Radiation-curable release agent composition and release liner

Abstract

The present invention provides a radiation-curable release agent composition that ensures easy peelability while exhibiting higher adhesion to substrates such as glassine paper and thermal paper. [Solution] A release agent composition containing component (A), component (B), and component (C). (A) Hydrocarbon compounds having a viscosity of 50 mPa·s to 2000 mPa·s at 25°C and containing one or more acryloyl groups per molecule: 50 to 99.99 parts by mass (B) Organopolysiloxane containing a (meth)acryloyl group, represented by formula (1): 0.01 to 50 parts by mass JPEG2026112975000009.jpg28170 (R 1 At least one of them is an organic group containing a (meth)acryloyl group, a is 2 or more, b is 0 or more, c is 0 or more, and d is 0 or more, 2 ≤ a + b + c + d ≤ 1,000 (the siloxane units shown in the parentheses above may be arranged randomly or form a block structure), and (C) Radical polymerization initiator: 0.1 to 15 parts by mass.

Description

[Technical Field]

[0001] The present invention relates to a radiation-curable release agent composition that exhibits excellent adhesion to various substrates, and a release liner having a cured product of the release agent composition. [Background technology]

[0002] Release liners such as release paper and release film, which have adhesive or tacky properties, are manufactured by applying an organopolysiloxane composition to the surface of various substrates such as paper, laminated paper, synthetic film, resin, and metal foil, and forming a hardened film through a crosslinking reaction.

[0003] There are various methods for curing polyorganosiloxane compositions, including condensation reactions with organometallic compounds, vulcanization using organic peroxides, and hydrosilylation reactions with platinum group metal catalysts. However, these curing methods require heating, and there is a demand for curing at lower temperatures or at room temperature to improve productivity and save energy. Recently, in addition to glassine paper, which is used in various fields such as food and pharmaceuticals, there has been an increase in applications using substrates with poor heat resistance, such as polyethylene terephthalate (PET) film for electronic components and optical materials, and thermal paper for cash registers and delivery labels.

[0004] Therefore, as a method of providing curing energy other than heat without using heating, radiation curing methods are attracting attention. Examples of radiation curing methods include radical polymerization using (meth)acrylic-modified polysiloxanes, cationic polymerization by ring-opening of epoxy groups in epoxy-modified polysiloxanes, and curing by ene-thiol reactions using mercapto-modified polyorganosiloxanes and alkenyl-modified polyorganosiloxanes.

[0005] Among these methods, radical polymerization using (meth)acrylic-modified polysiloxane has the advantage of excellent curing properties, although it requires equipment to reduce oxygen concentration because the presence of oxygen inhibits curing. This makes it possible to develop backing agents for adhesive tapes, release papers for adhesive labels, release films, and tapes using films with poor heat resistance that shrink when heated as substrates, and further market expansion is expected.

[0006] However, although many inventions have been proposed regarding release agents for (meth)acryloyl group-containing radical polymerizable organopolysiloxanes, there are several problems. For example, Patent Document 1 describes a radiation-curable organopolysiloxane using a (meth)acryloyl group-containing radical polymerizable organopolysiloxane containing silsesquioxane units in the molecule. Patent Document 1 states that the radiation-curable organopolysiloxane is easily peelable and that the peeling force does not change over time, but it does not mention peelability to strong adhesives or adhesion to substrates.

[0007] Patent Document 2 describes a radiation-curable organopolysiloxane using a mixture of a polyorganosiloxane having numerous (meth)acryloyl groups in its side chains and a polyorganosiloxane having (meth)acryloyl groups only at its terminals. Patent Document 2 states that a cured film with good peelability and substrate adhesion can be obtained by orienting the polyorganosiloxane containing numerous (meth)acryloyl groups in its side chains toward the substrate side and orienting the polyorganosiloxane containing (meth)acryloyl groups only at its terminals toward the surface, but does not provide details on substrate adhesion.

[0008] Patent Document 3 states that adhesion to a substrate is improved by using a composition comprising 100 parts by mass of polyorganosiloxane having a (meth)acryloyl group and 0.1 to 50 parts by mass of a polyfunctional acrylate compound. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] Japanese Patent Application Laid-Open No. 4-239526 [Patent Document 2] U.S. Patent No. 6268404 [Patent Document 3] Japanese Patent Application Laid-Open No. 2020-186284 [Summary of the Invention] [Problems to be Solved by the Invention]

[0010] As described above, in Patent Document 1, the peelability from a strong adhesive and the adhesion to a substrate are not mentioned. In Patent Document 2, the substrate adhesion is not also mentioned in detail. Further, although the composition described in Patent Document 3 has good adhesion to a PET film, further improvement in adhesion is required.

[0011]

[0012] Therefore, in a release coating agent using a polyorganosiloxane having a (meth)acryloyl group, a release coating agent having excellent adhesion to substrates other than a PET film, such as glassine paper and thermal paper, is required. Further, in the methods described in Patent Documents 1 to 3, since a large amount of polyorganosiloxane, which is more expensive than general organic compounds, is blended, there is also a demerit of high cost. [Means for Solving the Problems]

[0013] As a result of intensive studies to achieve the above object, the present inventors have found that a hydrocarbon compound containing a compound having one or more acryloyl groups in one molecule, particularly a hydrocarbon compound containing a compound having three or more acryloyl groups in one molecule, as a main component, and a small amount of an organopolysiloxane having a (meth)acryloyl group added thereto, gives a cured product having high substrate adhesion to a substrate such as glassine paper or thermal paper as compared with the cured product obtained from the conventional release agent composition described above, and thus have completed the present invention.

[0014] That is, the present invention provides [1] A release agent composition containing the following components (A), (B), and (C). (A) One or more hydrocarbon compounds having a viscosity of 50 mPa·s to 2000 mPa·s at 25°C and having one or more acryloyl groups in one molecule, which may have heteroatoms: 50 to 99.99 parts by mass (B) A (meth)acryloyl group-containing organopolysiloxane represented by the following formula (1): 0.01 to 50 parts by mass (however, the total of the above components (A) and (B) is 100 parts by mass) [Chemical formula] (In the formula, R 1 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 11 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, a hydroxyl group-containing organic group, a halogen atom-containing organic group, or a (meth)acryloyl group-containing organic group, at least one of R 1 is a (meth)acryloyl group-containing organic group, a is a number of 2 or more, b is a number of 0 or more, c is a number of 0 or more, d is a number of 0 or more, 2 ≤ a + b + c + d ≤ 1,000, and the siloxane units shown in the parentheses may be randomly arranged or form a block structure), and (C) A radical polymerization initiator: 0.1 to 15 parts by mass with respect to 100 parts by mass of the total of the above components (A) and (B).

[0015] The present invention further provides a release agent composition, a cured product, and a release liner having any of the following configurations. [2] The stripping agent composition according to [1] above, wherein component (A) contains one or more hydrocarbon compounds that may have heteroatoms, having three or more acryloyl groups in one molecule and a viscosity at 25°C of 100 mPa·s or more and less than 4000 mPa·s, in an amount of 50 parts by mass to 100 parts by mass per 100 parts by mass of component (A), and the total viscosity of component (A) at 25°C is 50 mPa·s to 2000 mPa·s. [3] The stripping agent composition according to [2] above, wherein component (A) further contains at least one hydrocarbon compound which may have heteroatoms, having two or more acryloyl groups in one molecule and a viscosity of 0.1 mPa·s or more and less than 100 mPa·s at 25°C. [4] The above (A) component is (A-1) 50 to 99 parts by mass of at least one hydrocarbon compound which may contain heteroatoms, having three or more acryloyl groups in one molecule and having a viscosity of 100 mPa·s or more and less than 4000 mPa·s at 25°C. (A-2) A hydrocarbon compound comprising 1 to 50 parts by mass of at least one heteroatom-containing hydrocarbon compound having two or more acryloyl groups in one molecule and having a viscosity of 0.1 mPa·s or more and less than 100 mPa·s at 25°C, The stripping agent composition according to [1] above, wherein the viscosity of the entire (A) component at 25°C is 50 mPa·s to 2000 mPa·s. [5] The stripping agent composition according to any one of [1] to [4] above, wherein component (A) contains (A-1) a hydrocarbon compound which may have heteroatoms and has three or more acryloyl groups in one molecule and a viscosity of 100 mPa·s or more and 2000 mPa·s or less at 25°C. [6] The stripping agent composition according to any one of [1] to [5] above, wherein the amount of component (A) is greater than 90 parts by mass and 99.99 parts by mass or less, and the amount of component (B) is 0.01 parts by mass or more and less than 10 parts by mass, with respect to 100 parts by mass of the total of component (A) and component (B). [7] The stripping agent composition according to any one of [1] to [5] above, wherein the (B) component comprises at least one of the following (B-1) component and (B-2) component. (B-1) A (meth)acryloyl group-containing organopolysiloxane in which, in the average composition formula (1) above, the ratio of the number of silicon atoms to which the (meth)acryloyl group-containing organic group is bonded to the total number of silicon atoms is 7.5% or more and 20% or less, and (B-2) A (meth)acryloyl group-containing organopolysiloxane in which, in the average composition formula (1) above, the ratio of the number of silicon atoms to which the (meth)acryloyl group-containing organic group is bonded to the total number of silicon atoms is 1% or more and less than 7.5%. [8] The stripping agent composition according to [7] above, wherein, with respect to 100 parts by mass of the total of component (A) and component (B), the amount of component (A) is more than 90 parts by mass and 99.99 parts by mass or less, and the amount of component (B) is 0.01 parts by mass or more and less than 10 parts by mass. [9] The stripping agent composition according to [7] or [8] above, wherein component (B) comprises at least component (B-2).

[10] The release agent composition according to any one of [1] to [9] above, wherein the amount of component (A) is 90.1 parts by mass or more and 98.5 parts by mass or less, and the amount of component (B) is 1.5 parts by mass or more and 9.9 parts by mass or less, with respect to 100 parts by mass of the total of component (A) and component (B).

[11] The stripping agent composition according to any one of [7] to

[10] above, wherein the amount of component (B-2) is 9.2 parts by mass or less with respect to 100 parts by mass of the total of component (A) and component (B).

[12] A cured product obtained by curing any one of the release agent compositions described in [1] to

[11] above.

[13] A release liner having a base material and a layer made of the cured product described in

[12] above, laminated on at least one surface of the base material. [Effects of the Invention]

[0016] The release liner obtained from the release agent composition of the present invention has higher adhesion to substrates such as glassine paper and thermal paper while ensuring easy release properties, compared to release liners having cured products of conventional organopolysiloxane compositions for release liners. [Modes for carrying out the invention]

[0017] The present invention relates to a radiation-curable release agent composition containing (A) a hydrocarbon compound having an acryloyl group, (B) an organopolysiloxane containing a (meth)acryloyl group, and (C) a radical polymerization initiator. The composition mainly consists of (A) an acryloyl group-containing hydrocarbon compound and (B) a small amount of an organopolysiloxane containing a (meth)acryloyl group. Furthermore, as described later, it is preferable that component (B) contains an organopolysiloxane containing a (meth)acryloyl group with a (meth)acryloyl group content of a certain amount or less.

[0018] A preferred embodiment of the present invention is a release agent composition comprising an organopolysiloxane with a limited acryloyl group content in the molecule. Another preferred embodiment of the present invention is a release agent composition comprising an acryloyl group-containing organopolysiloxane in a specific amount or less. This release agent composition provides a cured product with better peelability while maintaining the high substrate adhesion described above. Furthermore, by reducing the amount of organopolysiloxane with a limited acryloyl group content in the molecule, it is also possible to provide a cured product that ensures a good residual adhesion rate (adhesion of the tape after peeling from the release liner / adhesion of the tape not bonded to the release liner).

[0019] The following provides a more detailed explanation of each component.

[0020] (A) Hydrocarbon compounds having an acryloyl group Component (A) is one or more hydrocarbon compounds having a viscosity of 50 mPa·s to 2000 mPa·s at 25°C, having one or more acryloyl groups per molecule, and possibly containing heteroatoms. Component (A) functions as an adhesion-enhancing component in the release agent composition of the present invention.

[0021] Component (A) has a viscosity of 50 to 2,000 mPa·s at 25°C, preferably 60 to 1,600 mPa·s, and more preferably 70 to 1,200 mPa·s. The viscosity of component (A) being within the above range is preferable because the resulting composition has excellent coating properties in roll coating. If the viscosity of component (A) is less than 50 mPa·s, the roll may not rotate properly during coating of the composition, potentially resulting in poor coating. If the viscosity of component (A) is greater than 2,000 mPa·s, unevenness may occur on the coated surface of the composition, potentially preventing uniform coating. If component (A) is a combination of two or more compounds, it is sufficient that the viscosity of component (A) as a whole at 25°C is within the above range. Therefore, component (A) may include hydrocarbon compounds having a viscosity of less than 50 mPa·s at 25°C, and / or hydrocarbon compounds having a viscosity of more than 2,000 mPa·s at 25°C, which are included in components (A-1) and (A-2) described later. In this invention, the viscosity at 25°C is the value measured using a BM-type rotational viscometer (for example, manufactured by Toki Sangyo Co., Ltd.). The rotor, rotation speed, and rotation time are appropriately selected according to the viscosity based on conventional methods.

[0022] Component (A) may be a single hydrocarbon compound that may have one or more heteroatoms having one or more acryloyl groups in one molecule, or it may be a combination of two or more hydrocarbon compounds that may have one or more heteroatoms having one or more acryloyl groups in one molecule.

[0023] A hydrocarbon compound having one or more acryloyl groups in one molecule and which may have heteroatoms can be any conventionally known acryloyl group-containing hydrocarbon compound. Examples of such hydrocarbon compounds include hydrocarbon compounds having 4 to 25 carbon atoms that have acryloyl groups and which may have heteroatoms. Heteroatoms are oxygen atoms, nitrogen atoms, etc., and examples include acryloyl group-containing hydrocarbon compounds that may have structures such as ethers. Furthermore, in the present invention, component (A) is more preferably a hydrocarbon compound having one or more acryloyl groups in one molecule and which may have heteroatoms, but which does not have a urethane structure. Moreover, component (A) in the present invention may be an acrylic compound that does not have an oxyethylene structure.

[0024] More specifically, examples include acrylic compounds (acrylate monomers) having ether structures, selected from monofunctional acrylic compounds, difunctional acrylic compounds, trifunctional acrylic compounds, and tetrafunctional or more functional acrylic compounds having 4 to 25 carbon atoms.Examples of the acrylic compounds include monofunctional acrylic compounds such as hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-octyl acrylate, dodecyl acrylate, hexadecyl acrylate, stearyl acrylate, isostearyl acrylate, isobornyl acrylate, 4-tert-butylcyclohexyl acrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, tricyclodecanedimethanol diacrylate, and dipropylene glycol diacrylate. Acrylate, tripropylene glycol diacrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, difunctional acrylic compounds such as Viscoat #700HV (bisphenol AEO 3.8 molar adduct diacrylate) manufactured by Osaka Organic Chemical Industry Co., Ltd., trimethylolpropane triacrylate, pentaerythritol triacrylate, tris(2-acryloyloxyethyl) isocyanurate, α,α',α''-propane-1,2,3-triyltris[ω-(acryloyloxy)poly(oxyethylene)], TMPEOTA (trimethylolpropaneethoxytriacrylate) manufactured by Daicel Ornex Co., Ltd., and OTA manufactured by Daicel Ornex Co., Ltd. Examples include trifunctional acrylic compounds such as 480 (glycerin propoxy triacrylate), and tetrafunctional or more acrylic compounds such as pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, tripentaerythritol octaacrylate, ATM-4E (pentaerythritol EO adduct tetraacrylate) and ATM-4P (pentaerythritol PO adduct tetraacrylate) manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and A-9550 (dipentaerythritol polyacrylate) manufactured by Shin-Nakamura Chemical Industry Co., Ltd. .

[0025] Component (A) preferably contains a hydrocarbon compound (A-1) which has three or more acryloyl groups in one molecule and may have heteroatoms. Including this compound improves the adhesion of the composition to the substrate. Examples of the hydrocarbon compound are as described above, and preferably it is a trifunctional or higher acrylic compound (acrylate monomer) having 4 to 25 carbon atoms. Component (A-1) has one or more acryloyl groups in one molecule as described above and may have heteroatoms, but it is more preferable that it is a hydrocarbon compound that does not have a urethane structure. Furthermore, it may also be an acrylic compound that does not have an oxyethylene structure.

[0026] Component (A-1) preferably has a viscosity at 25°C of 100 mPa·s or more and less than 4000 mPa·s, more preferably 125 mPa·s or more and 3000 mPa·s, more preferably 150 mPa·s or more and 2500 mPa·s, and even more preferably 175 mPa·s or more and 2000 mPa·s. If component (A-1) has a viscosity at 25°C greater than 2000 mPa·s, it can be adjusted by mixing it with a hydrocarbon compound having a low viscosity, such as component (A-2) described later, so that the viscosity of component (A) as a whole at 25°C is in the range of 50 to 2000 mPa·s, preferably 60 to 1600 mPa·s, and even more preferably 70 to 1200 mPa·s.

[0027] Component (A) may consist only of component (A-1) described above, and in this embodiment, the viscosity of component (A-1) is preferably 100 mPa·s or more and 2000 mPa·s or less, more preferably 125 to 1600 mPa·s, and even more preferably 150 to 1200 mPa·s.

[0028] Component (A-1) is an acrylic compound having 4 to 25 carbon atoms and having 3 or more acryloyl groups in one molecule, preferably 3 to 8 acryloyl groups. From the viewpoint of improving adhesion to the substrate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, and tripentaerythritol octaacrylate, which have 3 or more acryloyl groups in the molecule, are preferred as component (A-1). Particularly preferred are pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, and tripentaerythritol octaacrylate, which have 4 or more acryloyl groups in the molecule.

[0029] Component (A) may further contain (A-2) a hydrocarbon compound which may have heteroatoms and has two or more acryloyl groups in one molecule and a viscosity of 0.1 mPa·s or more and less than 100 mPa·s at 25°C. Examples of the hydrocarbon compound are as described above, and are preferably bifunctional or more, more preferably bifunctional or trifunctional acrylic compounds having 4 to 25 carbon atoms. Component (A-2) is, as described above, a hydrocarbon compound which may have one or more acryloyl groups in one molecule and may have heteroatoms, but is more preferably a hydrocarbon compound which does not have a urethane structure. Furthermore, it may be an acrylic compound which does not have an oxyethylene structure. The viscosity of component (A-2) is preferably 0.5 mPa·s or more and less than 90 mPa·s, and more preferably 1 mPa·s or more and less than 80 mPa·s.

[0030] Component (A-2) is effective in reducing the viscosity of component (A). Component (A-2) is an acrylic compound that preferably has 2 to 5 acryloyl groups, preferably 2 or 3. If the viscosity of the acrylic compound (A-1) described above is high and the coating properties are poor, the viscosity of component (A) can be adjusted to the above range by using component (A) (A-2), which is a low-viscosity acrylic compound, in combination. Examples of low-viscosity acrylic compounds (A-2) include monofunctional acrylic compounds such as isobutyl acrylate, n-octyl acrylate, and hexadecyl acrylate; difunctional acrylic compounds such as 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, and tripropylene glycol diacrylate; and trifunctional acrylic compounds such as trimethylolpropane triacrylate and trimethylolpropaneethoxytriacrylate. It is preferable to use a difunctional or trifunctional acrylic compound so as not to impair substrate adhesion.

[0031] The amount of component (A) in this composition is 99.99 to 50 parts by mass, preferably 99.99 to 60 parts by mass, more preferably 99.99 to 90 parts by mass, even more preferably 99.99 parts by mass or less but greater than 90 parts by mass, and even more preferably 98.5 to 90.1% by mass, based on 100 parts by mass of the total of components (A) and (B). The release agent composition of the present invention is characterized by containing the above-mentioned hydrocarbon compound having an acrylic group (A) as the main component. The amount of component (A) in the whole release agent composition is 99.89 to 43.48% by mass, preferably 99.89 to 52.17% by mass, more preferably 99.89 to 78.26% by mass, and even more preferably 98.4 to 78.35% by mass.

[0032] The amount of component (A-1) in component (A) is preferably 50 to 100 parts by mass, more preferably 55 to 100 parts by mass, and even more preferably 60 to 100 parts by mass, per 100 parts by mass of component (A), in order to obtain a sufficient substrate adhesion effect. Component (A) may consist only of component (A-1).

[0033] The amount of component (A-2) in component (A) is preferably 0 to 50 parts by mass, more preferably 0 to 45 parts by mass, and even more preferably 0 to 40 parts by mass, per 100 parts by mass of component (A). If component (A-2) is essential, the amount is preferably 1 to 50 parts by mass, more preferably 3 to 45 parts by mass, and even more preferably 5 to 40 parts by mass, per 100 parts by mass of component (A).

[0034] More preferably, component (A) of the present invention is a combination of 50 to 99 parts by mass of component (A-1) and 1 to 50 parts by mass of component (A-2). The combination is preferably such that the viscosity of the entire component (A) at 25°C is 50 mPa·s to 2000 mPa·s. More preferably, it is a combination of 50 to 99 parts by mass of component (A-1) and 1 to 50 parts by mass of component (A-2), and even more preferably, a combination of 55 to 97 parts by mass of component (A-1) and 3 to 45 parts by mass of component (A-2). When using component (A-1) and component (A-2) in combination, it is preferable to mix them beforehand and adjust the viscosity so that it falls within the above range.

[0035] (B) Organopolysiloxane having a (meth)acryloyl group The present invention is characterized by incorporating an organopolysiloxane having a (meth)acryloyl group in a small amount relative to the amount of the hydrocarbon compound having an acrylic group (A) described above. The amount of component (B) is such that the weight ratio (A) / (B) with component (A) is 99.99 / 0.01 to 50 / 50, more preferably (A) / (B) is 99.99 / 0.01 to 60 / 40, even more preferably (A) / (B) is 99.99 / 0.01 to 90 / 10, even more preferably (A) / (B) is 99.9 / 0.1 to more than 90 / less than 10, and even more preferably (A) / (B) is 98.5 / 1.5 to 90.1 / 9.9. If the amount of component (B) relative to component (A) is greater than the above upper limit, the adhesion improvement effect of the cured product provided by component (A) may be insufficient. If the amount of component (B) relative to component (A) is less than the above lower limit, the peelability of the cured product provided by component (B) may be insufficient.

[0036] In other words, the amount of component (B) in this release agent composition is 0.01 to 50 parts by mass, more preferably 0.01 to 40 parts by mass, based on 100 parts by mass of the total of components (A) and (B).

[0037] From the viewpoint of the dispersibility of the release agent composition, the amount of component (B) is preferably 0.01 to 10 parts by mass per 100 parts by mass of the total of components (A) and (B), preferably 0.01 parts by mass or more and less than 10 parts by mass, more preferably 0.1 to 9.9 parts by mass, even more preferably 1.5 to 9.9 parts by mass, and even more preferably 1.5 to 9 parts by mass. By keeping the amount of component (B) below the above upper limit, it is possible to provide a release agent composition that has excellent substrate adhesion while also having superior dispersibility.

[0038] Component (B) is an organopolysiloxane having a (meth)acryloyl group represented by the following formula (1). [ka] In the above equation (1), R 1 These are independently substituted or unsubstituted monovalent hydrocarbon groups having 1 to 11 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, hydroxyl groups, hydroxyl group-containing organic groups, halogen atom-containing organic groups, or (meth)acryloyl group-containing organic groups, R 1 At least one of these is an organic group containing a (meth)acryloyl group, a is a number of 2 or more, b is a number of 0 or more, c is a number of 0 or more, d is a number of 0 or more, 2 ≤ a + b + c + d ≤ 1,000, and the siloxane units shown in the parentheses above may be arranged randomly or form a block structure.

[0039] R 1 These are, independently of each other, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 11 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, a hydroxyl group-containing organic group, a halogen atom-containing organic group, or a (meth)acryloyl group-containing organic group, R 1At least one of these is an organic group containing a (meth)acryloyl group. Examples of monovalent hydrocarbon groups having 1 to 11 carbon atoms include alkyl groups such as methyl, ethyl, propyl, and butyl groups, cycloalkyl groups such as cyclohexyl groups, and aryl groups such as phenyl and tolyl groups. Some or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with functional groups such as alkoxy groups or halogen atoms. Examples of alkoxy groups having 1 to 5 carbon atoms include methoxy, ethoxy, isopropoxy, and butoxy groups. Examples of organic groups containing a hydroxyl group include, for example, a group in which at least one of the hydrogen atoms bonded to the carbon atoms of the hydrocarbon group is substituted with a hydroxyl group, such as a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group. Examples of organic groups containing a halogen atom include, for example, a group in which at least one of the hydrogen atoms bonded to the carbon atoms of the hydrocarbon group is substituted with a halogen atom, such as a chloromethyl group, a chloroethyl group, a chloropropyl group, a bromomethyl group, a bromoethyl group, and a bromopropyl group.

[0040] In formula (1) above, the (meth)acryloyl group-containing organic group is, for example, a group in which at least one hydrogen atom bonded to the carbon atom of the hydrocarbon group is substituted with a (meth)acryloyl group. Preferably, it is a monovalent hydrocarbon group having 2 to 10 carbon atoms having at least one (meth)acryloyloxy group, or a (poly)oxyalkylene alkyl group having 4 to 25 carbon atoms. More preferably, it is a monovalent hydrocarbon group having 3 to 6 carbon atoms having at least one (meth)acryloyloxy group, or a (poly)oxyalkylene alkyl group having 5 to 16 carbon atoms. Even more preferably, it is a monovalent hydrocarbon group having 2 to 10 carbon atoms having one (meth)acryloyloxy group at its terminus, or a (poly)oxyalkylene alkyl group having 4 to 25 carbon atoms, and even more preferably, it is a monovalent hydrocarbon group having 3 to 6 carbon atoms, or a (poly)oxyalkylene alkyl group having 5 to 16 carbon atoms. The oxyalkylene group is preferably an oxyethylene group and an oxyisopropylene group, and may have two or more oxyalkylene groups.

[0041] In the above formula (1), R 1 at least one of which is a (meth)acryloyl group-containing organic group. The position where the (meth)acryloyl group-containing organic group binds is not particularly limited, and R 1 3SiO 1 / 2 unit, R 1 2SiO 2 / 2 unit, and R 1 SiO 3 / 2 It may be bonded to any silicon atom of the unit. Preferably, the (meth)acryloyl group-containing organic group is bonded to the silicon atom of the R 1 3SiO 1 / 2 unit or the R 1 2SiO 2 / 2 unit. Also, the number of (meth)acryloyl group-containing organic groups bonded to one silicon atom is preferably one. More preferably, RR 3 2SiO 1 / 2 unit or RR 3 SiO 2 / 2 The (meth)acryloyl group-containing siloxane unit represented by the unit (in the above formula, R is a (meth)acryloyl group-containing organic group among the groups represented by the above R 1 , and R 3 is a group other than the (meth)acryloyl group-containing organic group among the groups represented by the above R 1 ) has at least two in one molecule.

[0042] The (meth)acryloyl group-containing organic group more preferably has the following structure.

Chemical formula

[0043] In the above formula, R 2is a hydrogen atom or a methyl group. e is a positive number from 1 to 10, and f and g are independently positive numbers from 1 to 5. Preferably, e is a positive number from 1 to 7, and f and g are independently positive numbers from 1 to 3. More preferably, e is a positive number from 1 to 4, and f and g are independently 1 or 2. In the above formula, the bonding order of the ethylene oxide and propylene oxide shown in parentheses is not limited and may be randomly arranged or form a block structure. In the formula, the dashed line indicates a bond with the silicon atom of the organopolysiloxane.

[0044] In the average composition formula (1), a, b, c, and d are numbers satisfying a≧2, b≧0, c≧0, d≧0, and 2≦a+b+c+d≦1,000. Preferably, a is a number from 2 to 32, more preferably from 2 to 20. b is a number from 0 to 998, more preferably from 1 to 998, even more preferably from 10 to 798, and even more preferably from 20 to 600. Most preferably from 50 to 400. c is a number from 0 to 10, more preferably from 0 to 6, and even more preferably from 0 to 2. d is a number from 0 to 10, more preferably from 0 to 6. a+b+c+d is from 2 to 1000, preferably from 3 to 800, more preferably from 20 to 700, more preferably from 40 to 500, and even more preferably from 50 to 420.

[0045] In the above average composition formula (1), the ratio of the number of silicon atoms to which the (meth)acryloyl group-containing organic group is bonded to the total number of silicon atoms is preferably 1 to 50%, more preferably 2 to 40%, and more preferably 3 to 30%. In particular, when the number of silicon atoms to which the (meth)acryloyl group-containing organic group is bonded is greater than 1%, the curability when cured by radiation is good. Also, when the number of silicon atoms to which the (meth)acryloyl group-containing organic group is bonded is less than 50%, the peelability of the cured layer obtained by curing is good.

[0046] The above (B) (meth)acryloyl group-containing organopolysiloxane preferably satisfies the above range in terms of the ratio of silicon atoms to which the (meth)acryloyl group-containing organic group is bonded, and the organopolysiloxane has a viscosity of 5 to 10,000 mPa·s at 25°C, more preferably 10 to 5,000 mPa·s. Viscosity is a value measured with a BM-type rotational viscometer.

[0047] (B) component is more preferably (B-1) An organopolysiloxane containing a (meth)acryloyl group, represented by the average composition formula (1) above, wherein the number of silicon atoms to which the (meth)acryloyl group-containing organic group is bonded is 7.5% or more and 20% or less of the total number of silicon atoms, and (B-2) Preferably contains at least one selected from (meth)acryloyl group-containing organopolysiloxanes represented by the average composition formula (1) above, wherein the number of silicon atoms to which the (meth)acryloyl group-containing organic group is bonded is 1% or more and less than 7.5% of the total number of silicon atoms. Component (B) may be one or more selected from the (meth)acryloyl group-containing organopolysiloxanes represented by components (B-1) and (B-2) above. Preferably, it is either one of the above components (B-1) and (B-2), or a combination of at least one of the above components (B-1) and at least one of the above components (B-2).

[0048] In component (B-1), the proportion of silicon atoms to which the (meth)acryloyl group-containing organic group is bonded (hereinafter referred to as the acrylic group content) is preferably 7.5% to 15%, more preferably 7.5% to 12.5%. In component (B-2), the acrylic group content is preferably 1.5% to less than 7.5%, more preferably 2% to less than 7.5%. By incorporating an organopolysiloxane with an acrylic group content within the above range, a cured product with better release properties (light release properties) can be provided. The stripping agent composition of the present invention may further contain, in combination with component (B-1) and / or component (B-2), one or more of the above-mentioned (meth)acryloyl group-containing organopolysiloxanes other than components (B-1) and (B-2) represented by formula (1).

[0049] Component (B) preferably contains at least component (B-2) above. More preferably, the content of component (B-2) relative to 100 parts by mass of the total of components (A) and (B) above is less than 10 parts by mass. This is because, while component (B-2) exhibits good peelability, it acts as a migration component and may reduce the adhesive strength of the peeled tape. By including component (B-2) alone or in combination with component (B-1) at a level below the above upper limit, the adhesive strength of the tape peeled from the cured film is improved.

[0050] The amount of component (B-2) is preferably less than 10 parts by mass, more preferably 9.2 parts by mass or less, even more preferably 9 parts by mass or less, even more preferably 8 parts by mass or less, and may also be 4.8 parts by mass or less, based on 100 parts by mass of the total of components (A) and (B). The lower limit is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and even more preferably 0.5 parts by mass or more. That is, the amount of component (B-2) may be 0.01 parts by mass or more and less than 10 parts by mass, more preferably 0.1 parts by mass or more and 9.2 parts by mass or less, even more preferably 0.1 parts by mass or more and 9 parts by mass or less, even more preferably 0.1 parts by mass or more and 8 parts by mass or less, and even more preferably 0.5 parts by mass or more and 4.8 parts by mass or less.

[0051] The amount of component (B-1) is not particularly limited and should be appropriately adjusted so that the total amount of component (B) relative to the amount of component (A) falls within the range described above. Preferably, the amount of component (B-1) is 0.01 to 50 parts by mass, more preferably 0.01 to 40 parts by mass, more preferably 0.01 to 10 parts by mass, more preferably 0.01 parts by mass or more and less than 10 parts by mass, more preferably 0.1 to 9.9 parts by mass, even more preferably 1.5 to 9.9 parts by mass, and even more preferably 1.5 to 9 parts by mass, based on 100 parts by mass of the total of components (A) and (B). Component (B) of the present invention may consist only of the above-mentioned component (B-1) and may not contain the above-mentioned component (B-2), but it is preferable to include at least the above-mentioned component (B-2).

[0052] The (meth)acryloyl group-containing organopolysiloxanes described above can be obtained by known methods. For example, they can be obtained by an acid equilibration reaction using an acid catalyst as described in Japanese Patent Application Publication No. 04-239526.

[0053] (C) Radical polymerization initiator Component (C) is a radical polymerization initiator that generates radicals upon irradiation. The radical polymerization initiator is not particularly limited as long as it has the ability to generate radicals upon irradiation. For example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2-methylpropiophenone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]-phenyl}-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-mol Forin-4-ylphenyl)-butan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxydi-2-methyl-1-propan-1-one, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethyl Tylamino-1-(4-morpholinophenyl)-butanone-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, methyl benzoingate, benzyl, anisyl, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, ethyl(mesitylcarbonyl)phenylphosphine oxide D, Benzophenone, o-Methyl benzoylbenzoate, Michler ketone, 4,4'-Bis-diethylaminobenzophenone, 4,4'-Dichlorobenzophenone, 4-Benzoyl-4'-Methyldiphenyl sulfide, Thioxanthone, 2-Methylthioxanthone, 2-Ethylthioxanthone, 2-Chlorothioxanthone, 2-Isopropylthioxanthone, 2,4-Diethylthioxanthone, 1,2-Octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime)], Ethanone,Examples include 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]- and 1-(O-acetyloxime)bis(cyclopentadienyl)-bis(2,6-difluoro-3-(pyru-1-yl)titanium). The above radical polymerization initiators may be used individually or in combination of two or more depending on the desired performance.

[0054] (C) The amount of radical polymerization initiator added is 0.1 to 15 parts by mass, preferably 0.5 to 12 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of the total of components (A) and (B). If the amount of component (C) is less than the lower limit, sufficient curability may not be obtained. If it exceeds the upper limit, good release properties may not be obtained.

[0055] The release agent composition of the present invention is obtained by mixing the above components. The resulting composition may be cloudy, but it is preferable that it does not separate for a long period of time. For example, it is preferable that a uniform cloudy composition, obtained by mixing and stirring under light-shielding conditions at 25°C, is not separated into an upper and lower layer when the composition is visually inspected after being allowed to stand for a predetermined time under the same light-shielding conditions at 25°C. The standing time for checking the separation of the composition can be adjusted according to the amount of silicone component in the release agent composition, but may be, for example, 4 hours, 4.5 hours, or 5 hours. It is preferable that separation does not occur when the composition is allowed to stand for a desired time according to the amount of silicone component. As a result, the release agent composition has a good pot life and the quality when made into release liners is less likely to vary.

[0056] The separation of the above composition occurs when component (A) and component (B) separate. In order to extend the time until the composition separates and ensure a good pot life, it is more effective to reduce the amount of component (B) relative to component (A). Therefore, the amount of component (B) described above may more preferably be such that the weight ratio (A) / (B) of component (B) is 99.99 / 0.01 to more than 90 / less than 10, or such that the weight ratio (A) / (B) is 99.9 / 0.1 to 90.1 / 9.9, or even such that the weight ratio (A) / (B) is 98.5 / 1.5 to 90.1 / 9.9, or even such that the weight ratio (A) / (B) is 98.5 / 1.5 to 91 / 9. Including component (B) within the above range is preferable because it improves the dispersibility of component (B) in component (A) and extends the time until component (A) and component (B) separate.

[0057] In addition to components (A) to (C) above, the release agent composition of the present invention may further contain optional additives such as silicone resin, polydimethylsiloxane, fillers, antistatic agents, flame retardants, defoamers, flow regulators, light stabilizers, solvents, non-reactive resins, and radical polymerizable compounds. The amount of optional additives can be appropriately selected based on conventionally known release agent compositions, as long as it does not hinder the effects of the present invention.

[0058] The release agent composition of the present invention can be applied to various substrates and radiation-cured to form a release liner. The substrate is not particularly limited and can be any substrate commonly used for release liners. Examples include glassine paper, clay coated paper, fine paper, polyethylene laminated paper, thermal paper, plastic films such as polyester film, polystyrene film, polyethylene film, and polypropylene film, transparent resins such as polycarbonate, and metal foils such as aluminum foil. Furthermore, the amount of release agent composition applied is not particularly limited and is usually 0.05 to 3.0 g / m². 2 A certain degree is acceptable.

[0059] Radiation curing can be carried out according to conventionally known methods. For example, as the radiation energy beam, preferably an energy beam in the ultraviolet to visible light region (approximately 100 to approximately 800 nm) obtained from high-pressure or ultra-high-pressure mercury lamps, metal halide lamps, xenon lamps, carbon arc lamps, fluorescent lamps, semiconductor solid-state lasers, argon lasers, He-Cd lasers, KrF excimer lasers, ArF excimer lasers, F2 lasers, UV-LEDs, etc. is used. Preferably, the radiation light source has strong photohardness at 200 to 400 nm, and more preferably a metal halide lamp, high-pressure or ultra-high-pressure mercury lamp, or UV-LED. Furthermore, high-energy radiation such as electron beams and X-rays can also be used. The irradiation time of the radiation energy is usually sufficient to be about 0.1 to 10 seconds at room temperature, but if the transmittance of the energy beam is low or if the film thickness of the curable composition is thick, it may be preferable to irradiate for a longer time. If necessary, after irradiation with energy beams, it is also possible to heat at room temperature to 150°C for several seconds to several hours for after-curing.

[0060] If necessary, the stripping agent composition of the present invention may be diluted with an organic solvent before use. The type of organic solvent is not particularly limited and any conventionally known solvent used in stripping agent compositions may be used. Examples include aromatic hydrocarbon compounds such as toluene and xylene, aliphatic hydrocarbon compounds such as hexane, heptane, octane, and nonane, alcohols such as methanol, ethanol, isopropyl alcohol, and butanol, ester compounds such as ethyl acetate and butyl acetate, and ketone compounds such as acetone and methyl ethyl ketone.

[0061] The release agent composition of the present invention can be cured by radiation even in air, but it is preferable to cure it by lowering the oxygen concentration in order to improve curability. Since curability improves as the oxygen concentration decreases, a lower oxygen concentration is preferable. For example, the oxygen concentration is 1 volume%, preferably 0.1 volume%, and more preferably 0.01 volume%. [Examples]

[0062] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. Furthermore, the physical properties listed in the table below were measured using the following test methods. Viscosity is the value measured at 25°C using a BM-type rotational viscometer. In the structural formula, Me represents a methyl group.

[0063] [Peel force measurement test of release liner] Distribute the release agent composition at a rate of approximately 1.0 g / m² on polyethylene laminate paper. 2 The coating was applied using a roll coating method, and two 120W / cm metal halide lamps with an oxygen concentration of 150ppm were used to irradiate the 365nm wavelength at an energy of 100mJ / cm². 2 A release liner with a cured film was prepared by irradiating it with ultraviolet light to achieve the desired result. After storing the obtained release liner at 25°C for 20 hours, a 25 mm wide acrylic adhesive tape TESA7475 (Tesa SE) was applied to the surface of the cured film, and a 2 kg roller was pressed down once to prepare a sample for peel force measurement. 70 g / cm³ was applied to this sample. 2 The samples were aged at 25°C for 20-24 hours under a load. Afterward, a tensile testing machine was used to measure the force (N / 25mm) required to tensile and peel the bonded adhesive tapes at a 180° angle and a peeling speed of 0.3 m / min. The results are shown in Tables 1 and 2.

[0064] If the cured product of the release agent composition has a peeling force of 1.75 N / 25 mm or less, as measured by the method described above, the cured product is evaluated as having good peelability. Preferably, the peeling force of the cured product is 1.25 N / 25 mm or less, and more preferably 0.75 N / 25 mm or less.

[0065] [Residual adhesion rate of adhesive tape] A sample for measuring peeling force was prepared using the same method as described above. 70 g / cm³ was added to the sample. 2The tapes were aged at 25°C for 20-24 hours under a load. Afterward, the bonded tapes were peeled off at a 180° angle at a peeling speed of 0.3 m / min using a tensile testing machine, and the tape was then attached to a SUS plate. A 2 kg roller was applied for one pass, and the force (Y) required to peel the tape off after 30 minutes at 25°C was measured. For comparison, the force (Z) required to peel off TESA7475 acrylic adhesive tape (not bonded to a release liner) from the SUS plate was measured. The residual adhesion rate was calculated by dividing (Y) by (Z). The results are shown in Tables 1 and 2.

[0066] [Adhesion test of release liners (glassine paper, thermal paper)] The release agent composition is applied to glassine paper (manufactured by Sappi) and thermal paper (manufactured by Jujo Thermal) at a rate of approximately 1.0 g / m² each. 2 The coating was applied using a roll coating method, and two 120W / cm metal halide lamps with an oxygen concentration of 150ppm were used to irradiate the 365nm wavelength with an irradiation energy of 100mJ / cm². 2 Two types of release liners with a cured film were created by irradiating them with ultraviolet light. After storing the release liners in a moist heat dryer at 60°C and 90% RH for 7 days, the cured film was rubbed 10 times with a finger to check its adhesion to the substrate. A circle (○) was used if no clouding or detachment was observed in the cured film, and a cross (×) was used if clouding or detachment of the cured film from the substrate was observed. The results are shown in Tables 1 and 2.

[0067] The components used in the examples and comparative examples are as follows: (A) Hydrocarbon compounds having an acrylic group (a1-1) Ditrimethylolpropanetetraacrylate (manufactured by SINOCURE CHEMICAL, viscosity at 25°C: 890 mPa·s) (a2-1) Tripropylene glycol diacrylate (manufactured by Tokyo Chemical Industry Co., Ltd., viscosity at 25°C: 12 mPa·s) (a2-2) Trimethylolpropane triacrylate (manufactured by Tokyo Chemical Industry Co., Ltd., viscosity at 25°C: 70 mPa·s)

[0068] (B) Acryloyl group-containing polydimethylsiloxane (b1) Acryloyl group-containing polydimethylsiloxane represented by the following average composition formula (2) and having a viscosity of 420 mPa·s at 25°C. [ka] In the above component (b1), the acryloyl group-containing organic group (R) is relative to the total number of silicon atoms. 4 The proportion of silicon atoms having ) is 8.9%.

[0069] (b2) Acryloyl group-containing polydimethylsiloxane represented by the following average composition formula (3) and having a viscosity of 180 mPa·s at 25°C [ka] In the above component (b2), the acryloyl group-containing organic group (R) is relative to the total number of silicon atoms. 4 The proportion of silicon atoms containing ) is 4.9%.

[0070] (C) Radical polymerization initiator (c1)2-Hydroxy-2-methyl-1-phenylpropan-1-one

[0071] [Example 1] Mixing 81.8 parts by mass of (a1-1) ditrimethylolpropanetetraacrylate and 9.1 parts by mass of (a2-1) tripropylene glycol diacrylate prepared a mixture (A1) having a viscosity of 450 mPa·s at 25°C. A radiation-curable release agent composition was prepared by mixing 90.9 parts by mass of the above mixture (A1), 9.1 parts by mass of (b1) acryloyl group-containing polydimethylsiloxane represented by the above average composition formula (2), and 5 parts by mass of the above (c1) radical polymerization initiator.

[0072] [Example 2] In Example 1 described above, the process of Example 1 was repeated except that 9.1 parts by mass of component (b1) was replaced with 7.3 parts by mass of component (b1) and 1.8 parts by mass of acryloyl group-containing polydimethylsiloxane represented by the average composition formula (3) described above (b2) to obtain a release agent composition.

[0073] [Example 3] In Example 1 described above, the process of Example 1 was repeated except that 9.1 parts by mass of component (b1) was replaced with 9.1 parts by mass of component (b2) to obtain a release agent composition.

[0074] [Example 4] Mixing 85.5 parts by mass of (a1-1) ditrimethylolpropanetetraacrylate and 9.5 parts by mass of (a2-1) tripropylene glycol diacrylate prepared a mixture (A2) having a viscosity of 450 mPa·s at 25°C. A release agent composition was prepared by mixing 95 parts by mass of the above mixture (A2), 4 parts by mass of (b1) acryloyl group-containing polydimethylsiloxane represented by the above average composition formula (2), 1 part by mass of (b2) acryloyl group-containing polydimethylsiloxane represented by the above average composition formula (3), and (c1) 5 parts by mass of a radical polymerization initiator.

[0075] [Example 5] In Example 4 described above, the process of Example 4 was repeated except that 4 parts by mass of component (b1) and 1 part by mass of component (b2) were replaced with 5 parts by mass of component (b2) to obtain a release agent composition.

[0076] [Example 6] 88.2 parts by mass of (a1-1) ditrimethylolpropanetetraacrylate and 9.8 parts by mass of (a2-1) tripropylene glycol diacrylate were mixed to prepare a mixture (A3) having a viscosity of 450 mPa·s at 25°C. A release agent composition was prepared by mixing 98 parts by mass of the above mixture (A3), 1.6 parts by mass of (b1) acryloyl group-containing polydimethylsiloxane represented by the above average composition formula (2), 0.4 parts by mass of (b2) acryloyl group-containing polydimethylsiloxane represented by the above average composition formula (3), and (c1) 5 parts by mass of a radical polymerization initiator.

[0077] [Example 7] In Example 6, the process was repeated except that 1.6 parts by mass of component (b1) and 0.4 parts by mass of component (b2) were replaced with 2 parts by mass of component (b2) to obtain a release agent composition.

[0078] [Example 8] A mixture (A4) having a viscosity of 450 mPa·s at 25°C was prepared by mixing 63 parts by mass of (a1-1) ditrimethylolpropanetetraacrylate and 7 parts by mass of (a2-1) tripropylene glycol diacrylate. A release agent composition was prepared by mixing 70 parts by mass of the above mixture (A4), 24 parts by mass of (b1) acryloyl group-containing polydimethylsiloxane represented by the above average composition formula (2), 6 parts by mass of (b2) acryloyl group-containing polydimethylsiloxane represented by the above average composition formula (3), and 5 parts by mass of (c1) radical polymerization initiator.

[0079] [Example 9] 81.8 parts by mass of (a1-1) ditrimethylolpropanetetraacrylate and 9.1 parts by mass of (a2-2) trimethylolpropanetriacrylate were mixed to prepare a mixture (A5) having a viscosity of 611 mPa·s at 25°C. In Example 2 described above, the process of Example 2 was repeated except that the above mixture (A1) was replaced with 90.9 parts by mass of the above mixture (A5) to obtain a release agent composition.

[0080] [Example 10] The process of Example 2 was repeated except that the above mixture (A1) was replaced with 90.9 parts by mass of component (a1-1) (viscosity 890 mPa·s) to obtain a release agent composition.

[0081] [Comparative Example 1] A mixture (A6) having a viscosity of 450 mPa·s at 25°C was prepared by mixing 90 parts by mass of (a1-1) ditrimethylolpropanetetraacrylate and 10 parts by mass of (a2-1) tripropylene glycol diacrylate. A release agent composition was prepared by mixing 100 parts by mass of the above mixture (A6) with 5 parts by mass of the above (c1) radical polymerization initiator.

[0082] [Comparative Example 2] (b1) A release agent composition was prepared by mixing 100 parts by mass of acryloyl group-containing polydimethylsiloxane represented by the average composition formula (2) above with 5 parts by mass of the radical polymerization initiator (c1) above.

[0083] [Comparative Example 3] Nine parts by mass of (a1-1) ditrimethylolpropanetetraacrylate and one part by mass of (a2-1) tripropylene glycol diacrylate were mixed to prepare a mixture (A7) having a viscosity of 450 mPa·s at 25°C. A release agent composition was prepared by mixing 10 parts by mass of the above mixture (A7), 72 parts by mass of acryloyl group-containing polydimethylsiloxane represented by the above average composition formula (2) (b1), 18 parts by mass of acryloyl group-containing polydimethylsiloxane represented by the above average composition formula (3) (b2), and 5 parts by mass of a radical polymerization initiator (c1).

[0084] [Comparative Example 4] A release agent composition was prepared by mixing 10 parts by mass of (a2-2) trimethylolpropane triacrylate, 90 parts by mass of (b1) acryloyl group-containing polydimethylsiloxane represented by the average composition formula (2), and 5 parts by mass of (c1) radical polymerization initiator.

[0085] [Comparative Example 5] A mixture (A8) having a viscosity of 20 mPa·s at 25°C was prepared by mixing 18 parts by mass of (a1-1) ditrimethylolpropanetetraacrylate and 72 parts by mass of (a2-1) tripropylene glycol diacrylate. A release agent composition was prepared by mixing 90 parts by mass of the above mixture (A8), 10 parts by mass of (b1) acryloyl group-containing polydimethylsiloxane represented by the above average composition formula (2), and 5 parts by mass of the above (c1) radical polymerization initiator. When an attempt was made to create a release liner using this release agent composition, the viscosity was too low and roll coating was not possible.

[0086] The release agent compositions obtained in the above examples and comparative examples were evaluated for their release properties and substrate adhesion according to the method described above. The results are shown in Tables 1 and 2.

[0087] [Table 1]

[0088] [Table 2]

[0089] As shown in Table 2, the release liner obtained using the release agent compositions of Comparative Examples 3 and 4, which mainly consist of polyorganosiloxane having acryloyl groups and have a low content of hydrocarbon compounds having acrylic groups, and the release agent composition of Comparative Example 2, which does not contain hydrocarbon compounds having acrylic groups, exhibits poor adhesion to glassine paper and thermal paper. Furthermore, the release agent composition of Comparative Example 1, which does not contain organopolysiloxane, exhibits poor release properties. The release agent composition of Comparative Example 5, which has too low a viscosity for the acrylic group-containing hydrocarbon compound, has low viscosity and results in poor coating. In contrast, as shown in Table 1, the release liner having a cured layer made from the release agent composition of the present invention exhibits high adhesion to glassine paper and thermal paper.

[0090] Furthermore, as shown in the examples in Table 1, by adjusting the composition of organopolysiloxane (B), a release liner with superior ease of peeling while maintaining high substrate adhesion can be obtained. Also, as shown in the comparison between Example 2 and Example 3, the residual adhesion rate of the release liner can be adjusted while ensuring excellent substrate adhesion and ease of peeling, depending on the content ratio of organopolysiloxane with a low acrylic group content in the composition.

[0091] [Assessment of variance] The dispersibility of the release agent compositions of Examples 1 to 10 described above was evaluated. The evaluation method is as follows. Components (A), (B), and (C) were added to a 200 mL separable flask equipped with a stirring device, totaling 100 g. The mixture was stirred at a stirring speed of 200 rpm for 10 minutes at 25°C under light-shielded conditions to prepare the mixture. Then, 100 g of the resulting mixture was transferred to a glass bottle and allowed to stand for 4 hours at 25°C under light-shielded conditions. After standing, the mixture was visually inspected to see if a separation interface between the upper and lower layers was visible. As evaluated as described above, the release agent compositions of Examples 1-7, 9, and 10 exhibited excellent dispersibility. On the other hand, the release agent composition of Example 8 showed an interface between the upper and lower layers after 4 hours of standing, and its dispersibility was inferior to that of the release agent compositions of Examples 1-7, 9, and 10. Therefore, by further adjusting the amount of component (B) to less than 10% by mass relative to 100 parts by mass of the total of components (A) and (B), it is possible to provide a release agent composition with even better dispersibility while achieving the effects of the present invention described above. [Industrial applicability]

[0092] The cured product comprising the release agent composition of the present invention exhibits high adhesion to substrates such as glassine paper and thermal paper. Furthermore, it provides a release liner that is easily peeled while maintaining high adhesion to the substrate. Therefore, the release agent composition of the present invention is useful as a release liner composition for release paper and release film for various adhesive substances.

Claims

1. A stripping agent composition containing the following components (A), (B), and (C). (A) One or more hydrocarbon compounds having a viscosity of 50 mPa·s to 2000 mPa·s at 25°C, having one or more acryloyl groups in one molecule, and possibly containing heteroatoms: 50 to 99.99 parts by mass (B) Organopolysiloxane containing a (meth)acryloyl group, represented by the following formula (1): 0.01 to 50 parts by mass (provided that the total of component (A) and component (B) is 100 parts by mass) 【Chemistry 1】 (In the formula, R １ R is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 11 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, a hydroxyl group-containing organic group, a halogen atom-containing organic group, or a (meth)acryloyl group-containing organic group, １ At least one of them is an organic group containing a (meth)acryloyl group, where a is a number of 2 or more, b is a number of 0 or more, c is a number of 0 or more, d is a number of 0 or more, 2 ≤ a + b + c + d ≤ 1,000, and the siloxane units shown in the parentheses above may be arranged randomly or form a block structure), and (C) Radical polymerization initiator: 0.1 to 15 parts by mass per 100 parts by mass of the total of components (A) and (B).

2. The stripping agent composition according to claim 1, wherein component (A) contains one or more hydrocarbon compounds that may have heteroatoms, having three or more acryloyl groups in one molecule and a viscosity of 100 mPa·s or more and less than 4000 mPa·s at 25°C, in an amount of 50 parts by mass to 100 parts by mass per 100 parts by mass of component (A), and the total viscosity of component (A) at 25°C is 50 mPa·s to 2000 mPa·s.

3. The stripping agent composition according to claim 2, wherein the component (A) further contains at least one hydrocarbon compound which may have heteroatoms, having two or more acryloyl groups in one molecule and a viscosity of 0.1 mPa·s or more and less than 100 mPa·s at 25°C.

4. The above-mentioned component (A) is, (A-1) 50 to 99 parts by mass of at least one hydrocarbon compound which may have heteroatoms, having three or more acryloyl groups in one molecule and a viscosity of 100 mPa·s or more and less than 4000 mPa·s at 25°C. (A-2) A combination of 1 to 50 parts by mass of at least one hydrocarbon compound which may contain heteroatoms, having two or more acryloyl groups in one molecule and having a viscosity of 0.1 mPa·s or more and less than 100 mPa·s at 25°C, The stripping agent composition according to claim 1, wherein the viscosity of the entirety of component (A) at 25°C is 50 mPa·s to 2000 mPa·s.

5. The stripping agent composition according to claim 1, wherein component (A) is at least one hydrocarbon compound that may have heteroatoms, having three or more acryloyl groups in one molecule (A-1) and a viscosity of 100 mPa·s or more and 2000 mPa·s or less at 25°C.

6. The stripping agent composition according to claim 1, wherein, with respect to 100 parts by mass of the total of components (A) and (B), the amount of component (A) is greater than 90 parts by mass and 99.99 parts by mass or less, and the amount of component (B) is 0.01 parts by mass or more and less than 10 parts by mass.

7. The stripping agent composition according to claim 1, wherein the (B) component comprises at least one of the following (B-1) component and (B-2) component. (B-1) A (meth)acryloyl group-containing organopolysiloxane in which, in the average composition formula (1) above, the ratio of the number of silicon atoms to which the (meth)acryloyl group-containing organic group is bonded to the total number of silicon atoms is 7.5% or more and 20% or less, and (B-2) A (meth)acryloyl group-containing organopolysiloxane in the average composition formula (1) above, wherein the ratio of the number of silicon atoms to which the (meth)acryloyl group-containing organic group is bonded to the total number of silicon atoms is 1% or more and less than 7.5%.

8. The stripping agent composition according to claim 7, wherein, with respect to 100 parts by mass of the total of components (A) and (B), the amount of component (A) is greater than 90 parts by mass and 99.99 parts by mass or less, and the amount of component (B) is 0.01 parts by mass or more and less than 10 parts by mass.

9. The stripping agent composition according to claim 8, wherein component (B) comprises at least component (B-2).

10. The stripping agent composition according to claim 8, wherein, with respect to 100 parts by mass of the total of components (A) and (B), the amount of component (A) is 90.1 parts by mass or more and 98.5 parts by mass or less, and the amount of component (B) is 1.5 parts by mass or more and 9.9 parts by mass or less.

11. The stripping agent composition according to claim 9, wherein the amount of component (B-2) is 9.2 parts by mass or less with respect to 100 parts by mass of the total of component (A) and component (B).

12. A cured product obtained by curing the release agent composition according to any one of claims 1 to 11.

13. A release liner comprising a base material and a layer made of the cured product according to claim 12, which is laminated on at least one surface of the base material.

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