Active energy ray curable release agent composition, carrier release agent, method for forming a coating film using the same, method for forming a release liner

Abstract

A manufacturing process for producing high-precision electronic components that achieves both good coating surface appearance and light release force. Active energy ray curable release agent composition suitable for carriers, etc., carrier release agent and The present invention provides a coating film forming method and a release liner forming method using the coating film forming method. The present invention provides a compound having an average of three or more (meth)acryloyl groups per molecule, and the concentration of the (meth)acryloyl groups is (Meth)acrylate (A) containing a hydroxyl group with 8 equivalents or more per 1 kg, Isocyanurate (B) having at least two isocyanate groups, A straight-chain dimethylamino group having at least one hydroxyl group and a number average molecular weight of 1,000 to 5,000. (C) is a reactant of (A) and (B) in a mass ratio of (C) / ((A)+(B)+ (C)) = 0.002 to 0.009, and the thickness of the cured coating film is formed to be 0.5 to 2 μm. The present invention relates to an active energy ray-curable release agent composition for a release liner, which is used as a release agent for a release liner.

Description

[Technical Field]

[0001] The present invention relates to an active energy ray curable stripping agent composition, a carrier stripping agent, and a method using the same. Regarding a coating film formation method and a peel liner formation method, an electronic material that is excellent in peel strength and coating surface appearance. Active energy applicable to release liners used in adhesive tapes or adhesive sheets for various purposes. Ghee wire-curable release agent composition, carrier release agent, and coating-forming / release liner using the same. Regarding the formation method. [Background technology]

[0002] Adhesive tapes and adhesive sheets are used in various industries due to their ease of handling and excellent adhesive properties. It is used in the field of electronic equipment, and many adhesive tapes and Adhesive sheets are used. The release liner of the adhesive tape and adhesive sheet works as intended. Various release agents are applied to provide the necessary peeling force. Also, adhesive protection Apart from its use as a film, it is also used as a manufacturing process carrier in the production of electronic material components. It is an indispensable item.

[0003] The performance required of the stripping agents used in these applications includes not only stable stripping power, but also Many other performance features can be cited. For example, coating suitability for obtaining a smooth surface and the use of release agents. Residual adhesion rate after use, abrasion resistance so that the peeling force is not impaired even after the surface is rubbed and worn down, Furthermore, when a solvent-based adhesive is applied to a release sheet and dried by heat, solvent resistance is required. Furthermore, in the case of adhesive sheets used for electronic materials and the like, the release component is released from the release liner. If the silicone migrates to the adhesive sheet side, this silicone can cause malfunctions in electrical and electronic equipment. Non-migration properties of silicone are also an important performance characteristic, as they can cause problems.

[0004] Conventional paint removers are broadly classified into two types: thermoplastics and thermosetting resins. Thermoplastic resins are used after painting. Because it does not undergo reaction curing, it has low solvent resistance and heat resistance after film formation. On the other hand, thermosetting resins have low solvent resistance Although it has excellent solvent resistance and heat resistance, it is designed to be heat-cured after painting, so it is thin. It has the disadvantage of not being usable on heat-sensitive substrates. Also, it is one of the main resins of thermosetting resins. In addition, there are methods of curing alkyd resins with crosslinking agents such as melamine (Patent Document 1, Patent Document (See 2).

[0005] Although alkyd resins hardened with crosslinking agents such as melamine are high-performance, as mentioned above In addition to being a thermosetting process, some of the unreacted formaldehyde used as a raw material Because it is contained as an impurity, it is being re-evaluated from an environmental perspective. Therefore, heat There has long been a demand for a release agent that does not harden and does not contain environmental pollutants.

[0006] The inventors, taking the above objectives into consideration, diligently studied and developed a hydroxyl group-containing (meth)acrylate, an organic acrylate. Obtained by reacting a socianate with a linear dimethylorganopolysiloxane having a hydroxyl group. By incorporating a photopolymerization initiator into the resin, good peel strength, residual adhesion rate, coating suitability, and durability are achieved. A solvent-resistant, abrasion-resistant, and silicone-non-migratory active energy ray-curable release agent composition We found that this can be achieved (Patent Document 3). [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2008-156498 [Patent Document 2] Japanese Patent Application Laid-Open No. 2008-156499 [Patent Document 3] Japanese Patent Application Laid-Open No. 2010-265403 [Summary of the Invention] [Problems to be Solved by the Invention]

[0008] However, with the recent improvement in performance and miniaturization of electronic material devices, there has been an increasing tendency to demand higher precision for the electronic material parts used therein. Therefore, when manufacturing such members, the manufacturing process carrier used not only requires a light peeling force but also a high level of smoothness on the surface of the peeling layer. The peeling agents developed so far have become unable to meet the requirements of the industry. The present invention provides an active energy ray-curable peeling agent composition, a peeling agent for a carrier, and a coating film forming method and a peeling liner forming method using the same, which are suitable for manufacturing process carriers for high-precision electronic parts and can achieve both good coating surface appearance and light peeling force.

[0009] As a result of studying a peeling agent that forms a smoother peeling layer while maintaining a light peeling force, in addition to the knowledge obtained so far, the inventors have found that by limiting the molecular weight range and content of dimethyloorganopolysiloxane and using isocyanurate for organic isocyanate, it is possible to achieve both good coating surface appearance and light peeling force, which has not been possible before. The present invention provides a hydroxyl group-containing (meth)acrylate (A) having an average of three or more (meth)acryloyl groups in one molecule and a concentration of 8 equivalents or more per kg, an isocyanurate (B) having at least two or more isocyanate groups in one molecule, and one molecule...

[0010] A linear molecule having at least one hydroxyl group and a number average molecular weight of 1,000 to 5,000. Active energy ray curable release agent set containing dimethylorganopolysiloxane (C) reactants The product is such that the content of component (C) is (C) / ((A)+(B)+(C))=0 by mass ratio. The viscosity is 0.002 to 0.009, and the active energy ray curable release agent composition is coated onto the substrate. The cured coating film, irradiated with active energy rays, is formed to have a thickness of 0.5 to 2 μm. This is an active energy ray curable release agent composition for release liners. Furthermore, the present invention relates to [2] the hydroxyl group-containing (meth)acrylate (A) of the above (A) component, The activated energy rays described in [1] above, having the structure shown in general formula (1) or general formula (2) This is a curable release agent composition.

[0010] [ka] (In general formulas (1) and (2), X 1 ~X 10 Each of these is independently a (meth)acryloyl group or represents a hydroxyl group, X 1 ~X 6 At least three of these groups represent (meth)acryloyl groups. And, X 7 ~X 10 At least three of these represent (meth)acryloyl groups. Furthermore, in the present invention, [3] the dimethylorganopolysiloxane (C) of the above (C) component is The structure is made using at least one of the structures shown in general formulas (3), (4), and (5). The active energy ray curable release agent composition is as described in [1] or [2].

[0011] [ka] (In general formulas (3), (4), and (5), R 1 , R 3、 R 6 are each independently an alkyl group or is an alkylene ether group, and R 2 , R 4 , R 5 , R 7 are each independently an alkylene group or is an alkylene ether group. n represents a positive integer.)

[0012] Further, the present invention relates to [4] the isocyanurate (B) of the component (B) above, wherein the isocyanurate is composed of hexamethylene diisocyanate, and is the active energy ray-curable release agent composition according to any one of the above [1] to [3]. Further, the present invention relates to [5] the value obtained by subtracting the total amount of hydroxyl groups of the dimethylorganopolysiloxane (C) of the component (C) from the total amount of isocyanate groups of the isocyanurate (B) having at least two or more isocyanate groups in one molecule of the component (B) above, is smaller than the total amount of hydroxyl groups of the hydroxyl group-containing (meth)acrylate (A) of the component (A) above, and is adjusted to be the active energy ray-curable release agent composition according to any one of the above [1] to [4]. Further, the present invention relates to [6] a release agent for a manufacturing process carrier of an electronic material component obtained by curing the active energy ray-curable release agent composition according to any one of the above [1] to [5]. Further, the present invention relates to [7] a coating film forming method in which the active energy ray-curable release agent composition according to any one of the above [1] to [5] is applied to a substrate so that the film thickness after curing becomes 0.5 to 2 μm, and then irradiated with active energy rays to be cured. Further, the present invention relates to [8] a release liner forming method formed in the same manner as the coating film forming method described in [7] above. ​​​​​​​​​[Effects of the Invention]

[0013] This invention achieves both a good coating surface appearance (high smoothness of the release layer surface) and low peeling force. An active energy ray-curable release agent composition, a carrier release agent, and a release liner can be obtained. It is possible. By using such an active energy ray-curable release agent composition and release liner, Products manufactured using manufacturing process carriers can achieve higher precision, and coated products can be coated with thinner films. This becomes possible. [Modes for carrying out the invention]

[0014] The present invention provides a molecule having an average of three or more (meth)acryloyl groups, and the concentration (A) contains hydroxyl groups in amounts of 8 equivalents or more per 1 kg, and has a small amount per molecule. Isocyanurates (B) having at least two or more isocyanate groups, with a small amount in one molecule A linear dimethyl group having at least one hydroxyl group and a number-average molecular weight of 1,000 to 5,000. The reaction product consists of a ruorganopolysiloxane (C) and, if necessary, a photopolymerization initiator, in a mass ratio Then (C) / ((A)+(B)+(C)) is adjusted to be between 0.002 and 0.009. Adhesive tapes and adhesive sheets formed to have a cured coating film thickness of 0.5 to 2 μm, manufacturing This relates to an active energy ray-curable release agent composition for release liners used in process carriers, etc. .

[0015] The hydroxyl group-containing (meth)acrylic compound constituting the active energy ray-curable release agent composition of the present invention (A) contains an average of three or more (preferably five) (meth)acryloyl groups in one molecule. (The above) must be present, and its concentration must be 8 equivalents or more per 1 kg (preferably 10 equivalents or more) This is necessary. The reason is to ensure sufficient curability. Active energy ray curing The anti-corrosive agent composition undergoes a radical reaction and polymerization due to the (meth)acryloyl groups it contains. This causes hardening to progress. However, radicals are captured by oxygen molecules and deactivated, so oxygen is present. Under these conditions, hardening is inhibited, and this effect becomes more pronounced as the film thickness decreases. This is generally known. The active energy ray curable release agent composition of the present invention, which contains an active energy ray When providing an energy-curable release agent composition layer, cost issues and the need to obtain a smoother surface It is often coated or painted with a thin film of 0.05 to 2 μm. In this situation, The term is limited to active energy ray curable release agent compositions that exhibit curing properties. If this is not done, curing failure is more likely to occur even when irradiated with active energy rays. Even if it appears hardened, residual adhesion, abrasion resistance, solvent resistance, etc. will deteriorate, and peel strength will also increase. It is prone to becoming (meth)acrylate (A) contains (meth)acryloyl groups in one molecule. If there are three or more on average, and their concentration is 8 equivalents or more per 1 kg, then the aforementioned dilute It also has sufficient curability in film form. Note that (meth)acrylate is acrylate, This refers to methacrylates and mixtures thereof.

[0016] If you want better curing properties, do not include methacryloyl groups, and use acryloyl as a functional group. It is preferable to use a hydroxyl group-containing acrylate composed only of yl groups and hydroxyl groups. Among them, dipentaerythritol mono, which has the structure shown in the general formulas (1) and (2) above, Acrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate Crilate, dipentaerythritol tetraacrylate, dipentaerythritol pen Taacrylate, pentaerythritol monoacrylate, pentaerythritol diacrylate One or more selected from relate and pentaerythritol triacrylate. It is a mixture containing an average of three or more acryloyl groups per molecule, and its concentration Products that have been adjusted to contain 8 equivalents or more per 1 kg are particularly desirable.

[0017] Additionally, depending on the usage situation, dipentaerythritol hexaacrylate or pentaerythritol may be used. Acrylates that do not contain hydroxyl groups and contain only acryloyl groups, such as tol tetraacrylate. It is also possible to use them in combination.

[0018] Each molecule constituting the active energy ray-curable release agent composition of the present invention contains at least two or The isocyanate mono, which is a raw material for isocyanurate (B) having the above isocyanate group. M is tolylene diisocyanate, hydrogenated tolylene diisocyanate, diphenylmethane Isocyanates, hydrogenated diphenylmethane diisocyanate, lysine diisocyanate, na Phthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate Diisocyanates such as xylylene diisocyanate and hydrogenated xylylene diisocyanate Examples include well-known and commonly used compounds such as biuret compounds and adduct compounds. While there are many other isocyanate compounds besides rate, the design prioritizes the smoothness of the coated surface. Therefore, it is necessary to use isocyanurate compounds. In particular, hexamethylene diisocyanate. When using an isocyanurate consisting of the above, the best peeling force is achieved while maintaining a good coating surface appearance. It tends to become lighter, which is desirable.

[0019] The active energy ray-curable release agent composition of the present invention comprises linear dimethyl compounds having hydroxyl groups. Chilorganopolysiloxane (C) is an isocyanurate (B) having an isocyanate group. ) reacts with hydroxyl group-containing (meth)acrylate (A) via ), so there is a small amount in one molecule It must have at least one hydroxyl group. Also, in order to exhibit good peeling power Furthermore, it is required to be linear in structure. Additionally, its number-average molecular weight is 1,000 to 5,000. It needs to be such. If the number average molecular weight is 1,000 or more, the peeling force tends to be lighter. When the number-average molecular weight is 5,000 or less, the coated surface tends to become smoother, and smoothness is maintained. This makes it easier. Typical examples include structures with the general formulas (3), (4), and (5). This is one example. The peeling force is lightest in the order of general formulas (5), (3), and (4), and the coated surface is more likely to become rough. However, in all cases, the silicone content and number-average molecular weight are controlled within the aforementioned range. This allows for the application of a good coating surface appearance. The number average molecular weight is... (The text then mentions gel permeation chloroforms.) Measurements were taken using matrixing (GPC) and converted using a calibration curve for standard polystyrene. It is a value. A commercially available linear dimethylorganopolysiloxane (C) containing hydroxyl groups should be used. This is possible, for example, with the Cyraplane FM-4411, FM-4421, FM-4425 , FMDA11, FMDA21, FMDA26, FM0411, FM0421, FM04 25 (product name manufactured by JNC Corporation), X22-160AS, KF-6001, KF-600 2, KF-6003, X-22-170BX, X-22-170DX, X22-176D Examples include X and X-22-176F (product name manufactured by Shin-Etsu Chemical Co., Ltd.).

[0020] Hydroxyl group-containing (meth)acrylate (A), isocyanurate (B), dimethyl organol The mass ratio of polysiloxane (C) is (C) / ((A)+(B)+(C))=0.0 It must be within the range of 0.2 to 0.009. When the proportion of dimethylorganopolysiloxane (C) in the sea urchin exceeds the above range, peeling occurs. While the force is easily stabilized, the coated surface tends to become rough, and the high level of smoothness required for carriers in today's manufacturing processes is not met. It cannot be achieved. If it is 0.002 or higher, mild peeling is more likely to occur, and if it is 0.009 or lower... Having it makes it easier to keep the coated surface smooth. Preferably it is 0.003 to 0.008, Preferably, the range is 0.004 to 0.006.

[0021] Furthermore, isocyanurates having at least two or more isocyanate groups in one molecule. From the total amount of isocyanate groups in (B), the amount of dimethylorganopolysiloxane (C) The value obtained by subtracting the total amount of hydroxyl groups is the total amount of hydroxyl groups contained in the hydroxyl group-containing (meth)acrylate (A). By adjusting it to be smaller than, the dimethylorganopolysiloxane (C) capsule Furthermore, it tends to reduce unreacted products with hydroxyl group-containing (meth)acrylate (A). In other words, it does not possess active energy ray curing ability (a functional group derived from (meth)acrylate). The amount of silicone compound is reduced, and as a result, the non-migration properties of the silicone become even better. That is desirable.

[0022] The active energy rays used in this invention include electron beams, alpha rays, beta rays, gamma rays, infrared rays, Examples include publicly known and commonly used types of light, such as visible light and ultraviolet light. Among these, electron beams and ultraviolet light have been studied relatively extensively. It is progressing, and ultraviolet light in particular is desirable because it has advantages such as the availability of inexpensive irradiation equipment. .

[0023] When curing the active energy ray-curable release agent composition of the present invention with active energy rays, Using the electron beam mentioned above eliminates the need to mix in a photopolymerization initiator, but when curing with ultraviolet light... In addition, it is necessary to mix in a photopolymerization initiator. Examples of photopolymerization initiators include: ,2-dimethoxy-1,2-diphenylethane-1-one, benzophenone, 1-[4- (2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane -1-one, oxy-phenyl-acetyl acid 2-[2-oxo-2-phenyl- Acetoxy-ethoxy]ethyl ester, oxy-phenyl-acetyl acid 2-[ 2-Hydroxy-ethoxyethyl ester, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl)-butanone-1,2-dimethylamino-2-(4-meth Rubenzyl)-(4-1-morpholin-4-ylphenyl)-butan-1-one, bi (2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2 ,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxa Ido, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 1, 2-Octanedione, 1-[4-(phenylthio)-,2-(o-benzoyloxime) ], etanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]-,1-(o-acetyloxime),2-chlorothioxanthone,2,4- Diethylthioxanthone, [4-(methylphenylthio)phenyl]phenylmethanone, One or more known and commonly used substances such as ethylanthraquinone may be used. Yes, it is possible. In particular, 1-hydroxycyclohexylphenyl is considered to have excellent surface hardening properties. Lu-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, phen Luglyoxylic acid methyl ester, 2-hydroxy-1-{4-[4-(2-Hy) Droxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methylpropane- 1-ONE, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane -1- is preferred, and among them 2-hydroxy-1-{4-[4-(2-hydroxy-2- Methylpropionyl)-benzyl]-phenyl}-2-methylpropan-1-one in particular Desirable. Furthermore, the proportion of (A), (B), and (C) should be determined from the perspective of curing properties, cost, etc. It is desirable to adjust the amount to 5-15% by mass relative to the total quantity.

[0024] Furthermore, in order to enhance the effect of the above photopolymerization initiator, isoamyl p-dimethylaminobenzoate is used. Ester, p-dimethylaminobenzoate ethyl ester, N-methyldiethanolamine n, bisethylaminobenzophenone, ethyl-4-dimethylaminobenzoate, 2- Initiation aids such as ethylhexyl-4-dimethylaminobenzoate can also be used.

[0025] The active energy ray curable release agent composition of the present invention is typically an organic solvent for convenience of use. Although it is considered a solution, this organic solvent has good solubility with each component and does not react with them. If available, conventionally known substances can be used. Toluene, xylene, methanol, ethanol , isobutanol, n-butanol, methyl ethyl ketone, hexane, heptane, etc. It can be used alone or as a mixture of two or more, and the amount used is such that the resin solids content is 1 to 60 It is desirable to keep it within the range of mass percent.

[0026] The active energy ray curable release agent composition of the present invention is used when coated (painted) onto a substrate, and when it is solvent-based. The material can be removed by heating it to evaporate the solvent, and then curing it by irradiating it with active energy rays. A layer can be formed. The heating temperature is 50-100°C, depending on the film thickness and diluent. ru.

[0027] In the present invention, the active energy ray curable composition is applied to a substrate to produce a release liner. In addition, the release agent layer needs to have a thickness of 0.5 to 2 μm compared to the cured coating film thickness. If the above conditions are met, a mild peeling force will be more easily and stably exhibited, and if the film thickness is 2 μm or less, The surface becomes smoother, and when it exceeds 2 μm, the production cost per unit area decreases. It will increase in volume.

[0028] Specifically, the substrate for the release liner is polyethylene terephthalate film and Film substrates such as polyethylene naphthalate film, as well as high-quality paper, medium-quality paper, art paper, etc. Examples of paper substrates include paper, cast-coated paper, and coated paper. [Examples]

[0029] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Not applicable. Furthermore, in the examples, "parts" and "%" refer to parts by mass unless otherwise specified. It shows the mass percentage.

[0030] [Example 1] A flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube contains (meth)acrylo It has an average of three or more yl groups in one molecule, and its concentration is 8 equivalents or more per 1 kg. KAYARAD® DPHA is a hydroxyl group-containing (meth)acrylate (A). (Manufactured by Nippon Kayaku Co., Ltd. It has the structure shown in general formula (1), and contains pentaacrylate and hexa 2170 parts of a mixture of acrylates, each molecule containing at least two isocyanate groups Isocyanurate (B) having isocyanurate from hexamethylene diisocyanate 30 parts of nurate, linear dimethyl hydroxyl having at least one hydroxyl group in each molecule. Ganopolysiloxane (C) as Cyraplane (registered trademark) FMDA11 (JNC Corporation) Company-branded product name, number average molecular weight 1,000, has the structure shown in general formula (3), R 1 =-OH , R 2 =-(CH2)3OCH2CH2-, R 3 20 parts of (-CH2CH3), methyl ethyl We prepared 2220 parts of ketone, raised the temperature to 85°C, and kept it warm for 7 hours to allow the reaction to proceed, and then measured the results using IR. After confirming that the fruit isocyanate group has disappeared, the system temperature is lowered to 30°C, and then Ir gacure(registered trademark) 907 (manufactured by BASF Japan Ltd.) Photopolymerization initiator, 2-methyl Lu-1-(4-methylthiophenyl)-2-morpholinopropan-1-one) 111 The mixture was prepared and mixed to obtain an active energy ray-curable release agent composition A.

[0031] [Example 2] In a flask equipped similarly to that in Example 1, (meth)acryloyl groups were averaged to one molecule. A hydroxyl group-containing (meth)acrylate having three or more of these components, and whose concentration is 8 equivalents or more per 1 kg. As relate (A), KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., general formula (1) The structure shown is a mixture of pentaacrylate and hexaacrylate, and 2170 parts of it. As an isocyanurate (B) having at least two or more isocyanate groups in the molecule 126 parts of isocyanurate from hexamethylene diisocyanate, with at least one molecule As a linear dimethylorganopolysiloxane (C) having one or more hydroxyl groups, Laplane FM0411 (product name manufactured by JNC Corporation, number average molecular weight 1,000, general formula ( 5) It has the structure shown, R 6 =-OH, R 7 =-C3H6OC2H4-)9 parts, methyl ester 1665 parts of chilketone were added, the temperature was raised to 85°C and maintained for 7 hours to allow the reaction to proceed, followed by IR measurement. After confirming that the isocyanate group had disappeared, the system temperature was lowered to 30°C. Irgacure184 (BASF Japan Ltd. photopolymerization initiator, 1-hydroxy- 180 parts of cyclohexyl phenyl ketone were charged and mixed, and then activated by ray curing. A stripping agent composition B was obtained.

[0032] [Example 3] In a flask equipped similarly to that in Example 1, at least two or more isocya molecules are present per molecule. As an isocyanurate (B) having a nate group, derived from hexamethylene diisocyanate 70 parts isocyanurate, a linear dimethyl compound having at least one hydroxyl group in each molecule. Cyraplane FMDA21 (JNC Corporation) contains chloroorganopolysiloxane (C). Product name, number average molecular weight 5,000, having the structure shown in general formula (3)) 200 parts, methyl Add 270 parts of ethyl ketone, raise the temperature to 85°C and maintain the temperature for 7 hours to allow the reaction to proceed. Obtained. In another flask with similar equipment, KAYARAD DPHA (Nippon Kayaku Co., Ltd.) The company's product has the structure shown in general formula (1), and is a mixture of pentaacrylate and hexaacrylate. We added 960 parts of the substance, 81 parts of the reaction product obtained earlier, and 1000 parts of methyl ethyl ketone. The mixture was then heated to 85°C and kept warm for 7 hours to allow the reaction to proceed. IR measurement revealed that the isocyanate group had disappeared. After confirming that this has been done, lower the system temperature to 30°C and then install Irgacure127(BA Photopolymerization initiator manufactured by SF Japan Co., Ltd., 2-Hydroxy-1-{4-[4-(2-Hydroxy Xy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propane-1 -100 parts of (ON) were added and mixed to obtain the active energy ray curable release agent composition C.

[0033] [Example 4] In a flask equipped similarly to that in Example 1, at least two or more isocya molecules are present per molecule. As an isocyanurate (B) having a nate group, derived from hexamethylene diisocyanate 60 parts isocyanurate, a linear dimethyl compound having at least one hydroxyl group in each molecule. X-22-176DX (Shin-Etsu Chemical Co., Ltd.) contains chloroorganopolysiloxane (C). Product name, number average molecular weight 3,000, structure shown in general formula (3)) 150 parts, methyl Add 210 parts of ethyl ketone, raise the temperature to 85°C and maintain the temperature for 7 hours to allow the reaction to proceed. Obtained. In another flask with similar equipment, KAYARAD DPHA (Nippon Kayaku Co., Ltd.) The company's product has the structure shown in general formula (1), and is a mixture of pentaacrylate and hexaacrylate. We added 972 parts of the substance, 56 parts of the reaction product obtained earlier, and 1000 parts of methyl ethyl ketone. The mixture was then heated to 85°C and kept warm for 7 hours to allow the reaction to proceed. IR measurement revealed that the isocyanate group had disappeared. After confirming that this has been done, lower the system temperature to 30°C and then use Irgacure184(BA 100 units of SF Japan Co., Ltd.'s photopolymerization initiator were added and mixed, and activated energy rays were used. A chemical stripping agent composition D was obtained.

[0034] [Comparative Example 1] In a flask equipped similarly to that in Example 1, at least two or more isocya molecules are present per molecule. 336 parts of hexamethylene diisocyanate as an organic isocyanate having a nate group, A linear dimethylorganopolysiloxa having at least one hydroxyl group in each molecule. As (C), Cyraplane FMDA11 (product name manufactured by JNC Corporation, number average molecular weight 1 ,000 It has the structure shown in general formula (3), R 1 =-OH, R 2 =-(CH2)3OCH2 CH2-, R 3 We prepared 1000 parts of (-CH2CH3) and 1336 parts of methyl ethyl ketone. The temperature was raised to 85°C and maintained for 7 hours to allow the reaction to proceed, and the reactant was obtained. Another facility with similar equipment... In the flask, KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., structure shown in general formula (1)) Having a mixture of pentaacrylate and hexaacrylate, 960 parts were obtained earlier. Add 80 parts of the reaction mixture and 960 parts of methyl ethyl ketone, raise the temperature to 85°C, and hold for 7 hours. The reaction was carried out by heating, and IR measurement confirmed that the isocyanate group had disappeared. The system was then allowed to cool to 30°C. After lowering the internal temperature, Irgacure184 (manufactured by BASF Japan Co., Ltd.) is photopolymerized. Add 100 parts of the starting agent (1-hydroxycyclohexylphenyl ketone) and mix. This yielded an active energy ray-curable release agent composition E. This composition is identical to the composition described in Example 1 of Patent Document 3.

[0035] [Comparative Example 2] 336 parts of hexamethylene diisocyanate were placed in a flask equipped similarly to that in Example 1. 1000 copies of Cyraplane FMDA11 (product name manufactured by JNC Corporation), methyl ethyl ketol 1336 parts of the mixture were prepared, the temperature was raised to 85°C, and the mixture was kept warm for 7 hours to allow the reaction to proceed, and the reaction product was obtained. Add 8 units of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) to another flask equipped with the same equipment. 67 parts, 266 parts of the reaction mixture obtained earlier, and 867 parts of methyl ethyl ketone were added, and 85 The reaction was carried out by raising the temperature to °C and maintaining the temperature for 7 hours, and IR measurement revealed that the isocyanate group had disappeared. After confirming this, lower the system temperature to 30°C and then use Irgacure184 (BASF JAR). Add 100 parts of Pan Co., Ltd.'s photopolymerization initiator and mix, then use activated energy ray curing for peeling. A formulation F was obtained. This composition is identical to the composition described in Example 2 of Patent Document 3.

[0036] [Comparative Example 3] 336 parts of hexamethylene diisocyanate were placed in a flask equipped similarly to that in Example 1. 15,000 copies of Cyraplane FMDA26 (product name manufactured by JNC Corporation), methyl ethyl 15336 parts of ketone were added, the temperature was raised to 85°C and maintained for 7 hours to allow the reaction to proceed, and the reaction product was obtained. In another flask with similar equipment, KAYARAD DPHA (Nippon Kayaku Co., Ltd.) was added. We prepared 970 parts of the (manufactured) product, 60 parts of the reaction product obtained earlier, and 970 parts of methyl ethyl ketone. The mixture was heated to 85°C and kept warm for 7 hours to allow the reaction to proceed. IR measurement revealed that the isocyanate group had disappeared. After confirming that this has been done, lower the system temperature to 30°C and then use Irgacure184(BAS 100 parts of F Japan Co., Ltd.'s photopolymerization initiator were added and mixed, and then cured by active energy rays. A stripping agent composition G was obtained. This composition is identical to the composition described in Example 4 of Patent Document 3.

[0037] [Comparative Example 4] 570 parts of hexamethylene diisocyanate were placed in a flask equipped similarly to that in Example 1. 1000 copies of Cyraplane FM0411 (product name manufactured by JNC Corporation), methyl ethyl ketol 1570 parts of the mixture were prepared, the temperature was raised to 85°C, and the mixture was kept warm for 7 hours to allow the reaction to proceed, and the reaction product was obtained. In another flask equipped with the specified equipment, add 9 units of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.). Add 53 parts, 94 parts of the reaction mixture obtained earlier, and 953 parts of methyl ethyl ketone, and heat to 85°C. The mixture was heated to a certain temperature and kept warm for 7 hours to allow the reaction to proceed. IR measurement revealed that the isocyanate group had disappeared. After confirming and lowering the system temperature to 30°C, Irgacure184 (BASF Japan) Mix 100 parts of the photopolymerization initiator manufactured by [Company Name] and an activated energy ray curable release agent. Composition H was obtained. This composition is identical to the composition described in Example 9 of Patent Document 3.

[0038] [Comparative Example 5] In a flask equipped similarly to that in Example 1, (meth)acryloyl groups were averaged to one molecule. A hydroxyl group-containing (meth)acrylate having three or more of these components, and whose concentration is 8 equivalents or more per 1 kg. As relate (A), KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., general formula (1) (Having the structure shown, a mixture of pentaacrylate and hexaacrylate) 989 parts, 1 part As an isocyanurate (B) having at least two or more isocyanate groups in the molecule, 10 parts of isocyanurate from xamethylene diisocyanate, with at least one molecule per molecule As a linear dimethylorganopolysiloxane (C) having more than one hydroxyl group, cyrap Lane FM0411 (product name manufactured by JNC Corporation, number average molecular weight 1,000, general formula (5)) It has the structure shown, R 1 =-OH, R 2 =-(CH2)3OCH2CH2-, R 3 =-CH Add 1 part 2CH3 and 1000 parts methyl ethyl ketone, raise the temperature to 85°C, and hold for 7 hours. The reaction was allowed to proceed by heating, and IR measurement confirmed the disappearance of the isocyanate group, and the temperature was reduced to 30°C. After lowering the system temperature, Irgacure907 (BASF Japan Co., Ltd. photopolymerization) is performed. Fifty parts of the initiator were added and mixed to obtain an activated energy ray-curable release agent composition I.

[0039] [Comparative Example 6] A flask equipped with the same equipment as in Example 1 contains hydroxyl group-containing (meth)acrylate (A). 2170 copies of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), and isocyanurate ( B) 30 parts of isocyanurate from hexamethylene diisocyanate, containing hydroxyl groups X-22-176DX (Shin-etsu) is a linear dimethylorganopolysiloxane (C) that is used. Add 23 parts (product name from Chemical Industry Co., Ltd.) and 2223 parts of methyl ethyl ketone, and heat to 85°C. The mixture was then heated and kept warm for 7 hours to allow the reaction to proceed, and IR measurement revealed that the isocyanate group had disappeared. After confirming and lowering the system temperature to 30°C, Irgacure907 (BASF Japan) Add 11 parts of the photopolymerization initiator manufactured by [Company Name] and mix, then add an activated energy ray curable release agent. Composition J was obtained.

[0040] [Comparative Example 7] In a flask equipped similarly to that in Example 1, add 170 parts of hexamethylene diisocyanate. , as dimethylorganopolysiloxane (C), Cyraprene FM0411 (JNC Corporation) Charge 1000 units of (product name manufactured by Co., Ltd.) and 1170 units of methyl ethyl ketone, and raise the temperature to 85°C. The reaction was allowed to proceed by incubating the temperature for 7 hours to obtain the reaction product. In another flask with similar equipment, KA 994 parts of YARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), and 12 parts of the reaction mixture obtained earlier. Add 994 parts of methyl ethyl ketone, raise the temperature to 85°C, and maintain the temperature for 7 hours to allow the reaction to proceed. IR measurement confirmed the disappearance of the isocyanate group, and the system temperature was lowered to 30°C. Then, Irgacure184 (BASF Japan Ltd. photopolymerization initiator, 1-Hydro) 100 parts of roxycyclohexylphenyl ketone were charged and mixed, and the active energy A linearly curable release agent composition K was obtained.

[0041] [Comparative Example 8] 336 parts of hexamethylene diisocyanate were placed in a flask equipped similarly to that in Example 1. 1000 copies of Cyraplane FMDA11 (product name manufactured by JNC Corporation), methyl ethyl acetate 1336 parts were prepared, the temperature was raised to 85°C, and the mixture was kept warm for 7 hours to allow the reaction to proceed, yielding the reaction product. In another flask with similar equipment, KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) ) 990 parts, 20 parts of the reaction product obtained earlier, and 990 parts of methyl ethyl ketone were charged in. The reaction was carried out by raising the temperature to 85°C and maintaining the temperature for 7 hours, and IR measurement revealed that the isocyanate group had disappeared. After confirming this, lower the system temperature to 30°C and then use Irgacure184 (BASF 100 parts of the photopolymerization initiator manufactured by Japan Co., Ltd. were added and mixed to obtain the release agent composition L.

[0042] Performance evaluation was conducted according to the following method.

[0043] Untreated polyethylene terephthalate with a thickness of 100 μm was used as the substrate for the release film used for evaluation. Using a PET (hereinafter abbreviated as PET) film, Examples 1-4 and Comparative Examples 1-7 were used. In the case of Comparative Example 8, the resin composition was coated to a solid content film thickness of 1.0 μm, and the resin The lipid composition was coated to a thickness of 0.15 μm. Active energy ray curable release agent composition A ~L is treated by evaporating the solvent at 70°C for 1 minute after painting, and then using an ultraviolet irradiation device (1 high-pressure mercury lamp, 8 Using 0 W / cm, 200 mJ / cm 2 The material is irradiated with ultraviolet light to harden it, and then a peelable film is used for evaluation. A film (peel-off liner) was obtained.

[0044] 1) Peeling force: Polyester adhesive tape (Nitto 31) on the treated surface of the prepared release film B. (Product name of Nitto Denko Corporation) is pressed once back and forth with a 2kg roller and cut to a width of 25mm. The obtained test specimens were then pulled 180° at a speed of 300 mm / min, and the peeling force was measured. It was decided.

[0045] 2) Appearance of the coated surface: After coating the substrate with the test resin and forming the film, the condition of the coated surface is visually inspected and the following is observed: It was evaluated according to the following criteria. "○": Rainbow interference patterns are almost invisible. "△": The outline of the rainbow interference pattern is clearly defined. "×": Shows intense iridescent interference patterns or brushing.

[0046] Table 1 shows the components (A) used in the active energy ray-curable release agent compositions A to L prepared above. The number of acryloyl groups in one molecule, the equivalent amount per 1 kg, and the isocyanure of component (B). (C) Structure, number average molecular weight and (A), (B), ( The mass ratio of component (C) to the total of C) is summarized below. Table 2 also shows the examples and comparative examples. The performance evaluation results are summarized below.

[0047] [Table 1] HDI: Hexamethylene diisocyanate HDI Nurate: Isocyanurate from Hexamethylene Diisocyanate

[0048] [Table 2]

[0049] As shown in Tables 1 and 2, comparative examples where the content of component (C) is greater than 0.009 are available. In 1 and 4, although the peeling force is light, the appearance of the coated surface is poor, and the ratio with an even higher content of component (C) Comparative Example 2 and Comparative Example 3, in which the molecular weight of component (C) is greater than 5000, show further deterioration in the appearance of the coated surface. The transformation is significant. Conversely, in Comparative Example 5, where the content of component (C) is less than 0.002, the coated surface Although the appearance is good, it shows significantly more severe peeling compared to other examples and comparative examples. In contrast, Examples 1-4, in which the content and molecular weight of component (C) are appropriate, exhibit a light peeling force and It maintains a good coating surface appearance, and in addition to its performance as a release agent, it has good coating performance. By utilizing its surface appearance and, consequently, its high smoothness, it can be used as a manufacturing process carrier for high-precision electronic components, etc. It can be seen that this composition is more suitable than the composition described in the comparative example.

Claims

1. A hydroxyl group-containing (meth)acrylate (A) has an average of three or more (meth)acryloyl groups in one molecule, and its concentration is 8 equivalents or more per 1 kg. Isocyanurate (B) having at least two or more isocyanate groups in one molecule, and This is an active energy ray-curable release agent composition obtained using a linear dimethylorganopolysiloxane (C) having at least one hydroxyl group in one molecule and a number average molecular weight of 1,000. The dimethylorganopolysiloxane (C) component (C) is made using at least one of the structures shown in the following general formulas (3) and (5). 【Chemistry 1】 (In general formulas (3) and (5), R １ , R ３ , R ６ Each of them independently adds an alkyl group, R ２ , R ７ Each of these independently represents either an alkylene group or an alkylene ether group. n represents a positive integer. The difference between the total amount of isocyanate groups in the isocyanurate (B) having at least two or more isocyanate groups in one molecule of component (B) and the total amount of hydroxyl groups in the dimethylorganopolysiloxane (C) of component (C) is smaller than the total amount of hydroxyl groups in the hydroxyl-containing (meth)acrylate (A) of component (A). The reaction product of component (A), component (B), and component (C), and unreacted component (A), wherein the content of component (C) is (C) / ((A)+(B)+(C)) = 0.004 to 0.009 by mass ratio. An active energy ray-curable release agent composition for a release liner, which is used by coating the aforementioned active energy ray-curable release agent composition onto a substrate and irradiating it with active energy rays to form a cured coating film with a thickness of 0.5 to 2 μm.

2. The active energy ray-curable release agent composition according to claim 1, wherein the hydroxyl group-containing (meth)acrylate (A) of component (A) has a structure represented by general formula (1) or general formula (2). 【Chemistry 2】 (In general formulas (1) and (2), X １ to X １０ each independently represents a (meth)acryloyloxy group or a hydroxyl group, and at least three or more of X １ to X ６ represent (meth)acryloyloxy groups, and at least three or more of X ７ to X １０ represent (meth)acryloyloxy groups.)

3. The active energy ray-curable release agent composition according to claim 1 or 2, wherein the isocyanurate (B) of component (B) is an isocyanurate composed of hexamethylene diisocyanate.

4. A release agent for a manufacturing process carrier of an electronic material component, obtained by curing the active energy ray curable release agent composition according to any one of claims 1 to 3.

5. A method for forming a coating film, comprising coating a substrate with an active energy ray-curable release agent composition according to any one of claims 1 to 3 such that the film thickness after curing is 0.5 to 2 μm, irradiating it with active energy rays, and curing it.

6. A method for forming a release liner, similar to the coating film forming method described in claim 5.

Images