of 8 equivalent or more per 1 kg, (B) an isocyanurate having at least two isocyanate groups in one molecule and (C) a straight-chain dimethyl organopolysiloxane having at least one hydroxyl group in one molecule and having a number average molecular weight of 1,000 to 5,000; has, by mass ratio, (C)/((A)+(B)+(C))=0.002 to 0.009; and is used by forming a cured coating film so that the film thickness thereof is 0.5 to 2 μm.SELECTED DRAWING: None

Description

  The present invention relates to an active energy ray-curable release agent composition, a release agent for carriers, a method for forming a coating film using the same, and a method for forming a release liner, which have excellent release force and coated surface appearance, adhesion for electronic material applications The present invention relates to an active energy ray-curable release agent composition applicable to a release liner used for a tape or an adhesive sheet, a release agent for carrier, and a method for forming a coating / release liner using the same.

  Pressure-sensitive adhesive tapes and pressure-sensitive adhesive sheets are used in various industries because of their good handleability and good adhesive properties. Also in the electronic device field, many adhesive tapes and adhesive sheets are used for adhesion of various members. The release liners of the pressure-sensitive adhesive tape and the pressure-sensitive adhesive sheet are coated with various release agents in order to impart a targeted release force. In addition to the use as a protective film of an adhesive, it is also essential as a manufacturing process carrier used when manufacturing electronic material parts.

  The performance required for the release agent used for these includes not only a stable peel force but also many other performances. For example, coating appropriate for obtaining a smooth surface, residual adhesion after using a release agent, abrasion resistance that does not impair the peeling force even after the surface is rubbed and abrasion, and peeling of a solvent-based adhesive In the case of coating on a sheet and drying by heat, solvent resistance is required. Furthermore, in the case of a pressure-sensitive adhesive sheet used for electronic materials and the like, if silicone which is a release component is transferred from the release liner to the pressure-sensitive adhesive sheet side, this silicone causes the failure of electric and electronic devices Is also one of the important performances.

  Conventional release agents are roughly classified into thermoplastic and thermosetting resins. Thermoplastic resins are not reacted and cured after coating, so that their solvent resistance and heat resistance after film formation are low. On the other hand, although thermosetting resins are excellent in solvent resistance, heat resistance, and the like, they are premised to be heat-cured after coating, and therefore have the disadvantage that they can not be used on thin substrates that are weak in heat. Further, 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).

  An alkyd resin cured with a crosslinking agent such as melamine has high performance, but in addition to the thermosetting mentioned above, it also contains some unreacted formaldehyde as a raw material, which causes environmental problems. It is being reconsidered from the viewpoint of For this reason, there is a long-felt need for release agents that are heat-free curing systems and do not contain environmental contaminants.

  The present inventors diligently investigate in consideration of the above object, and mix a photopolymerization initiator to a resin obtained by reacting a hydroxyl group-containing (meth) acrylate, an organic isocyanate, and a linear dimethyl organopolysiloxane having a hydroxyl group. It has been found that an active energy ray-curable release agent composition having good peel strength, residual adhesion rate, coating suitability, solvent resistance, abrasion resistance, non-migratory property of silicone can be obtained (patent document 3).

JP, 2008-156498, A JP 2008-156499 A Unexamined-Japanese-Patent No. 2010-265403

However, with the recent trend toward higher performance and miniaturization of electronic material devices, there is a tendency for higher definition of electronic material parts used for the same to be required year by year. Therefore, not only the lightness of the peeling force but also the smoothness of the surface of the peeling layer is required at a high level, and the carrier used in manufacturing the member is required to have a high level of smoothness. It has not been possible to meet the demand.
The present invention uses an active energy ray-curable release agent composition suitable for use as a production process carrier for producing high-definition electronic components, which has both a good coated surface appearance and a light peel strength, a release agent for carrier, and the like The present invention provides a method of forming a coating film and a method of forming a release liner.

As a result of examining the release agent for forming a higher smooth release layer while maintaining a light release force, the inventors limited the molecular weight range and content of dimethylorganopolysiloxane in addition to the findings obtained so far. By using isocyanurate as the organic isocyanate, it has been found that it is possible to achieve both a good coated surface appearance and a light peel strength which have never been achieved.
The present invention has a hydroxyl group-containing (meth) acrylate (A) having one or more [1] (meth) acryloyl groups on average in one molecule and a concentration of at least 8 equivalents per kg, in one molecule Isocyanurate (B) having at least two or more isocyanate groups, linear dimethylorganopolysiloxane having a number average molecular weight of 1,000 to 5,000, having at least one or more hydroxyl groups in one molecule (B) An active energy ray-curable release agent composition containing a reactant of C), wherein the content of the component (C) is a mass ratio of (C) / ((A) + (B) + (C)) = 0 .002 to 0.009, the active energy ray-curable release agent composition is applied to a substrate, and the film thickness of a cured coating film irradiated with active energy rays is formed to be 0.5 to 2 .mu.m Active energy for release liners used A ghee ray curable release composition.
Further, the present invention is the activity according to the above [1], wherein the hydroxyl group-containing (meth) acrylate (A) of the [2] component (A) has a structure shown in the general formula (1) or the general formula (2) It is an energy ray curable release agent 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。）
また、本発明は、［３］上記（Ｃ）成分のジメチルオルガノポリシロキサン（Ｃ）が、一般式（３）、（４）、（５）に示す構造のうち、少なくとも一種以上を使用してなる上記［１］又は［２］に記載の活性エネルギー線硬化性剥離剤組成物である。

(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 three or more of X ^{1 to} X ⁶ are (meth) acryloyl groups And at least three or more of X ^{7 to} X ¹⁰ indicate (meth) acryloyl groups.
In the present invention, [3] at least one or more of the structures represented by the general formulas (3), (4) and (5) is used as the dimethylorganopolysiloxane (C) of the component (C). It is an active energy ray curable release agent composition as described in said [1] or [2] which becomes.

（一般式（３）、（４）、（５）中、Ｒ^１、Ｒ^３、Ｒ^６は、それぞれ独立にアルキル基又はアルキレンエーテル基を、Ｒ^２、Ｒ^４、Ｒ^５、Ｒ^７は、それぞれ独立にアルキレン基又はアルキレンエーテル基を示す。ｎは、正の整数を示す。）

(In the general formulas (3), (4) and (5), R ¹ , R ^{3 and} R ⁶ each independently represent an alkyl group or an alkylene ether group, and R ² , R ⁴ , R ⁵ and R ^{7 each} represent Each independently represents an alkylene group or an alkylene ether group, n represents a positive integer.

Further, the present invention is the active energy ray according to any one of the above [1] to [3], wherein the isocyanurate (B) of the component (B) is an isocyanurate composed of hexamethylene diisocyanate. It is a curable release agent composition.
In the present invention, the total amount of isocyanate groups possessed by the isocyanurate (B) having at least two or more isocyanate groups in one molecule of the component (B) of the present invention (5) is The value obtained by subtracting the total amount of hydroxyl groups contained in the siloxane (C) is adjusted to be smaller than the total amount of hydroxyl groups contained in the hydroxyl group-containing (meth) acrylate (A) of the component (A). It is an active energy ray curable release agent composition as described in any one of 4].
The present invention is also a release agent for a manufacturing process of an electronic material component obtained by curing the active energy ray-curable release agent composition according to any one of [6] [1] to [5].
The present invention also provides a film thickness after curing of the active energy ray curable release agent composition according to any one of [7] [1] to [5] above as 0.5 to 2 μm. It coats so that it may become, It is the coating film formation method which irradiates an active energy ray and hardens.
The present invention is also a release liner formation method formed in the same manner as the coating film formation method described in [8] above [7].

  According to the present invention, it is possible to obtain an active energy ray-curable release agent composition that achieves both a good coated surface appearance (high smoothness of the release layer surface) and a light release force, a carrier release agent and a release liner. By using such an active energy ray-curable release agent composition and a release liner, the product using the production process carrier can be more easily obtained with higher accuracy, and the coated product can be thin film coated.

  In the present invention, at least two hydroxyl group-containing (meth) acrylates (A) having at least three (meth) acryloyl groups in one molecule and at a concentration of at least 8 equivalents per kg are contained in one molecule. Reactant of isocyanurate (B) having at least one isocyanate group, and linear dimethylorganopolysiloxane (C) having a number average molecular weight of 1,000 to 5,000 having at least one hydroxyl group in one molecule And a photopolymerization initiator as required, and the mass ratio is adjusted to be (C) / ((A) + (B) + (C)) = 0.002 to 0.009, and the film of the cured coating film The present invention relates to an active energy ray-curable release agent composition for a release liner used for a pressure-sensitive adhesive tape and a pressure-sensitive adhesive sheet formed to have a thickness of 0.5 to 2 μm, a carrier for a production process, and the like.

  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) averages of (meth) acryloyl groups in one molecule. And its concentration should be at least 8 equivalents (preferably 10 equivalents) per kg. The reason is to maintain sufficient curability. In the active energy ray-curable release agent composition, the contained (meth) acryloyl group causes a radical reaction to polymerize, thereby curing proceeds. However, it is generally known that radicals are trapped by oxygen molecules and inactivated, so that they are inhibited from curing in the presence of oxygen, and the effects become more pronounced as they become thin films. The active energy ray-curable release agent composition of the present invention has a thickness of 0.05 to 2 μm in order to obtain a cost problem and a smoother surface when the active energy ray-curable release agent composition layer is provided on a substrate. It is often coated and painted with a thin film. Active energy ray curable release agent compositions that exhibit sufficient curability in such a situation are limited. If the resin does not have sufficient curability, curing failure is likely to occur even when irradiated with active energy rays. As a result, even if the appearance is cured, the residual adhesion rate, the abrasion resistance, the solvent resistance and the like are deteriorated, and the peeling force also tends to be heavy. If the (meth) acrylate (A) has at least three (meth) acryloyl groups in one molecule and its concentration is at least 8 equivalents per kg, even the thin film as described above is sufficient. Curable. In addition, (meth) acrylate means acrylate, methacrylate and mixtures thereof.

  If a better curability is desired, it is desirable to use a hydroxyl group-containing acrylate which is composed only of an acryloyl group and a hydroxyl group as a functional group without containing a methacryloyl group. Among them, dipentaerythritol monoacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate having a structure represented by the above general formulas (1) and (2) It is one or a mixture of two or more selected from pentaerythritol monoacrylate, pentaerythritol diacrylate and pentaerythritol triacrylate, and the content of acryloyl groups on average is at least three in one molecule, and the concentration thereof Is particularly preferably adjusted to at least 8 equivalents per kg.

  In addition, according to the use situation, it is also possible to use in combination an acrylate containing only an acryloyl group, such as dipentaerythritol hexaacrylate or pentaerythritol tetraacrylate, which does not contain a hydroxyl group.

  The isocyanate monomer as a raw material of the isocyanurate (B) having at least two or more isocyanate groups in one molecule constituting the active energy ray-curable release agent composition of the present invention is tolylene diisocyanate, hydrogenated tolylene diisocyanate Well-known and commonly used diisocyanate compounds such as diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, lysine diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate and the like can be mentioned. There are many isocyanate compounds other than isocyanurate such as biuret type and adduct type, but if the smoothness of the coated surface is designed with top priority, it is necessary to use an isocyanurate body. In particular, when an isocyanurate composed of hexamethylene diisocyanate is used, the peelability tends to be minimized while maintaining a good coated surface appearance, which is desirable.

The linear dimethylorganopolysiloxane (C) having a hydroxyl group constituting the active energy ray-curable release agent composition of the present invention has a hydroxyl group-containing (meth) acrylate via an isocyanate group-containing isocyanurate (B) In order to react with (A), it is necessary to have at least one or more hydroxyl groups in one molecule. In addition, in order to express a good peeling force, it is required to be linear. Furthermore, its number average molecular weight needs to be 1,000 to 5,000. When the number average molecular weight is 1,000 or more, the peeling force tends to be light, and when the number average molecular weight is 5,000 or less, the coated surface tends to be smooth, and the smoothness can be easily maintained. As typical examples, those having the structures shown in the general formulas (3), (4) and (5) can be mentioned. Peeling power is light in the order of general formula (5), (3), (4), and the coated surface tends to be rough, but by controlling the content of silicone and the number average molecular weight in the above ranges, Good coated surface appearance can be imparted. The number average molecular weight is a value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve.
A commercial item can be used for linear dimethyl organopolysiloxane (C) which has a hydroxyl group, For example, Silaprene FM-4411, FM-4421, FM-4425, FMDA11, FMDA21, FMDA26, FMDA26, FM0411, FM0421 , FM0425 (trade name of JNC Co., Ltd.), X22-160AS, KF-6001, KF-6002, KF-6003, X-22-170BX, X-22-170DX, X22-176DX, X-22-176F (Shin-Etsu Co., Ltd.) Chemical Industry Co., Ltd. trade name).

  The ratio by mass of the hydroxyl group-containing (meth) acrylate (A), the isocyanurate (B) and the dimethylorganopolysiloxane (C) is as follows: (C) / ((A) + (B) + (C)) = 0. It should be in the range of 002 to 0.009. As described in the claim of Patent Document 3, when the proportion of dimethylorganopolysiloxane (C) is larger than the above range, the peeling force is likely to be stable but the coated surface is likely to be rough, and it is required for the recent manufacturing process carrier High smoothness can not be realized. It becomes easy to express light exfoliation that it is 0.002 or more, and it becomes easy to keep a coated surface smooth that it is 0.009 or less. Preferably it is 0.003 to 0.008, and more preferably in the range of 0.004 to 0.006.

  Furthermore, a value obtained by subtracting the total amount of hydroxyl groups possessed by dimethylorganopolysiloxane (C) from the total amount of isocyanate groups possessed by isocyanurate (B) having at least two or more isocyanate groups in one molecule is a hydroxyl group containing (meta ) By adjusting to be smaller than the total amount of hydroxyl groups possessed by the acrylate (A), the dimethyl organopolysiloxane (C) tends to reduce the unreacted matter with the hydroxyl group-containing (meth) acrylate (A) It is in. That is, it is desirable because the amount of the silicone compound having no active energy ray curing ability (functional group derived from (meth) acrylate) is reduced, and as a result, the non-migratory property of silicone is further improved.

  Examples of the active energy ray used in the present invention include known and customary ones such as electron beam, α ray, β ray, γ ray, infrared ray, visible light and ultraviolet ray. Among them, electron beams and ultraviolet rays are relatively researched, and in particular, ultraviolet rays are desirable because they have advantages such as availability of the irradiation apparatus at low cost.

  When the active energy ray-curable release agent composition of the present invention is cured by active energy rays, it is not necessary to mix the photopolymerization initiator if the above electron beam is used, but when it is cured by ultraviolet light, the photopolymerization initiator Need to be mixed. As a thing used for a photoinitiator, 2, 2- dimethoxy- 1, 2- diphenyl ethane 1-one, benzophenone, 1- [4- (2-hydroxy ethoxy) -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) -phenyl phosphine oxa Dehydrobis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide 1,2-octanedione 1- [1 4- (phenylthio)-, 2- (o-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o- Acetyl oxime), 2-chlorothioxanthone, 2,4-diethylthioxanthone, [4- (methylphenylthio) phenyl] phenylmethanone, ethyl anthraquinone, etc. using one or a mixture of two or more of known conventional ones it can. In particular, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-hydroxy that is considered to be excellent in surface curing properties -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 desirable, among which 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methylpropane-1 -On is particularly desirable. Moreover, as for the compounding quantity, it is desirable to adjust to 5-15 mass% with respect to the total mass of (A), (B), and (C) from surfaces, such as hardenability 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, It is also possible to use initiation aids such as 2-ethylhexyl-4-dimethylaminobenzoate.

  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 does not have reactivity. If it exists, a conventionally well-known thing can be used. Toluene, xylene, methanol, ethanol, isobutanol, n-butanol, methyl ethyl ketone, hexane, heptane, etc. can be used alone or as a mixture of two or more, and the amount thereof used is 1 to 60% by mass of 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 (painting) on a substrate, heating in the case of a solvent type to volatilize the solvent, and then curing by irradiation with an active energy ray. Layers can be formed. Although heating temperature is based on a film thickness and a dilution solvent, it is 50-100 degreeC.

  When the active energy ray-curable composition of the present invention is applied to a substrate to prepare a release liner, the release agent layer needs to have a thickness of 0.5 to 2 μm as a cured coating film thickness. When the film thickness is 0.5 μm or more, a light peeling force is easily exhibited stably, and when the film thickness is 2 μm or less, the coated surface is easily smoothed, and when it exceeds 2 μm, per unit area Production costs will increase.

  Specifically, film substrates such as polyethylene terephthalate film and polyethylene naphthalate film, and paper substrates such as high quality paper, medium paper, art paper, cast coated paper, coated paper etc. Can be mentioned.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Moreover, "part" and "%" shown in an Example show a mass part and mass%, unless it shows clearly.

Example 1
Hydroxyl group having an average of three or more (meth) acryloyl groups in one molecule and a concentration of at least 8 equivalents per kg in a flask equipped with a stirrer, thermometer, reflux condenser and nitrogen introduction tube 2170 parts of KAYARAD (registered trademark) DPHA (made by Nippon Kayaku Co., Ltd., having a structure shown in the general formula (1), and a mixture of pentaacrylate and hexaacrylate) as the contained (meth) acrylate (A), at least in one molecule 30 parts of isocyanurate from hexamethylene diisocyanate as isocyanurate (B) having two or more isocyanate groups, and silaplane as a linear dimethylorganopolysiloxane (C) having at least one hydroxyl group in one molecule (Registered trademark) FMDA 11 (trade name of JNC Corporation, number average molecular weight 1, Has a structure shown in 00 formula ^{(3), R 1 = -OH} , R 2 = - (CH 2) 3 OCH 2 CH 2 -, R 3 = -CH 2 CH 3) 20 parts of methyl ethyl ketone was placed 2220 parts Then, the temperature is raised to 85 ° C., and the mixture is kept for 7 hours to react, and as a result of IR measurement, it is confirmed that the isocyanate group has disappeared, and after lowering the system temperature to 30 ° C., Irgacure (registered trademark) 907 (BASF Japan) 111 parts of photopolymerization initiator, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one) was charged and mixed, and the active energy ray-curable release agent composition A was prepared Obtained.

Example 2
A hydroxyl group-containing (meth) acrylate (A having an average of 3 or more (meth) acryloyl groups in one molecule and a concentration of 8 or more equivalents per 1 kg in a flask having the same equipment as in Example 1) ) Is an isocyanurate having 2170 parts of KAYARAD DPHA (made by Nippon Kayaku Co., Ltd. and a mixture of pentaacrylate and hexaacrylate) and at least two or more isocyanate groups in one molecule 126 parts of isocyanurate from hexamethylene diisocyanate as B), straight-chain dimethylorganopolysiloxane having at least one hydroxyl group in one molecule (C) Silaplain FM 0411 (trade name, number average manufactured by JNC Corporation) has the structure shown in molecular weight of 1,000 general formula (5), ^{R 6} = -O _{^{, R 7 = -C 3 H 6}} OC 2 H 4 -) 9 parts of methyl ethyl ketone was placed 1665 parts, allowed to undergo the reaction by incubating was heated to 85 ° C. 7 hours, that the results isocyanate groups of IR measurement disappeared After confirming the system temperature to 30 ° C., charge 180 parts of Irgacure 184 (photopolymerization initiator made by BASF Japan Ltd., 1-hydroxy-cyclohexyl-phenyl-ketone) and mix, and the active energy ray-curable peeling Agent composition B was obtained.

[Example 3]
In a flask equipped in the same manner as in Example 1, 70 parts of isocyanurate from hexamethylene diisocyanate as isocyanurate (B) having at least two or more isocyanate groups in one molecule, at least one or more in one molecule Silane plain FMDA 21 (trade name of number average molecular weight 5,000, general compound (3) manufactured by JNC Co., Ltd., 200 parts of methyl ethyl ketone, 270 parts of methyl ethyl ketone as a linear dimethylorganopolysiloxane having a hydroxyl group of (C) The reaction mixture was heated to 85 ° C. and kept warm for 7 hours for reaction to obtain a reaction product. In a separate flask equipped similarly, 960 parts of KAYARAD DPHA (made by Nippon Kayaku Co., Ltd., a mixture of pentaacrylate and hexaacrylate having the structure shown in the general formula (1)) and the reaction product obtained above Charge 81 parts and 1000 parts of methyl ethyl ketone, raise temperature to 85 ° C and keep warm for 7 hours to react, confirm that the isocyanate group has disappeared as a result of IR measurement, lower the system temperature to 30 ° C, and then Irgacure 127 ( BASF Japan Ltd. photopolymerization initiator, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one) 100 parts was charged and mixed to obtain an active energy ray-curable release agent composition C.

Example 4
In a flask equipped in the same manner as in Example 1, 60 parts of isocyanurate from hexamethylene diisocyanate as isocyanurate (B) having at least two or more isocyanate groups in one molecule, at least one or more in one molecule X-22-176DX (trade name of Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,000, having a structure represented by the general formula (3)) 150 parts as a linear dimethylorganopolysiloxane (C) having a hydroxyl group of Then, 210 parts of methyl ethyl ketone was charged, the temperature was raised to 85 ° C., and the mixture was kept warm for 7 hours for reaction to obtain a reaction product. In a separate flask equipped similarly, 972 parts of KAYARAD DPHA (made by Nippon Kayaku Co., Ltd., a mixture of pentaacrylate and hexaacrylate having the structure shown in the general formula (1)), the reaction product obtained above Charge 56 parts, 1000 parts of methyl ethyl ketone, raise the temperature to 85 ° C and keep it warm for 7 hours to react, confirm that the isocyanate group has disappeared as a result of IR measurement, lower the system temperature to 30 ° C, and then Irgacure 184 ( 100 parts of BASF Japan photopolymerization initiators) were charged and mixed to obtain an active energy ray-curable release agent composition D.

Comparative Example 1
In a flask equipped in the same manner as in Example 1, 336 parts of hexamethylene diisocyanate as an organic isocyanate having at least two isocyanate groups in one molecule, and a linear one having at least one hydroxyl group in one molecule Silaplane FMDA 11 (trade name of a number average molecular weight of 1,000, manufactured by JNC Corporation) as a dimethyl organopolysiloxane (C) of the general formula (3), R ¹ = -OH, R ² =-(CH ₂ 1000 parts of ₃ OCH ₂ CH _2- , R ³ = -CH ₂ CH ₃ ) and 1336 parts of methyl ethyl ketone were charged, heated to 85 ° C and kept warm for 7 hours for reaction to obtain a reaction product. In a separate flask equipped similarly, 960 parts of KAYARAD DPHA (made by Nippon Kayaku Co., Ltd., a mixture of pentaacrylate and hexaacrylate having the structure shown in the general formula (1)) and the reaction product obtained above Charge 80 parts of methyl ethyl ketone, 960 parts of methyl ethyl ketone, heat to 85 ° C, keep warm for 7 hours, react, confirm that the isocyanate group has disappeared as a result of IR measurement, lower the system temperature to 30 ° C, and then Irgacure 184 ( 100 parts of BASF Japan photopolymerization initiators, 1-hydroxy-cyclohexyl-phenyl-ketone) were charged and mixed to obtain an active energy ray-curable release agent composition E.
This composition is the same as the composition described in Example 1 of Patent Document 3.

Comparative Example 2
In a flask equipped with the same equipment as in Example 1, 336 parts of hexamethylene diisocyanate, 1000 parts of Silaprene FMDA 11 (trade name of JNC Co., Ltd.) and 1336 parts of methyl ethyl ketone are charged, heated to 85 ° C. and kept warm for 7 hours. The reaction was carried out to obtain a reaction product. In a separate flask equipped with the same equipment, 867 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), 266 parts of the reaction product obtained earlier, 867 parts of methyl ethyl ketone, heated to 85 ° C and kept warm for 7 hours It is confirmed that the isocyanate group has disappeared as a result of IR measurement and the system temperature is lowered to 30 ° C., 100 parts of Irgacure 184 (photopolymerization initiator manufactured by BASF Japan Ltd.) is charged and mixed, and the activity is activated. An energy ray-curable release agent composition F was obtained.
This composition is the same as the composition described in Example 2 of Patent Document 3.

Comparative Example 3
In a flask equipped as in Example 1, 336 parts of hexamethylene diisocyanate, 15000 parts of Silaprene FMDA 26 (trade name of JNC Corporation), 15336 parts of methyl ethyl ketone are charged, heated to 85 ° C., and kept warm for 7 hours. The reaction product was obtained. In a separate flask equipped with the same equipment, 970 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), 60 parts of the reaction product obtained above and 970 parts of methyl ethyl ketone are charged, and the temperature is raised to 85 ° C for 7 hours As a result of confirming that the isocyanate group has disappeared as a result of IR measurement, the system temperature is lowered to 30 ° C., 100 parts of Irgacure 184 (photopolymerization initiator manufactured by BASF Japan Ltd.) is charged and mixed, An active energy ray-curable release agent composition G was obtained.
This composition is identical to the composition described in Example 4 of Patent Document 3.

Comparative Example 4
In a flask equipped with the same equipment as in Example 1, 570 parts of hexamethylene diisocyanate, 1000 parts of Silaprene FM 0411 (trade name of JNC Co., Ltd.) and 1570 parts of methyl ethyl ketone are charged, heated to 85 ° C. and kept warm for 7 hours. The reaction was carried out to obtain a reaction product. In a separate flask equipped with the same equipment, 953 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), 94 parts of the reaction product obtained earlier, 953 parts of methyl ethyl ketone, heated to 85 ° C and kept warm for 7 hours It is confirmed that the isocyanate group has disappeared as a result of IR measurement and the system temperature is lowered to 30 ° C., 100 parts of Irgacure 184 (photopolymerization initiator manufactured by BASF Japan Ltd.) is charged and mixed, and the activity is activated. An energy ray-curable release agent composition H was obtained.
This composition is the same as the composition described in Example 9 of Patent Document 3.

Comparative Example 5
A hydroxyl group-containing (meth) acrylate (A having an average of 3 or more (meth) acryloyl groups in one molecule and a concentration of 8 or more equivalents per 1 kg in a flask having the same equipment as in Example 1) And 989 parts of KAYARAD DPHA (made by Nippon Kayaku Co., Ltd., and a mixture of pentaacrylate and hexaacrylate) (isocyanurate having at least two or more isocyanate groups in one molecule). 10 parts of isocyanurate from hexamethylene diisocyanate as B), and straight-chain dimethylorganopolysiloxane (C) having at least one hydroxyl group in one molecule Silaplane FM 0411 (trade name, number average manufactured by JNC Corporation) has the structure shown in molecular weight of 1,000 general formula ^{(5), R 1 = -OH} , _{^{2 = - (CH 2) 3}} OCH 2 CH 2 -, R 3 = -CH 2 CH 3) 1 part were charged 1,000 parts of methyl ethyl ketone, allowed to undergo the reaction by incubating was heated to 85 ° C. 7 hours, the IR measurement Result Confirm that the isocyanate group has disappeared, lower the system temperature to 30 ° C, add 50 parts of Irgacure 907 (photopolymerization initiator manufactured by BASF Japan Ltd.) and mix, and then the active energy ray-curable release agent composition I got an object I.

Comparative Example 6
In a flask equipped as in Example 1, 2170 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a hydroxyl group-containing (meth) acrylate (A), and isocyanurate 30 from hexamethylene diisocyanate as isocyanurate (B) 23 parts of X-22-176DX (trade name of Shin-Etsu Chemical Co., Ltd.) and 2223 parts of methyl ethyl ketone are charged as linear dimethyl organopolysiloxane (C) having hydroxyl groups, and the temperature is raised to 85 ° C. for 7 hours The mixture is kept warm and reacted, and as a result of IR measurement, it is confirmed that the isocyanate group has disappeared, and after lowering the system temperature to 30 ° C., 111 parts of Irgacure 907 (photopolymerization initiator manufactured by BASF Japan Ltd.) is charged and mixed. An active energy ray-curable release agent composition J was obtained.

Comparative Example 7
In a flask equipped as in Example 1, 170 parts of hexamethylene diisocyanate, 1000 parts of Silaprene FM 0411 (a trade name of JNC Corporation) as dimethylorganopolysiloxane (C), and 1170 parts of methyl ethyl ketone are charged to 85 ° C. The temperature was raised and kept for 7 hours for reaction to obtain a reaction product. In a separate flask equipped with the same equipment, 994 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), 12 parts of the reaction product obtained above and 994 parts of methyl ethyl ketone are charged, and heated to 85 ° C for 7 hours As a result of confirming that the isocyanate group has disappeared as a result of IR measurement, the system temperature is lowered to 30 ° C., and then Irgacure 184 (photopolymerization initiator manufactured by BASF Japan Ltd., 1-hydroxy-cyclohexyl-phenyl- 100 parts of ketone) was charged and mixed to obtain an active energy ray-curable release agent composition K.

Comparative Example 8
In a flask equipped in the same manner as in Example 1, 336 parts of hexamethylene diisocyanate, 1000 parts of Silaprene FMDA 11 (trade name of JNC Corporation), 1336 parts of methyl ethyl ketone are charged, heated to 85 ° C. and kept warm for 7 hours. The reaction product was obtained.
In a separate flask equipped with the same equipment, 990 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), 20 parts of the reaction product obtained above and 990 parts of methyl ethyl ketone are charged, and heated to 85 ° C for 7 hours As a result of confirming that the isocyanate group has disappeared as a result of IR measurement, the system temperature is lowered to 30 ° C., 100 parts of Irgacure 184 (photopolymerization initiator manufactured by BASF Japan Ltd.) is charged and mixed, A release agent composition L was obtained.

  Performance evaluation was performed according to the following method.

As a base material of the peeling film for evaluation, an untreated polyethylene terephthalate (abbreviated as PET hereinafter) film having a thickness of 100 μm is used, and in each of Examples 1 to 4 and Comparative Examples 1 to 7, a resin composition is used as a solid content. It painted so that it might be set to 1.0 micrometer in film thickness, and in Comparative Example 8, it painted so that a resin composition might be set to 0.15 micrometer. The active energy ray curable release agent compositions A to L volatilize the solvent content at 70 ° C. for 1 minute after coating, and an ultraviolet ray of 200 mJ / cm ² using an ultraviolet irradiation device (high pressure mercury lamp 1 lamp 80 W / cm) And cured to obtain a release film for evaluation (release liner).

1) Peeling force: A polyester adhesive tape (Knit 31B, trade name made by Nitto Denko Corporation) was reciprocated by one reciprocation pressure with a 2 kg roller onto the treated surface on the produced peeling film, and cut into 25 mm width. The film was pulled to 180 ° at a speed of 300 mm / min and its peel force was measured.

2) Coated surface appearance: A test resin was coated on a substrate, and after film formation, the state of the coated film surface was visually confirmed and evaluated according to the following criteria.
"○": Rainbow interference pattern hardly visible "が ほ ぼ": Contour of rainbow interference pattern is clear "×": Rainbow interference pattern appears violently or brushed

  The number of acryloyl groups in one molecule, the equivalent amount per 1 kg, and the isocyanurate of the component (B) in the component (A) used for the active energy ray-curable release agent compositions A to L prepared above in Table 1 Or, the organic isocyanate, the structure of the (C) component, the number average molecular weight, and the mass ratio of the (C) component to the total of (A), (B) and (C) are collectively shown. Table 2 collectively shows the performance evaluation results of the respective examples and comparative examples.

ＨＤＩ：ヘキサメチレンジイソシアネート
ＨＤＩヌレート：ヘキサメチレンジイソシアネートからのイソシアヌレート

HDI: Hexamethylene Diisocyanate HDI Nurate: Isocyanurate from Hexamethylene Diisocyanate

As shown in Tables 1 and 2, in Comparative Examples 1 and 4 in which the content of the component (C) is more than 0.009, although the peel strength is light, the appearance of the coated surface is poor, and the content of the component (C) is included. In Comparative Example 2 in which the amount is further larger and Comparative Example 3 in which the molecular weight of the component (C) is larger than 5000, the deterioration of the coated surface appearance is further remarkable. Conversely, in Comparative Example 5 in which the content of the component (C) is less than 0.002, although the appearance on the coated surface is good, heavy peeling is large compared to other examples and comparative examples.
On the other hand, in Examples 1 to 4 in which the content of the component (C) and the molecular weight are appropriate, light peel strength and good coated surface appearance are maintained, and of course peel strength which is performance as a release agent. It turns out that it is more suitable than the composition as described in a comparative example as a manufacturing process carrier, such as a high-definition electronic component, using a favorable coated surface external appearance and by extension high smoothness.

Claims (8)

Hydroxyl group-containing (meth) acrylate (A) having an average of three or more (meth) acryloyl groups in one molecule, and having a concentration of at least 8 equivalents per kg,
Isocyanurate (B) having at least two or more isocyanate groups in one molecule,
Active energy ray curable release agent composition comprising a reactant of linear dimethylorganopolysiloxane (C) having at least one or more hydroxyl group in one molecule and having a number average molecular weight of 1,000 to 5,000 And the content of the component (C) is (C) / ((A) + (B) + (C)) = 0.002 to 0.009 in mass ratio, and the active energy ray-curable peeling Energy ray curable release agent composition for a release liner used by coating the base composition on a substrate and forming the cured coating film irradiated with active energy rays to have a thickness of 0.5 to 2 .mu.m . The active energy ray curable release agent composition according to claim 1, wherein the hydroxyl group-containing (meth) acrylate (A) of the component (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 three or more of X ^{1 to} X ⁶ are (meth) acryloyl groups And at least three or more of X ^{7 to} X ¹⁰ indicate (meth) acryloyl groups. The dimethylorganopolysiloxane (C) of the component (C) is formed by using at least one or more of the structures represented by the general formulas (3), (4) and (5). Active energy ray curable release agent composition as described.

(In the general formulas (3), (4) and (5), R ¹ , R ^{3 and} R ⁶ each independently represent an alkyl group or an alkylene ether group, and R ² , R ⁴ , R ⁵ and R ^{7 each} represent Each independently represents an alkylene group or an alkylene ether group, n represents a positive integer.   The active energy ray curable release agent composition according to any one of claims 1 to 3, wherein the isocyanurate (B) of the component (B) is an isocyanurate composed of hexamethylene diisocyanate.   From the total amount of isocyanate groups possessed by the isocyanurate (B) having at least two or more isocyanate groups in one molecule of the component (B), the total amount of hydroxyl groups possessed by the dimethylorganopolysiloxane (C) of the component (C) The active energy according to any one of claims 1 to 4, wherein the value obtained by subtracting is smaller than the total amount of hydroxyl groups possessed by the hydroxyl group-containing (meth) acrylate (A) of the component (A). Radiation curable release agent composition.   The release agent for carriers of the manufacturing process of the electronic material component which hardened the active energy ray hardening release agent composition as described in any one of Claims 1-5.   The active energy ray-curable release agent composition according to any one of claims 1 to 5 is coated on a substrate so that the film thickness after curing is 0.5 to 2 μm, and the active energy ray is irradiated , A method of forming a coating to be cured.   A method for forming a release liner, which is formed in the same manner as the method for forming a coating film according to claim 7.