Silicone release agent composition

Abstract

To provide a silicone release agent composition having lower odor than conventional one.SOLUTION: There is provided a silicone release agent composition which comprises (A) 83 to 99.5 pts.mass of a linear, branched or cyclic organopolysiloxane having at least two alkenyl group-containing organic groups in one molecule and 0.001 to 0.20 mol of an alkenyl group in 100 g of an organopolysiloxane, (B) a polyorganohydrogensiloxane having at least three SiH groups in one molecule in an amount such that the ratio of the number of moles of SiH groups in the component (B) to the number of moles of alkenyl groups in the component (A) is 0.6 to 20, (C) a platinum group metal-based catalyst in a catalytic amount, (D) 1 to 20000 pts.mass of at least one solvent selected from terpene and a terpene derivative based on 100 pts.mass of the total of the components (A), (B) and (C), and (E) 0.5 to 10 pts.mass of an addition reaction controlling agent based on 100 pts.mass of the total of the components (A), (B) and (C).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a silicone release agent using an organic solvent.

Background Art

[0002] Conventionally, by forming a cured film of a silicone release agent composition on the surface of a sheet-like substrate such as paper or a plastic film, a sheet-like article having non-adhesiveness and releasability to an adhesive material has been manufactured and used in various fields. These release papers and release films are used not only for protecting the adhesive surface of adhesive tapes and adhesive labels, but also for food processing such as baking molds for pancakes and baking papers, process papers and process films used in the manufacturing processes of synthetic leather and ceramic capacitors, etc., and are widely used in many applications regardless of whether they are daily necessities or industrial products.

[0003] As a method of forming a cured film of a silicone release agent composition on the surface of a sheet-like substrate, for example, as a known technique, a method of forming a release film on the substrate surface by subjecting an alkenyl group-containing organopolysiloxane and an organohydrogenpolysiloxane to an addition reaction using a platinum-based compound as a catalyst has been reported. As other methods of forming a cured film, those by a condensation reaction or irradiation with energy rays such as ultraviolet rays are also used, but the curing method by an addition reaction, which is excellent in terms of curability, release characteristics, equipment cost, etc., has become the mainstream.

[0004] The composition of the silicone release agent cured by addition reaction has in common the point that it contains the above-mentioned alkenyl group-containing organopolysiloxane and organohydrogenpolysiloxane as components for forming a cured film. Furthermore, it is provided on the market in three forms: a solvent type containing a solvent as a diluent, an emulsion type dispersed in water, and a solvent-free type containing no diluent. Although the solvent-free type, which is excellent in safety and risk due to not using a solvent, currently occupies the mainstream of the market, the demand for the solvent type still remains strong. One of the advantages of choosing the solvent type is that thin film coating can be achieved by diluting the silicone release agent composition with a solvent at an arbitrary ratio. In addition, because it has good wettability, coatability, leveling property, uniformity, surface smoothness, and adhesion to the substrate, the solvent type is still often used in applications with high requirements in these property aspects. Although the emulsion type can also be diluted with water as a diluent at an arbitrary ratio, its wettability and coatability are not sufficient compared to the solvent type, and improvement in terms of properties is required to replace the solvent type.

[0005] Previously, awareness of the environment has been increasing in various fields, and many initiatives aiming at sustainable growth under the leadership of countries, regions, or industries have been implemented globally. In addition, new concepts considering the environment, such as the SDGs (Sustainable Development Goals), which are international goals adopted at the United Nations Summit in 2015, are also spreading around the world, which is also boosting efforts regarding the environment.

[0006] As one of those initiatives, it has been proposed to use plant-derived chemicals, which are attracting attention as more sustainable resources, instead of chemicals made from fossil resources as raw materials. For example, cellulose is a useful chemical generally obtained from natural resources such as wood. However, compared with fossil resources that are formed over a long period of time, plant-derived chemicals are excellent from the perspective of sustainability because the collection period is short.

[0007] To produce the above-mentioned solvent-based silicone release agent composition, since the above-mentioned alkenyl group-containing organopolysiloxane, which is the main raw material, is a high-viscosity silicone raw rubber (gum), an organic solvent is required to dissolve it. When processing the silicone release agent composition, an organic solvent in an amount equal to or more than the solid content of the silicone release agent composition is used to adjust the viscosity and coating amount of the coating liquid. From the perspective of compatibility with silicone materials, aromatic solvents such as toluene and xylene are currently mainstream, but hydrocarbon solvents such as hexane and isoparaffin, and ester solvents such as ethyl acetate and butyl acetate are also used (Patent Documents 1 to 3).

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0009] However, due to the specific odors and risks of the above-mentioned organic solvents, sufficient care must be taken in handling them in the working environment. Although there are individual differences in terms of odor, the odors of solvents such as toluene and xylene mentioned above are generally not preferred. Even for the same organic solvent, it is preferable to use a solvent with lower risk and lower odor.

[0010] Therefore, an object of the present invention is to provide a silicone release agent composition with lower odor than conventional ones.

Means for Solving the Problems

[0011] As a result of intensive studies to achieve the above object, the present inventors have found a plant-derived organic solvent that is compatible with a base organopolysiloxane and can volatilize upon heating to form a cured film, and have invented a silicone release agent containing the organic solvent.

[0012] That is, the present invention [1] 83 to 99.5 parts by mass of a linear, branched or cyclic organopolysiloxane having at least two alkenyl group-containing organic groups in one molecule and having 0.001 to 0.20 mol of alkenyl groups in 100 g of the organopolysiloxane, (B) an amount such that the ratio of the number of moles of SiH groups in the component (B) to the number of moles of alkenyl groups in the component (A) of a polyorganohydrogensiloxane having at least three SiH groups in one molecule is 0.6 to 20 (C) a platinum group metal-based catalyst in a catalytic amount, and (D) at least one solvent selected from terpenes and terpene derivatives, 1 to 20,000 parts by mass with respect to 100 parts by mass in total of the components (A), (B) and (C) (E) an addition reaction control agent, 0.5 to 10 parts by mass with respect to 100 parts by mass in total of the components (A), (B) and (C) A silicone release agent composition characterized by containing the same.

[0013] Further, the present invention provides a silicone release agent composition further having at least one configuration selected from the following [2] to [8]. [2] The silicone release agent composition, wherein the component (A1) is represented by the following average formula (1). [Chemical formula] (In formula (1), R 1 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms which may contain a hetero atom, and at least two of R 1 are alkenyl group-containing organic groups having 2 to 10 carbon atoms, a is a positive number of 2 or more, b is a positive number of 1 or more, c and d are positive numbers of 0 or more, and 500 ≦ a + b + c + d ≦ 15000) [3] The component (B) has an average compositional formula: R 2 e H f SiO (4-e-f) / 2 (wherein R 2 are, independently of each other, unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, e > 0, f > 0, and further 0 < e + f ≦ 3) The silicone release agent composition represented by the above formula. [4] The component (D) has a boiling point of 220°C or lower, and the above silicone release agent composition. [5] The component (D) has a boiling point of 200°C or lower, and the above silicone release agent composition. [6] An organopolysiloxane having 10 mol% or more of a siloxane unit having a glycidyl group and / or a glycidoxy group bonded to a silicon atom via a carbon atom in one molecule, and further containing 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (A), the above silicone release agent composition. [7] The above silicone release agent composition further containing 0.1 to 20 parts by mass of one or more selected from a release force control component containing an acrylic-silicone graft copolymer and (G2) linear phenylmethylpolysiloxane with respect to 100 parts by mass of the component (A). [8] (H) R 6 3SiO 1 / 2 units and SiO 4 / 2 units, and (R 6 3SiO 1 / 2 units) / (SiO 4 / 2 units) has a molar ratio of 0.5 to 1.5, a resinous organopolysiloxane (in the above formula, R 6 are, independently of each other, monovalent hydrocarbon groups having 1 to 10 carbon atoms or alkenyl groups having 2 to 10 carbon atoms that do not have an aliphatic unsaturated bond, and optionally R 6Part of it may be a hydrolyzable group or a hydroxyl group having 1 to 10 carbon atoms) is further contained in an amount of 1 to 100 parts by mass based on 100 parts by mass of the component (A). When the component (H) has at least one alkenyl group, the ratio of the number of moles of the SiH group in the component (B) to the number of moles of the alkenyl group in the component (A) and the component (H) is 0.6 to 20. The silicone release agent composition described above. [9] Further, the present invention provides a release sheet having a base material and a cured product formed by curing the above silicone release agent composition on at least one surface of the base material surface.

[10] Further, the present invention provides a method for producing a release sheet by applying the above silicone release agent composition to at least one side of a base material and curing it.

Effects of the Invention

[0014] Since the silicone release agent composition of the present invention has a low odor, it is possible to reduce the odor of the resulting adhesive article and reduce the burden on the operator.

Modes for Carrying Out the Invention

[0015] Hereinafter, the details of the present invention will be described.

[0016] (A) Alkenyl group-containing organopolysiloxane The component (A) is a linear, branched or cyclic organopolysiloxane having at least two alkenyl group-containing organic groups in one molecule. The alkenyl group-containing organic group preferably has 2 to 10 carbon atoms. For example, alkenyl groups such as vinyl group, allyl group, hexenyl group, octenyl group, undecenyl group, acryloylpropyl group, acryloylmethyl group, methacryloylpropyl group, etc. Acryloylalkyl groups and methacryloylalkyl groups, cycloalkenylalkyl groups such as cyclohexenylethyl group, alkenyloxyalkyl groups such as vinyloxypropyl group, and the like. Particularly preferred is a vinyl group.

[0017] The amount of alkenyl groups contained in component (A) is 0.001 to 0.2 mol, preferably 0.001 to 0.15 mol, and more preferably 0.002 to 0.1 mol per 100 g of organopolysiloxane. If it is less than 0.001 mol, the curability when the composition is applied and cured may decrease, while if it is more than 0.2 mol, the releasability of the cured coating of the composition may decrease.

[0018] The alkenyl group-containing organopolysiloxane has a siloxane unit number of 500 to 15,000, preferably 1,000 to 12,000. If the number of siloxane units is less than the lower limit, the composition may have poor coatability and may be difficult to form a uniform coating film. If the number of siloxane units is greater than the upper limit, the composition may have a very high viscosity, resulting in poor handleability. The (A) component may be linear, branched, or cyclic, but is preferably a linear or branched organopolysiloxane, and more preferably a linear organopolysiloxane.

[0019] The organopolysiloxane is preferably represented by the following average formula (1). [ka] In formula (1), R 1 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms which may contain a heteroatom, and R 1 At least two of the above are alkenyl-containing organic groups having 2 to 10 carbon atoms. a is a positive number of 2 or more, b is a positive number of 1 or more, c and d are positive numbers of 0 or more, and 500≦a+b+c+d≦15000. There are no particular limitations on the bonding sites of the alkenyl-containing organic groups, but R 1 3SiO 1 / 2 and R 1 2SiO 2 / 2 R bonded to unit 1 At least two of these are preferably alkenyl-containing organic groups.

[0020] In the above formula (1), R1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms which may contain a heteroatom, and R 1 Among them, at least two are alkenyl group-containing organic groups. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group, etc. Some or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with halogen atoms or other groups. For example, trifluoromethyl group, 3,3,3-trifluoropropyl group, etc. are exemplified. Among them, a saturated aliphatic group or an aromatic group is preferable, and a methyl group and a phenyl group are particularly preferable. The alkenyl group-containing organic group is as described above.

[0021] Regarding a to d in the above formula (1), a is a positive number of 2 or more, preferably 2 to 100, more preferably 2 to 80, still more preferably 2 to 60. When a is less than 2, the viscosity becomes too high and it becomes difficult to handle the composition. b is a positive number of 1 or more, preferably 1000 to 12000. When it is smaller than the above lower limit value, the viscosity is too low and the coatability of the composition deteriorates. c and d are positive numbers of 0 or more, preferably positive numbers of 0 to 30. It is not preferable that c and d are simultaneously 0 because the curability of the composition may be lowered. 500 ≦ a + b + c + d ≦ 15000, preferably 1000 ≦ a + b + c + d ≦ 12000. When a + b + c + d is smaller than the above lower limit value, the coatability of the composition deteriorates and it may be difficult to form a uniform coating film. When it is larger than the above upper limit value, the viscosity of the composition becomes very high and there is a risk that the handleability deteriorates.

[0022] Component (A) is usually produced by ring-opening polymerization of a cyclic low molecular weight siloxane such as octamethylcyclotetrasiloxane using a catalyst. Since it contains the cyclic low molecular weight siloxane which is the raw material after polymerization, it is preferable to use the one from which the cyclic low molecular weight siloxane is distilled off while passing an inert gas through the reaction product under heating and reduced pressure.

[0023] (A) component preferably includes, but is not limited to, linear or branched organopolysiloxanes represented by the following general formula. R 1-1 R 1-2 2SiO(R 1-2 2SiO) L SiR 1-2 2R 1-1 R 1-1 R 1-2 2SiO(R 1-2 2SiO) L (R 1-1 R 1-2 SiO) m SiR 1-2 2R 1-1 R 1-1 3SiO(R 1-2 2SiO) L (R 1-1 R 1-2 SiO) m SiR 1-2 2R 1-1 3 R 1-2 3SiO(R 1-2 2SiO) L (R 1-1 R 1-2 SiO) k SiR 1-2 2R 1-2 3 In the formula, R 1-1 is, independently of each other, an alkenyl group-containing organic group having 2 to 10 carbon atoms, and R 1-2 is, independently of each other, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, L ≧ 498, m ≧ 1, and k ≧ 2.

[0024] The details of the above R 1-1 and R 1-2 are as described for the above R 1 . Preferably, 498 ≦ L ≦ 11,998, preferably 1 ≦ m ≦ 1,000, more preferably 2 ≦ m ≦ 800, preferably 2 ≦ k ≦ 1,000, and more preferably 2 ≦ k ≦ 800.

[0025] As the component (A), more specifically, organopolysiloxanes represented by the following general formula can be mentioned, but are not limited thereto. In the following formula, Me, Vi, and Ph represent a methyl group, a vinyl group, and a phenyl group, respectively. M Vi 2D n (498 ≦ n ≦ 11,998) M Vi 2D n D Vi o (497 ≦ n ≦ 11,997, 1 ≦ o ≦ 1,000) M2D n D Vi o (496 ≦ n ≦ 11,996, 2 ≦ o ≦ 1,000) M Vi3 2D n D Vi o (498 ≦ n ≦ 11,998, 0 ≦ o ≦ 1,000) M Vi 2D n D Ph p (498 ≦ n ≦ 11,998, 0 ≦ p ≦ 1,000) M Vi 2D n D Vi o D Ph p (496 ≦ n ≦ 11,997, 1 ≦ o ≦ 1,000, 1 ≦ p ≦ 4,000) M Vi (q+2) D n D Vi o T q (496 ≦ n ≦ 11,996, 1 ≦ o ≦ 1,000, 1 ≦ q ≦ 10) M Vi (q+2r+2) D n D Vi o T q Q r (496 ≤ n ≤ 11,996, 1 ≤ o ≤ 1,000, 0 ≤ q ≤ 10, 1 ≤ q ≤ 10)

[0026] The structure of each siloxane unit in the above formula is as follows. [Chemical formula]

[0027] (B) Polyorganohydrogensiloxane Component (B) is a polyorganohydrogensiloxane having at least 3 SiH groups in one molecule and functions as a curing agent for component (A). Component (B) preferably has 2 to 500 siloxane units, more preferably 3 to 400 siloxane units. The polyorganohydrogensiloxane is preferably linear or branched.

[0028] Component (B) is preferably represented by the following average composition formula. R 2 e H f SiO (4-e―f) / 2 In the above formula, R 2 are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, e > 0, f > 0, and further 0 < e + f ≤ 3.

[0029] R 2 is a monovalent hydrocarbon group having 1 to 10 carbon atoms. For example, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, and decyl group, cycloalkyl groups such as cyclohexyl group, alkenyl groups such as vinyl group, allyl group, hexenyl group, and octenyl group, aryl groups such as phenyl group, etc. A part or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with halogen atoms or other groups. For example, trifluoromethyl group, 3,3,3-trifluoropropyl group, etc. are exemplified. Saturated aliphatic groups or aromatic groups are preferred, and particularly methyl group and phenyl group are preferred.

[0030] In the above average composition formula, e and f are numbers satisfying e > 0, f > 0 and 0 < e + f ≤ 3. Preferably, they are numbers satisfying 0.5 ≤ e ≤ 1.5, 0.5 ≤ f ≤ 1.5, and 1 ≤ e + f ≤ 2.5. If e is less than the above lower limit value, the storage stability of the composition may decrease. Also, if f is less than the above lower limit value, the composition may not harden. Further, if e + f is less than the above lower limit value or exceeds the above upper limit value, the curability of the composition may decrease. Component (B) preferably has 2 to 500 siloxane units, more preferably 3 to 400 siloxane units, and even more preferably 10 to 200 siloxane units. The polyorganohydrogensiloxane is preferably linear or branched.

[0031] Component (B) more specifically includes, but is not limited to, those represented by the following general formula. R 2-1 R 2-2 2SiO(R 2-2 2SiO) s (R 2-1 R 2-2 SiO) t SiR 2-2 2R 2-1 R 2-2 3SiO(R 2-2 2SiO) s (R 2-1 R 2-2 SiO) p SiR 2-2 3 R 2-2 3SiO(R 2-1 R 2-2 SiO) p SiR 2-2 3 In the above formula, R 2-1 is a hydrogen atom, R 2-2 are, independently of each other, monovalent hydrocarbon groups having 1 to 10 carbon atoms, and s ≥ 8, t ≥ 1, p ≥ 3. Examples of R 2-1 and R 2-2 include the groups exemplified by the above R 2 . Note that 8 ≤ s ≤ 98 is preferred, 1 ≤ t ≤ 198 is preferred, and 3 ≤ t ≤ 198 is more preferred. p is preferably 3 ≤ p ≤ 98.

[0032] (B) The amount is such that the ratio of the number of moles of SiH groups in component (B) to the number of moles of alkenyl groups in component (A) is 0.6 to 20, preferably 1 to 15, particularly preferably in the range of 1 to 12. If it is less than the above lower limit, the curability may be low, and the adhesion to the substrate when forming a cured film may also be low. If it exceeds the above upper limit, the mold release property of the cured film deteriorates, which is not preferable.

[0033] (B) Component is usually produced by ring-opening polymerization of cyclic low-molecular siloxanes such as octamethylcyclotetrasiloxane and Si-H-containing siloxanes such as tetramethylcyclotetrasiloxane using an acid catalyst. However, since it contains cyclic low-molecular siloxanes as raw materials after polymerization, it is preferable to use the one obtained by distilling off while passing an inert gas through the reaction product under heating and reduced pressure.

[0034] (B) Examples of those representing the detailed structure of the component include, but are not limited to, the following. In the following formula, Me represents a methyl group. M2D u D H v (1 ≦ u ≦ 95, 7 ≦ v ≦ 98) M2D H v (8 ≦ v ≦ 98) M H 2D u D H v (1 ≦ u ≦ 97, 7 ≦ v ≦ 98) M (w+2) D u D H v T w (1 ≦ u ≦ 95, 7 ≦ v ≦ 98, 1 ≦ w ≦ 5) M (w+2x+2) D u D H v T w Q x (1 ≤ u ≤ 95, 7 ≤ v ≤ 98, 0 ≤ w ≤ 5, 1 ≤ x ≤ 5)

[0035] The structure of each siloxane unit in the above formula is as follows. [Chemical formula]

[0036] (C) Platinum group metal-based catalyst The (C) component is a platinum group metal-based catalyst for curing by hydrosilylation reaction of the alkenyl group in the (A) component and the Si-H group in the (B) component. Examples of the central metal include platinum, palladium, iridium, rhodium, osmium, ruthenium, etc., and platinum is particularly preferred. Examples of the platinum catalyst include chloroplatinic acid, an alcohol solution of chloroplatinic acid, a reaction product of chloroplatinic acid and alcohol, a platinum complex obtained by the reaction of chloroplatinic acid and an olefin compound, a complex of platinum and a vinyl group-containing siloxane, a complex of platinum and a vinyl group-containing polysiloxane, etc.

[0037] The blending amount of the (C) component may be a catalytic amount. The catalytic amount is an effective amount for the addition reaction of the above organopolysiloxane to proceed. Preferably, it is an amount such that the metal amount is 1 to 500 mass ppm with respect to the total mass of the (A) and (B) components, and any (G) component and any (H) component, more preferably 2 to 450 mass ppm, and even more preferably 20 to 350 mass ppm. If it is less than the above lower limit, the reaction may be slow and the curability may decrease. If it exceeds the above upper limit, the pot life may decrease and the cost may increase.

[0038] (D) Terpene-based solvent The silicone release agent composition of the present invention is characterized by using a terpene-based solvent as a plant-derived organic solvent that is compatible with organopolysiloxane and can volatilize upon heating to form a cured film. The component (D) is a terpene or a derivative of terpene (hereinafter collectively referred to as a terpene-based solvent) that is compatible with the components contained in the silicone release agent composition. The solvent compatible with the components contained in the silicone release agent composition means a solvent that forms a transparent solution when the silicone release agent composition and the solvent are mixed. When all of the above components (A) to (C) contained in the silicone release agent composition are mixed, the viscosity becomes high and handling becomes difficult. The (D) terpene-based solvent functions for diluting the above components (A) to (C). The (D) terpene-based solvent also contributes to improving the wettability to the substrate during processing and the smoothness after curing.

[0039] In order for the solvent to volatilize during processing, the (D) terpene-based solvent preferably has high volatility, and the boiling point of the solvent is preferably 220°C or lower, more preferably 200°C or lower. If the boiling point exceeds 220°C, the curability of the release agent may deteriorate. The derivative of terpene is, for example, a terpenoid compound having a carbonyl group or a hydroxy group. In the present invention, the terpene-based solvent is preferably at least one selected from a monoterpene compound having 10 carbon atoms and a terpenoid compound having a carbonyl group or a hydroxy group.

[0040] (D) Terpene solvents, more specifically, include pinene (boiling point: 156 °C), limonene (boiling point: 178 °C), terpineol (boiling point: 218 °C), menthane (boiling point: 172 °C), linalyl acetate (boiling point: 220 °C), linalool (boiling point: 200 °C), farnandrene (boiling point: 171 °C), cymene (boiling point: 177 °C), menthol (boiling point: 212 °C), neomenthol (boiling point: 212 °C), terpinene (boiling point: 173 °C), terpinolene (boiling point: 185 °C), fencon (boiling point: 193 °C), camphene (boiling point: 159 °C), etc. In addition to these, turpentine oil with α-pinene as the main component can also be used. From the viewpoints of boiling point and compatibility with components (A) to (C), turpentine oil, α-pinene, and p-menthane are preferred. The terpene solvent may be used alone or in combination of two or more.

[0041] By using the above terpene solvent, the odor during handling can be reduced compared to the case of using a general-purpose solvent such as toluene. The amount of the terpene solvent in the silicone release agent composition of the present invention is 1 to 20,000 parts by mass, more preferably 10 to 15,000 parts by mass, still more preferably 500 to 10,000 parts by mass, still more preferably more than 1000 to 8000 parts by mass, and still more preferably 1500 to 6000 parts by mass with respect to 100 parts by mass in total of components (A), (B), and (C). Although the optimal viscosity of the coating liquid varies depending on the coating method, generally, if it is less than 1 part by mass or exceeds 20,000 parts by mass, the coating workability deteriorates and the smoothness of the coated film surface also deteriorates.

[0042] (E) Addition reaction controller (E) component is a control agent. The control agent is used to suppress the progress of the addition reaction in the process from formulating the silicone release agent composition to coating it on a substrate and heating and curing it, so as to control the addition reaction so that the formulated silicone composition does not thicken or gel. The reaction control agent coordinates with the platinum group metal which is an addition reaction catalyst to suppress the addition reaction, and when heated and cured, the coordination is released and the catalytic activity is expressed. Any of the reaction control agents conventionally used in addition reaction curable silicone compositions can be used. For example, acetylene alcohols such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-pentyn-3-ol, 2-phenyl-3-butyn-2-ol, acetylene compounds such as 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, reaction products of these acetylene compounds with alkoxysilane or siloxane or hydrogen silane, vinyl siloxanes such as tetramethylvinylsiloxane cyclic body, organic nitrogen compounds such as benzotriazole and other organic phosphorus compounds, oxime compounds, organic chloro compounds, etc. can be mentioned.

[0043] The content of the (E) component is 0.1 to 10 parts by mass, preferably 0.2 to 8 parts by mass, more preferably 0.3 to 5 parts by mass, based on 100 parts by mass in total of the (A) to (C) components. When the amount of the (E) component is less than the above lower limit value, it may not be possible to obtain a sufficient pot life. When the amount of the (E) component is more than the above upper limit value, the control ability may be too strong and the curability may decrease.

[0044] (F) Adhesive The silicone release agent composition of the present invention can further contain 0.1 to 20 parts by mass of an organopolysiloxane having 10 mol% or more of a siloxane unit having a glycidyl group and / or a glycidoxy group bonded to a silicon atom via a carbon atom per 100 parts by mass of the component (A). By blending the component (F) into the silicone release agent composition, the effect of improving the adhesion of the resulting cured product is achieved. The component (F) is a compound having a high effect of maintaining the substrate adhesion under heating and humidifying conditions of the resulting cured film, and is blended in expectation of an adhesion improving effect under particularly severe use conditions.

[0045] (F) component is an organopolysiloxane containing 10 mol% or more of a siloxane unit having a glycidyl group and / or a glycidoxy group bonded to a silicon atom via a carbon atom. When the number of the above siloxane units is less than 10 mol%, the effect of obtaining the adhesion effect to the substrate decreases. Preferably, it is an organopolysiloxane containing 20 to 100 mol%, more preferably 50 to 100 mol% of a siloxane unit having a glycidyl group and / or a glycidoxy group.

[0046] (F) component preferably has an average degree of polymerization of 2 to 50, more preferably 2 to 20. If the average degree of polymerization is within this range, the coating property of the composition is good and the adhesion improving effect is easily obtained. In the present invention, the average degree of polymerization is the weight average degree of polymerization in terms of polystyrene by gel permeation chromatography (GPC).

[0047] (F) component may be any of linear, branched, or cyclic organopolysiloxanes, or a mixture thereof. It is preferably a partial hydrolysis condensate of an organoalkoxysilane. Among the organoalkoxysilanes that are raw materials of the component (F), as the alkoxysilane having a glycidyl group and / or a glycidoxy group bonded to a silicon atom via a carbon atom, a unit trifunctional organoalkoxysilane is preferred. More preferably, the component (F) is preferably a partial hydrolysis condensate of an organoalkoxysilane represented by the following general formula (5-1). [Chemical formula]

[0048] In the above formula (5-1), the monovalent organic group having a glycidoxy group That is The hydrogen atom on the group represented by JPEG2025095514000006.jpg2064 may be replaced by a substituent. From the viewpoints of safety and economy, an epoxycyclohexyl group is excluded. For example, a 3,4-epoxycyclohexylmethyl group, a 2-(3,4-epoxycyclohexyl)ethyl group, a 3-(3,4-epoxycyclohexyl)propyl group, etc. are excluded.

[0049] R 7 is a C1-C20 group having no aliphatic unsaturated bond. Specifically, it is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, a tolyl group, an aralkyl group such as a benzyl group, a phenethyl group, or a hydroxypropyl group in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with hydroxy groups. Among these groups, R 7 is preferably a hydrogen atom, an alkyl group, more preferably an alkyl group having 1 to 5 carbon atoms.

[0050] Specific examples of the organoalkoxysilane represented by the above formula (5-1) include the following compounds. [Chemical formula] [Chemical formula] [Chemical formula]

[0051] As the other organoalkoxysilane that is co-hydrolytically condensed together with the above alkoxysilane, organoalkoxysilanes represented by the following general formulas (5-2), (5-3), or (5-4) are preferably used, and more preferably trifunctional and tetrafunctional alkoxysilanes of the following general formula (5-3) or (5-4) are used. By having such a branched structure or three-dimensional cross-linked structure in the molecule or endowing the ability to form it during the process of forming a cured product, the strength of the cured product is improved, and the dissolution and dispersibility in a silicone cured film layer excellent in releasability mainly composed of a linear structure are moderately reduced. As a result, the above organoalkoxysilane tends to gather near the interface between the base material and the silicone cured film. Therefore, it is considered to exhibit a high adhesion improving effect. (R 7-1 )2-Si(OR 7 )2(5-2) R 7-1 -Si(OR 7 )3(5-3) Si(OR 7 )4(5-4) In the above formulas, R 7 is independently of each other an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms or a hydroxyl group which may contain an oxygen atom and does not have an aliphatic unsaturated bond, and R 7-1 is an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms. y is an integer of 3 to 10.

[0052] More specifically, the following compounds can be mentioned as the organoalkoxysilane represented by the above formula (5-2), (5-3), or (5-4). (CH3)2-Si(OCH3)2, (CH3)2-Si(OC2H5)2, (CH3)2-Si(OC3H7)2, (C6H5)2-Si(OCH3)2, (C6H5)2-Si(OC2H5)2, (C6H5)2-Si(OC3H7)2, (CH3)-Si(OCH3)3, (CH3)-Si(OC2H5)3, (CH3)-Si(OC3H7)3, (C6H5)-Si(OCH3)3, (C6H5)-Si(OC2H5)3, (C6H5)-Si(OC3H7)3 (C8H 17 )-Si(OCH3)3, (C 10 H 21 )-Si(OCH3)3, Si(OCH3)4, Si(OC2H5)4, Si(OC3H7)4

[0053] The following siloxane units formed by the partial hydrolysis and condensation reaction of the organoalkoxysilanes represented by the above general formulas (5-1) to (5-4) are respectively designated as T E , D, T, and Q, and the (F) component can be represented by the average formula of DaT E bTcQd. [Chemical formula] Here, a + b + c + d is 2 to 50, b / (a + b + c + d) is 0.1 to 1, and a, c, and d are 0 to 35 respectively. The molecular terminals that do not form siloxane bonds with other siloxane units are alkoxy groups or silanol groups. If the (F) component has an alkenyl group in the molecule, the adhesion effect to the substrate will decrease.

[0054] The blending amount of the (F) component is in the range of 0.1 to 20 parts by mass, preferably 0.5 to 15 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the (A) component. If the blending amount is within this range, it is easy to obtain the effect of improving the adhesion to the substrate, and it will not affect the peeling characteristics and the strength of the cured film.

[0055] Examples of the (F) component include the following compounds. [Chemical formula] Compounds represented by the above formula, where a + b is 2 to 50, a is a number of 1 or more, and b is 0 or a number of 1 to 49. The molecular terminals are blocked by a + b + 2 or fewer methoxy groups, ethoxy groups, or propoxy groups, and a part of them is substituted with hydroxyl groups, or mixtures thereof.

[0056]

Chem.

[0057] As a more preferred example, the following compound of an average hexamer can be mentioned.

Chem.

[0058] As a more preferred example, the following compound of an average hexamer can be mentioned.

Chem.

[0059] (G) Light release agent The silicone release agent composition of the present invention can further contain a (G) release force control component. As the (G) component, a release force control component containing a (G1) acrylic-silicone graft copolymer and / or a (G2) methylphenylpolysiloxane having a linear structure can be included. The blending amount is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 15 parts by mass, and even more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the (A) component. If the blending amount is within this range, the release force control effect can be easily obtained, and the adhesion of the cured film to the substrate is also maintained well. When the (G1) component and the (G2) component are used in combination, the total may be within the above range. Hereinafter, each component will be described in detail.

[0060] (G1) Release force control component containing an acrylic-silicone graft copolymer (G1) component is a release force control component containing an acrylic-silicone graft copolymer. By blending this component, a very small release force can be obtained, and an excellent release film with a high residual adhesion rate of the peeled adhesive sheet can be provided.

[0061] The acrylic-silicone graft copolymer used in the present invention is a copolymer obtained by radical polymerization of an organopolysiloxane compound (g1) having an acrylic group and / or a methacrylic group (hereinafter also referred to as a (meth)acrylic group) and a radical polymerizable monomer (g2) having one radical polymerizable group in one molecule, and having a weight average molecular weight of 1,000 to 100,000.

[0062] The weight average molecular weight of the acrylic-silicone graft copolymer is 1,000 to 100,000 in terms of polystyrene conversion based on the measurement results of gel permeation chromatography (hereinafter abbreviated as "GPC") using toluene as a developing solvent, preferably 1,500 to 50,000, and more preferably 2,000 to 30,000. When the weight average molecular weight is less than 1,000, the residual adhesion rate decreases, and when it exceeds 100,000, the dispersibility in the silicone composition decreases.

[0063] (g1) Organopolysiloxane compound having a (meth)acrylic group The organopolysiloxane compound (g1) is not particularly limited as long as it has a (meth)acrylic group. However, from the viewpoints of the ease of copolymerization with the radical polymerizable monomer (g2) having one radical polymerizable group in one molecule, the ease of synthesis of the organopolysiloxane compound itself, and the effect of the release force control component, etc., it is preferably a radical polymerizable silicone macromonomer represented by the following general formula (3).

Chemical formula

[0064] In the above formula (3), g is an integer of 0 to 1,000, preferably 0 to 500, more preferably 0 to 200.

[0065] In the above formula (3), R 4 is, independently of each other, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 18 carbon atoms, a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, or a substituent represented by the following general formula (4).

Chemical formula

[0066] In the above formula (4), R 4 and R 5The unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms represented by, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, a tolyl group, an aralkyl group such as a benzyl group, a phenethyl group, or a part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a hydroxy group, a cyano group, a halogen atom, etc., such as a hydroxypropyl group, a cyanoethyl group, a 3-chloropropyl group, a 3,3,3-trifluoropropyl group. Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like. R 3 is preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 5 carbon atoms. R 4 is preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 5 carbon atoms.

[0067] In the above formula (4), h is an integer of 0 to 300, preferably an integer of 0 to 100, more preferably an integer of 0 to 50.

[0068] Examples of the organopolysiloxane compound having the above (g1) (meth) acrylic group include, but are not limited to, the following compounds. In the following formulas, Me, OMe, and Ph represent a methyl group, a methoxy group, and a phenyl group, respectively.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0069] (g2) Radical polymerizable monomer The radical polymerizable monomer (g2) may be used alone or in combination of two or more, and is not particularly limited as long as it is a compound having one radical polymerizable group in one molecule.

[0070] Examples of the component (g2) include compounds having one radical polymerizable group in one molecule, such as acrylic, methacrylic, styryl, cinnamic acid ester, vinyl, allyl, etc. More specifically, ester compounds of (meth)acrylic acid such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, trifluoropropyl (meth)acrylate, perfluorobutylethyl (meth)acrylate, perfluorooctylethyl (meth)acrylate; epoxy group-containing radical polymerizable monomers such as glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate; hydroxyl group-containing radical polymerizable monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate; radical polymerizable silane compounds such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltributoxysilane, γ-methacryloxypropyltriisopropenoxysilane, γ-acryloxypropyltrimethoxysilane, acryloxymethyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldiethoxysilane, styryltrimethoxysilane, styryltriethoxysilane, α-methylstyryltrimethoxysilane; radical polymerizable monomers containing a polyoxyalkylene group; and glycerol (meth)acrylate are exemplified.

[0071] Considering the light peeling effect and high residual adhesion rate effect obtained by the peeling force control component, it is preferable to contain an alkyl (meth)acrylate having 1 to 30 carbon atoms, and more preferably to contain methyl (meth)acrylate.

[0072] In the production of the acrylic-silicone graft copolymer (G1), the polymerization mass ratio [(g1) / (g2)] of the organopolysiloxane compound (g1) having a (meth)acrylic group and the radically polymerizable monomer (g2) having one radically polymerizable group in one molecule is preferably in the range of 30 / 70 to 99 / 1, more preferably 40 / 60 to 97 / 3, and even more preferably 50 / 50 to 95 / 5. When the polymerization mass ratio [(g1) / (g2)] is less than 30 / 70, the silicone component decreases, so the compatibility with the silicone composition decreases, and the peel force control component may separate. When it is greater than 99 / 1, the light peeling effect may decrease.

[0073] The copolymerization of the monomer raw material containing the organopolysiloxane compound (g1) having a (meth)acrylic group and the radically polymerizable monomer (g2) having one radically polymerizable group in one molecule is carried out in the presence of ordinary radical polymerization initiators such as peroxides such as benzoyl peroxide, dicumyl peroxide, lauroyl peroxide, and tert-butyl 2-ethylperoxyhexanoate, and azo compounds such as 2,2'-azobis(2-methylbutyronitrile). It is also possible to apply any of the solution polymerization method, emulsion polymerization method, suspension polymerization method, and bulk polymerization method. Thereby, an acrylic-silicone graft copolymer (G1) is obtained.

[0074] In the present invention, among these polymerization methods, the solution polymerization method is particularly preferable because it is easy to adjust the molecular weight of the obtained acrylic-silicone graft copolymer to an optimal range. Examples of the solvent used in this case include one or a mixture of two or more of aromatic hydrocarbons such as benzene, toluene, and xylene, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, esters such as ethyl acetate, n-butyl acetate, and isobutyl acetate, and alcohols such as ethanol, isopropanol, n-butanol, and isobutanol.

[0075] The coincidence temperature is preferably in the range of 50 to 180 °C, particularly preferably in the range of 60 to 120 °C. Under this temperature condition, the polymerization reaction can be completed in about 1 to 10 hours. The method for extracting the copolymer from the copolymerization solution is not particularly limited, and examples include a method of evaporating the solvent, a method of adding a poor solvent such as water or methanol to the copolymerization solution to precipitate and dry the copolymer.

[0076] (Component (G2) is a linear methylphenylpolysiloxane, which may have no functional group or may have an alkoxy group and / or a silanol group at the terminal. It is an organopolysiloxane having a 30 mass% toluene-diluted viscosity at 25 °C of 0.01 to 70 Pa·s. If it is less than 0.01 Pa·s, the effect of controlling the peeling force is small, and if it exceeds 70 Pa·s, the productivity decreases.

[0077] More preferably, (CH3)3SiO((CH3)2SiO) p ((C6H5)2SiO) q It is a methylphenylpolysiloxane represented by Si(CH3)3, and p + q is a number such that the viscosity of the methylphenylpolysiloxane is 0.01 to 70 Pa·s at a 30 mass% toluene-diluted viscosity at 25 °C. The (CH3)3SiO unit is 0.01 to 20% based on the total number of all siloxane units, the (CH3)2SiO unit is 60 to 95%, and the (C6H5)2SiO unit is preferably 0.5 to 20%. 1 / 2 The unit is 0.01 to 20%, the (CH3)2SiO 2 / 2 The unit is 60 to 95%, and the (C6H5)2SiO 2 / 2 The unit is preferably 0.5 to 20%.

[0078] (The blending amount of component (G) is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, based on 100 parts by mass of component (A). If the amount of component (G) is too small, the light peeling effect may be small, and if it is too large, the curability may decrease. When components (G1) and (G2) are used in combination, the total mass of these is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, based on 100 parts by mass of component (A).

[0079] (H) Resinous organopolysiloxane (H) component is R 6 3SiO 1 / 2 units and SiO 4 / 2 units, and is a resinous organopolysiloxane having (R 6 3SiO 1 / 2 units) / (SiO 4 / 2 units) preferably in a molar ratio of 0.5 to 1.5, more preferably 0.6 to 1.3. More preferably, the (H) component is R 6 3SiO 1 / 2 units and SiO 4 / 2 units only, and is a resinous organopolysiloxane. If the molar ratio of (R 6 3SiO 1 / 2 units) / (SiO 4 / 2 units) is within the above range, the compatibility with other components in the composition is good, and the effect of controlling the releasability of the cured film of the composition is also great.

[0080] In the above, R 6 is, independently of each other, a monovalent hydrocarbon group having 1 to 10 carbon atoms without an aliphatic unsaturated bond or an alkenyl group having 2 to 10 carbon atoms, and optionally some of the R 6 may be a hydrolyzable group having 1 to 10 carbon atoms or a hydroxyl group. As the monovalent hydrocarbon group having 1 to 10 carbon atoms, more preferably, an alkyl group having preferably 2 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, etc., and an aryl group having preferably 6 to 10 carbon atoms such as a phenyl group, a tolyl group, a benzyl group, etc. can be mentioned. As the alkenyl group having 2 to 10 carbon atoms, a vinyl group, an allyl group, a butenyl group, a hexenyl group, an octenyl group, a decanyl group, etc. can be mentioned. As the hydrolyzable group having 1 to 10 carbon atoms, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc. can be mentioned.

[0081] (H) component may be used in combination of two or more resinous organopolysiloxanes. Also, within a range not impairing the characteristics of the present invention, R 6 2SiO 3 / 2 units and R 6 SiO 2 / 2 units can also be contained in (H). R 6is as described above. R 6 2SiO 3 / 2 units and R 6 SiO 2 / 2 When included, it is preferably 10% or less, more preferably 5% or less, based on the total number of siloxane units.

[0082] The above (H) resinous organopolysiloxane preferably has a number average molecular weight (Mw) of 2000 to 5000, more preferably 2500 to 4500. The number average molecular weight (Mw) in the present invention is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard substance.

[0083] (The (H) component may be pre-condensed in the presence of a catalyst before being mixed with the above (A) component and (B) component. This is an operation to react the hydrolyzable groups present on the surface of the (H) component, and an improvement in the curability and mold release control effect of the cured film of the composition can be expected. An alkaline catalyst is used, and the reaction is carried out at room temperature to reflux temperature, and neutralization may be carried out as necessary.

[0084] Examples of the alkaline catalyst include metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide; carbonates such as sodium carbonate and potassium carbonate; hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; metal alkoxides such as sodium methoxide and potassium butoxide; organometals such as butyllithium; potassium silanolate; nitrogen compounds such as ammonia gas, aqueous ammonia, methylamine, trimethylamine, and triethylamine. Among them, ammonia gas or aqueous ammonia is preferred. The temperature of the condensation reaction may be carried out from room temperature to the reflux temperature of the organic solvent. The reaction time is not particularly limited, but it may be 0.5 to 20 hours, preferably 1 to 16 hours.

[0085] Furthermore, after the reaction is completed, a neutralizing agent for neutralizing the alkaline catalyst may be added if necessary. Examples of the neutralizing agent include acidic gases such as hydrogen chloride and carbon dioxide; organic acids such as acetic acid, octylic acid, and citric acid; and mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid. When ammonia gas or aqueous ammonia or a low-boiling amine compound is used as the alkaline catalyst, an inert gas such as nitrogen may be passed through and distilled off.

[0086] In the silicone release agent composition for a release film of the present invention, the blending amount of the component (H) is preferably 0 to 100 parts by mass, more preferably 0 to 70 parts by mass, and even more preferably 0 to 40 parts by mass with respect to 100 parts by mass of the component (A). If the blending amount of (H) is within this range, the appearance of the cured film is kept good. When the component (H) has at least one alkenyl group, the ratio of the number of moles of the SiH group in the component (B) to the number of moles of the alkenyl group in the component (A) and the component (H) is 0.6 to 20, preferably 1 to 15, particularly preferably 1 to 12.

[0087] Other components In addition to the above-mentioned components (A) to (H), components usually blended in the silicone release agent composition for release paper or release film may be appropriately added as long as the effects of the present invention are not impaired. For example, non-reactive organopolysiloxanes having no alkenyl group or Si-H group, silicone oligomers, silane compounds, and other organic compounds can be mentioned. From the functional aspect, there are a light release agent for improving the releasability of the cured film, a heavy release control agent for suppressing the releasability, a promoter for assisting the function of the platinum group metal-based catalyst to improve the curability, an anchor additive for improving the adhesiveness to the substrate, a crosslinking agent for increasing the strength of the cured film, an antioxidant for enhancing the stability, etc. In addition, an antistatic agent, a lubricity imparting agent, a leveling agent, a pigment, a dye, a phosphorescent agent, a foaming agent, a plasticizer, etc. may be added.

[0088] In addition to the above-mentioned (D) terpene-based solvent, if necessary, a general solvent used for diluting silicone may be used in combination. Specifically, aliphatic hydrocarbon solvents such as hexane, heptane, octane, isooctane, decane, cyclohexane, methylcyclohexane, and isoparaffin, hydrocarbon solvents such as industrial gasoline, petroleum benzine, and solvent naphtha, ketone solvents such as acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, and cyclohexanone, ester solvents such as ethyl acetate, propyl acetate, and isopropyl acetate, ether solvents such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, and 1,2-dimethoxyethane, siloxane solvents such as hexamethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, tris(trimethylsiloxy)methylsilane, and tetrakis(trimethylsiloxy)silane, or a mixed solvent thereof. The blending amount of other solvents is preferably 0.5 to 1000 parts by mass with respect to a total of 100 parts by mass of components (A) and (B). When using other solvents, the amount is preferably 50% or less with respect to the blending amount of the above-mentioned (D) terpene-based solvent.

[0089] Method for producing silicone release agent composition The silicone release agent composition of the present invention can be obtained by mixing the above components (A) to (H) in a predetermined amount and other optional components as necessary. The viscosity of the obtained silicone release agent composition at 25°C is preferably 1 to 100 mPa·s, and more preferably 5 to 50 mPa·s. Since the silicone release agent composition has a tendency for its pot life, that is, its curability over time, to gradually decrease, a method of premixing components other than the platinum group metal-based catalyst of component (C) and adding and mixing component (C) immediately before use is preferred.

[0090] Method for using silicone release agent composition The silicone release agent composition of the present invention may be applied using a known coating method. For example, it is applied to a sheet-shaped substrate such as paper or a plastic film by a coating machine (three-roll, five-roll, gravure roll, offset gravure roll comma coater, lip coater, knife coater, screen coating, dip coating, etc.), and then heat-cured by a conventional method. In this way, a silicone cured film of the silicone release agent composition of the present invention is formed on one side of the sheet-shaped substrate and is suitably used as a release sheet or the like.

[0091] As a substrate for applying the silicone release agent composition, for example, in the case of a paper substrate, glassine paper, polyethylene laminated paper, polyvinyl alcohol resin coated paper, clay coated paper, etc. may be mentioned. In the case of a plastic film substrate, films such as polyolefins such as polyethylene and polypropylene; polyesters such as polyethylene terephthalate may be mentioned.

[0092] The coating amount of the silicone release agent composition may be an amount sufficient to form a silicone cured film on the surface of the sheet-shaped substrate, for example, 0.1 to 50.0 g / m 2 or so. Applying too much amount may conversely cause a decrease in release performance.

[0093] The conditions during heat curing vary depending on the type of substrate and the coating amount, but by heating at 80 to 200 °C, preferably 100 to 180 °C, for 1 to 60 seconds, preferably 2 to 30 seconds, a cured film can be formed on the substrate.

Examples

[0094] Hereinafter, examples will be shown to explain the present invention in detail, but the present invention is not limited to the following examples. Also, Me represents a methyl group, Vi represents a vinyl group, and Ph represents a phenyl group.

[0095] [Preparation of Release Paper Sample] A test solution of a silicone release agent composition obtained by adding a curing catalyst (C) component to a silicone release agent mixture containing (A), (B), (D), and (E) components and any (G), (F), and (H) components, and quickly mixing and stirring, was applied to a polyethylene laminated paper using a bar coater so that the thickness of the release agent layer after curing was set to 0.8 μm. This was heated in a dryer at 140 °C for 30 seconds to produce a release paper.

[0096] [Measurement of Release Force] An acrylic solvent-based adhesive (Oribain BPS-5127 manufactured by Toyochem Co., Ltd.) was applied to the silicone-coated surface of the above release paper using an applicator so that the thickness was 130 μm. After heating and drying at 100 °C for 3 minutes, the papers were laminated and crimped by reciprocating a roller covered with a rubber layer weighing 2 kg once. This was left standing at 25 °C for 1 day, and the force (N / 25 mm) required to peel the adhesive surface from the release paper at an angle of 180° at a speed of 300 mm / min using a tensile tester was measured.

[0097] [Measurement of Residual Adhesion Rate] A 25-mm-wide polyester adhesive tape (NO31B, trade name manufactured by Nitto Denko Corporation) was attached to the silicone-coated surface of the above release paper, and heat-treated for 20 hours under a load of 20 gf / cm in a dryer at 70 °C. 2 Thereafter, the polyester adhesive tape was peeled from the release paper, the polyester adhesive tape was attached to a stainless steel plate, and crimped by reciprocating a roller covered with a 2-kg rubber layer once. Next, using a tensile tester, the polyester adhesive tape was peeled from the stainless steel plate at an angle of 180° at a speed of 300 mm / min, and the adhesive force F was measured. Also, the polyester adhesive tape was laminated to a tetrafluoroethylene plate instead of the release agent layer, treated in the same manner, and the adhesive force F0 was measured. And the residual adhesion rate was determined from the formula (adhesive force F / adhesive force F0) × 100 (%).

[0098] [Adhesion] In the production of the above release paper sample, the polyethylene laminated paper was changed to a PET film, and using a bar coater, it was coated by setting the thickness of the release agent layer after curing to be 0.2 μm. This was heated in a dryer at 120 °C for 30 seconds to produce a release film. The release film was stored at 25 °C and 50% RH for one week. After rubbing the silicone coating layer with a finger 10 times, the presence or absence of fogging and peeling was visually observed and evaluated according to the following criteria. For the release paper sample that showed no fogging and peeling after being stored at 25 °C and 50% RH for one week, the presence or absence of fogging and peeling was confirmed after rubbing the silicone coating layer with a finger 10 times after storing it at 60 °C and 90% RH for one month. AA: Even after storing at 60 °C and 90% RH for one month, no fogging and peeling were observed. A: After storing at 25 °C and 50% RH for one week, no fogging and peeling were observed. B: Slight fogging and peeling were observed during storage at 25 °C and 50% RH for one week. C: Fogging or peeling was observed during storage at 25 °C and 50% RH for one week.

[0099] [Curing property] In the production of the above release paper sample, the polyethylene laminated paper was changed to a PET film, and using a bar coater, it was coated by setting the thickness of the release agent layer after curing to be 0.2 μm. It was heated in a hot air dryer at 100 °C for a specified number of seconds to form a release agent layer. After rubbing the release agent layer with a finger 10 times, the presence or absence of fogging and peeling was visually observed and evaluated according to the following criteria. A: No fogging and peeling were observed in 30 seconds. B: Fogging and peeling were observed in 30 seconds but not in 60 seconds. C: Fogging and peeling were observed in 60 seconds.

[0100] [Evaluation of odor] When producing the above release paper sample, 10 professional panelists confirmed the odor in the state before putting the substrate coated with the treatment bath into the dryer. Scoring was done according to the following criteria, and the average score was calculated. Criteria 5: Weak odor 4: Slightly weak odor 3: Slightly strong odor 2: Strong odor 1: Intense odor

[0101] The components used in the examples and comparative examples are as follows. (A) component (A1) Methyl vinyl polysiloxane Polysiloxane represented by the following structure, having a vinyl value of 0.007 mol / 100 g and a viscosity of 20,000 mPa·s at 25°C in a 30% by mass toluene solution [(CH2=CH)3SiO 1 / 2 2[(CH2=CH)(CH3)SiO 2 / 2 41 [(CH3)SiO) 2 / 2 )] 8957 (A2) Methyl phenyl vinyl polysiloxane Polysiloxane represented by the following structure, having a vinyl value of 0.002 mol / 100 g, a phenyl group content of 2 mol%, and a viscosity of 20,000 mPa·s at 25°C in a 30% by mass toluene solution JPEG2025095514000026.jpg8170 (A3) Methyl vinyl polysiloxane Polysiloxane represented by the following structure, having a vinyl value of 0.10 mol / 100 g and a viscosity of 20,000 mPa·s at 25°C in a 30% by mass toluene solution [(CH2=CH)(CH3)2SiO 1 / 2 2[(CH2=CH)(CH3)SiO 2 / 2 680 [(CH3)2SiO 2 / 2 8318

[0102] (B) component (B1) Methyl hydrogen polysiloxane Represented by the following formula, both ends of the molecular chain are blocked with trimethylsiloxy groups, (CH3)HSiO 2 / 2 unit and (CH3)2SiO 2 / 2 ​​​Methylhydrogenpolysiloxane consisting of units. It has an Si-H group content of 1.18 mol / 100 g and a kinematic viscosity of 110 mm 2 / s. [(CH3)3SiO 1 / 2 2[(CH3)HSiO 2 / 2 75 [(CH3)2SiO 2 / 2 23 Average composition formula (CH3) 1.27 (H) 0.75 SiO 1.98 / 2

[0103] (B2) Methylhydrogenpolysiloxane Methylhydrogenpolysiloxane represented by the following formula, with both ends of the molecular chain blocked by trimethylsiloxy groups and all other positions consisting of (CH3)HSiO units. It has an Si-H group content of 1.59 mol / 100 g and a kinematic viscosity of 35 mm 2 / s. [(CH3)3SiO 1 / 2 2[(CH3)HSiO 2 / 2 60 Average composition formula (CH3) 1.06 (H) 0.97 SiO 1.97 / 2

[0104] (D) Component (D1) α-Pinene (D2) p-Menthan (Comparative D3) Toluene

[0105] (E) Component (E1) 3-Methyl-1-butyn-3-ol

[0106] (F) Component (F1) Epoxy group-containing siloxane: An epoxy group-containing siloxane oligomer obtained by subjecting 236.3 parts by mass (1 mol) of 3-glycidoxypropyltrimethoxysilane and 9 parts by mass (0.5 mol) of water to partial hydrolysis and condensation at 70 °C for 5 hours in the presence of hydrochloric acid The viscosity at 25 °C is 0.005 Pa·s ​​​Average degree of coincidence 2: 100 mol% of siloxane units having an epoxy group bonded to a silicon atom through a carbon atom Silanol group content 0.02 mol / 100 g

[0107] (G) component (peeling force control component) (G1) Acrylic-silicone graft copolymer obtained by the following synthesis example [Synthesis example] 30.0 parts of toluene was charged into a glass reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser, and a dropping device. After heating to 90 - 100 °C, a mixture of 55.7 parts (0.067 mol) of a radically polymerizable silicone macromonomer represented by the following formula (8), 9.8 parts (0.098 mol) of methyl methacrylate, 2.5 parts (0.012 mol) of tert-butyl 2-ethylperoxyhexanoate, and 51.8 parts of toluene was dropped over 4 hours under nitrogen ventilation. After further polymerization at 90 - 100 °C for 2 hours, 0.4 part (0.002 mol) of tert-butyl 2-ethylperoxyhexanoate was added and polymerization was carried out for 2 hours. Then, it was dried in a vacuum dryer under the conditions of 150 °C / 10 mmHg to obtain an acrylic-silicone graft copolymer. The weight average molecular weight in terms of polystyrene by GPC was 12,000. [Chemical formula]

[0108] (G2) Linear methylphenylpolysiloxane With respect to the total number of all siloxane units, the trimethylsiloxane unit represented by (CH3)3SiO 1 / 2 is 0.7%, the dimethylsiloxane unit represented by (CH3)2SiO 2 / 2 is 94.3%, and the diphenylsiloxane unit represented by (C6H5)2SiO 2 / 2 is an organopolysiloxane having 5%, and has a viscosity of 3.00 Pa·s at 25 °C.

[0109] (H) component (H-1) Methylvinylpolysiloxane A polysiloxane represented by the following average structure, having a vinyl value of 0.08 mol / 100 g and a viscosity of 5 mPa·s at 25°C in a 30% by mass toluene solution [(CH2=CH)(CH3)2SiO 1 / 2 29 [(CH3)3SiO 1 / 2 221 [SiO 4 / 2 250

[0110] [Examples 1 - 7] The methyl vinyl polysiloxane selected from the above (A1) - (A3), the methyl hydrogen polysiloxane of the above (B1) or (B2), the terpene - based solvent selected from the above (D1) - (D3), the above (E1) 3 - methyl - 1 - butyn - 3 - ol, the above (F1) adhesive, the light release agent of the above (G1) or (G2), and the release force control agent of the above (H1) were mixed in the composition and blending amounts shown in Table 1 and stirred until homogeneous. Then, a complex of (C) platinum and vinyl siloxane was added so that it became 200 ppm in terms of the mass of platinum atoms relative to the total mass of the components (A), (B), (G), and (H), and stirred until homogeneous to obtain a silicone release agent composition. The viscosity of the obtained silicone release agent composition was 5 - 20 mm 2 / s, and SiH / Vi (the ratio of the Si - H group in component (B) to the alkenyl group in component (A) (hereinafter the same)) was 1.3 - 15.9. Details of the composition and viscosity are described in Table 1 below.

[0111] [Comparative Examples 1 - 3] A test solution was prepared in the same manner as in Examples 1 - 3, except that the (D) terpene - based solvent in the above examples was (D3) toluene.

[0112] Using the test solutions of the silicone release agent compositions obtained in the above examples and comparative examples, release paper samples were prepared by the method described above. For the release paper samples, the release force, residual adhesion rate, adhesion, curability, and odor were evaluated according to the method described above. The results are shown in Table 1 below.

[0113]

Table 1

[0114] The release papers of Examples 1 to 7 prepared using a silicone release agent composition using α-pinene and p-menthane as solvents had the same release force, residual adhesion rate, and adhesion as the release papers of Comparative Examples 1 to 3 prepared using a conventional silicone release agent composition using a toluene solvent. Also, the silicone release agent compositions of Examples 1 to 7 had a lower odor than the compositions of Comparative Examples 1 to 3. Although the boiling points of α-pinene and p-menthane are higher than 130°C which is the curing temperature, in the case of curing a coating material, if the solvent has a certain degree of volatility, the solvent can be removed even at a temperature below the boiling point.

[0115] Since the silicone release agent composition of the present invention has a low odor, it is possible to reduce the odor of the resulting pressure-sensitive article and reduce the burden on the operator.

Claims

1. (A) 83 to 99.5 parts by mass of a linear, branched or cyclic organopolysiloxane having at least two alkenyl group-containing organic groups in one molecule and having 0.001 to 0.20 mol of alkenyl groups in 100 g of the organopolysiloxane, (B) an amount such that the ratio of the number of moles of SiH groups in the component (B) to the number of moles of alkenyl groups in the component (A) of a polyorganohydrogensiloxane having at least three SiH groups in one molecule is 0.6 to 20, (C) a platinum group metal-based catalyst in a catalytic amount, and (D) at least one solvent selected from terpenes and derivatives of terpenes, 1 to 20,000 parts by mass based on 100 parts by mass in total of the components (A), (B) and (C), (E) an addition reaction control agent, 0.5 to 10 parts by mass based on 100 parts by mass in total of the components (A), (B) and (C), A silicone release agent composition characterized by containing the same.

2. The silicone release agent composition according to claim 1, wherein the component (A) is represented by the following average formula (1). [Chemical 1] (In formula (1), R １ is, independently of one another, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms which may contain a heteroatom, and at least two of R １ are alkenyl group-containing organic groups having 2 to 10 carbon atoms, a is a positive number of 2 or more, b is a positive number of 1 or more, c and d are positive numbers of 0 or more, and 500 ≦ a + b + c + d ≦ 15000)

3. Component (B) has an average composition formula: R ２ ｅ H ｆ SiO （４－ｅ－ｆ）／２ (wherein, R ２ is, independently of one another, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, e > 0, f > 0, and further 0 < e + f ≦ 3) The silicone release agent composition according to claim 1, represented by

4. The silicone release agent composition according to claim 1, wherein the component (D) has a boiling point of 220°C or lower.

5. The silicone release agent composition according to claim 1, wherein the component (D) has a boiling point of 200°C or lower.

6. An organopolysiloxane having 10 mol% or more of a siloxane unit having a glycidyl group and / or a glycidoxy group bonded to a silicon atom via a carbon atom in one molecule, further containing 0.1 to 20 parts by mass based on 100 parts by mass of the component (A), the silicone release agent composition according to claim 1.

7. The silicone release agent composition according to claim 1, further containing one or more selected from (G1) a release force control component containing an acrylic-silicone-based graft copolymer and (G2) a linear phenylmethylpolysiloxane, 0.1 to 20 parts by mass based on 100 parts by mass of the component (A).

8. (H)R ６ ３ SiO １／２ units and SiO ４／２ units, and (R ６ ３ SiO １／２ units) / (SiO ４／２ units) is 0.5 to 1.5 in molar ratio, and a resinous organopolysiloxane (in the above formula, R ６ is, independently of one another, a monovalent hydrocarbon group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms that does not have an aliphatic unsaturated bond, and optionally a part of R 6 may be a hydrolyzable group having 1 to 10 carbon atoms or a hydroxyl group) is further contained in an amount of 1 to 100 parts by mass based on 100 parts by mass of the component (A). When the component (H) has at least one alkenyl group, the ratio of the number of moles of SiH groups in the component (B) to the number of moles of alkenyl groups in the component (A) and the component (H) is 0.6 to 20. The silicone release agent composition according to claim 1.

9. A release sheet having a base material and a cured product formed by curing the silicone release agent composition according to any one of claims 1 to 8 on at least one surface of the surface of the base material.

10. A method for producing a release sheet by applying the silicone release agent composition according to claim 1 to at least one side of a substrate and curing it.

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