Active energy ray-curable silicone composition and cured product thereof

Abstract

The problem to be solved by the present invention is to provide: a novel actinic-ray-curable silicone composition capable of giving cured objects having a higher hardness than those obtained from conventional actinic-ray-curable silicone compositions; and a cured object obtained from the actinic-ray-curable silicone composition. This actinic-ray-curable silicone composition comprises the following A, B, and C components: A component, an organopolysiloxane having a thiol group; B component, an organpolysiloxane having an alkenyl group; and C component, an actinic-ray reaction initiator. The C component is contained in an amount of 0.01-20 parts by mass per 100 parts by mass of the sum of the A and B components.

Description

Technical Field

[0001] The present invention relates to an active energy ray-curable silicone composition and a cured product thereof.

Background Art

[0002] Silicone has characteristics such as high heat resistance, water repellency, electrical insulation, excellent chemical resistance, excellent biocompatibility, oxygen permeability, and transparency, and is therefore used in various technical fields such as in-vehicle, electronic devices, paints, medical devices, and materials for 3D printing.

[0003] Active energy ray-curable silicone does not cure until irradiated with a specific active energy ray, and cures immediately after irradiation with the active energy ray, and is therefore used in various fields.

[0004] Active energy ray-curable silicone compositions having various structures have been proposed for various applications, but the hardness of the cured products of the active energy ray-curable silicone compositions is not always sufficient (Patent Documents 1 to 3), and the development of active energy ray-curable silicone compositions having higher hardness is eagerly desired.

[0005] Also, active energy ray-curable silicone compositions having high hardness have been proposed (Patent Document 4), but curing using radical polymerization of acrylic reactive groups has problems such as shrinkage during curing and curing failure due to oxygen inhibition.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0007] An object of the present invention is to provide a novel active energy ray-curable silicone composition that can provide a cured product having a higher hardness than conventional active energy ray-curable silicone compositions.

Means for Solving the Problems

[0008] Under such circumstances, as a result of intensive studies on active energy ray-curable silicone compositions of various compositions, the present inventors have found that in an active energy ray-curable silicone composition containing an organopolysiloxane that cures by the reaction of a thiol group and an alkenyl group and an active energy ray reaction initiator, by combining an organopolysiloxane containing T units and D units and an organopolysiloxane containing Q units as the organopolysiloxane, the hardness of the cured product of the active energy ray-curable silicone composition can be increased. The present inventors have further completed the present invention after extensive trial and error regarding the composition of each organopolysiloxane, the type of active energy ray reaction initiator, the blending ratio of each component, and the like.

[0009] Therefore, the present invention provides the following items: Item 1. An active energy ray-curable silicone composition containing the following Component A, Component B, and Component C, Component A: An organopolysiloxane having a thiol group Component B: An organopolysiloxane having an alkenyl group Component C: An active energy ray reaction initiator An active energy ray-curable silicone composition containing 0.01 to 20 parts by mass of Component C with respect to a total of 100 parts by mass of Component A and Component B.

[0010] Item 2. Component A is (a) R 1 SiO 3 / 2 units (wherein R 1 represents a thiolalkyl group) and (b) R 2 2SiO2 / 2 Unit (wherein R 2 represents an alkyl group), and an organopolysiloxane in which the molar ratio of (a) to (b) is in the range of 1:0 to 20, the active energy ray-curable silicone composition according to claim 1.

[0011] Item 3. The B component is (c) R 3 n SiO (4-n) / 2 Unit (wherein R 3 each independently represents a monovalent hydrocarbon group having 1 to 10 carbon atoms. n is an integer of 1 to 3) and (d) SiO 4 / 2 Unit, wherein the (c) unit contains an alkenyl group as R 3 and the molar ratio of the (c) unit to the (d) unit is in the range of 0.5 to 1.5:1, the active energy ray-curable silicone composition according to claim 1.

[0012] Item 4. The proportion of the (c) unit in the B component where n is 2 is less than 10 mol% with respect to the total of the constituent units of the B component, the active energy ray-curable silicone composition according to any one of claims 1 to 3.

[0013] Item 5. A cured product of the active energy ray-curable silicone composition according to any one of claims 1 to 4.

[0014] Item 6. A cured product of the active energy ray-curable silicone composition according to claim 5, having a hardness of 10 to 65 as measured by a durometer type D according to JIS K 6253.

Effect of the Invention

[0015] According to the present invention, it is possible to provide a novel active energy ray-curable silicone composition and a cured product thereof that can provide a cured product having a higher hardness than conventional active energy ray-curable silicone compositions.

Mode for Carrying Out the Invention

[0016] In this specification, the singular forms (such as "a", "an", "the", etc.) shall include both singular and plural forms, unless otherwise explicitly stated in this specification or clearly inconsistent with the context. Active energy ray-curable silicone composition and cured product thereof The present invention relates to an active energy ray-curable silicone composition containing the following Component A, Component B, and Component C, Component A: An organopolysiloxane having a thiol group Component B: An organopolysiloxane having an alkenyl group Component C: An active energy ray reaction initiator Provided is an active energy ray-curable silicone composition containing 0.01 to 20 parts by mass of Component C with respect to a total of 100 parts by mass of Component A and Component B. The present invention also provides a cured product of the above active energy ray-curable silicone composition.

[0017] In a preferred embodiment, the present invention relates to an active energy ray-curable silicone composition containing the following Component A, Component B, and Component C, Component A: (a) R 1 SiO 3 / 2 units (wherein R 1 represents a thiolalkyl group) and (b) R 2 2SiO 2 / 2 units (wherein R 2 represents an alkyl group), and an organopolysiloxane in which the molar ratio of (a) to (b) is in the range of 1:0 to 20 Component B: (c) R 3 n SiO (4-n) / 2 units (wherein R 3 independently represents a monovalent hydrocarbon group having 1 to 10 carbon atoms. n represents an integer of 1 to 3.) and (d) SiO 4 / 2 units, wherein the (c) unit contains an alkenyl group as R 3 , and an organopolysiloxane in which the molar ratio of the (c) unit to the (d) unit is in the range of 0.5 to 1.5:1 Component C: An active energy ray reaction initiator An active energy ray-curable silicone composition containing 0.01 to 20 parts by mass of Component C with respect to a total of 100 parts by mass of Component A and Component B Provided thereby. The present invention also provides a cured product of the above active energy ray-curable silicone composition.

[0018] In the present invention, examples of the monovalent hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, and the like.

[0019] In the present invention, the alkyl group means a linear or branched monovalent saturated hydrocarbon. More specifically, examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, and the like. The number of carbon atoms of the alkyl group is, for example, 1 to 6, preferably 1 to 3, and more preferably 1.

[0020] In the present invention, the thioalkyl group means an alkyl group having one or more (preferably 1 to 2, more preferably 1) thiol groups (mercapto groups). More specifically, examples of the thioalkyl group include a mercaptomethyl group, a 2-mercaptoethyl group, a 3-mercaptopropyl group, a 2-mercaptopropan-2-yl group, a 3,3-dimercaptopropyl group, a 4-mercaptobutyl group, a 1-mercapto-2-methylpropan-2-yl group, a 3-mercapto-2-methylpropyl group, a 5-mercaptopentyl group, a 6-mercaptohexyl group, and the like. The number of carbon atoms of the thioalkyl group is, for example, 1 to 6, preferably 1 to 3, and more preferably 1.

[0021] In the present invention, the alkenyl group means a linear or branched monovalent hydrocarbon having at least one (preferably one) carbon-carbon double bond. More specifically, examples of the alkenyl group include a vinyl group, a 1- or 2-propenyl group, an i-propenyl group, a 1-, 2- or 3-butenyl group, a 2-methyl-2-propenyl group, a 2-, 3- or 4-pentenyl group, a 5-hexenyl group, and the like. The number of carbon atoms of the alkenyl group is, for example, 2 to 6, preferably 2 to 3, and more preferably 2.

[0022] In the present invention, the alkynyl group means a linear or branched monovalent hydrocarbon having at least one (preferably one) carbon-carbon triple bond. More specifically, examples of the alkynyl group include ethynyl group, 1- or 2-propynyl group, 1-, 2- or 3-butynyl group, 1-methyl-2-propynyl group, 2-, 3- or 4-pentynyl group, 5-hexynyl group and the like. Examples of the number of carbon atoms of the alkynyl group include 2 to 6, preferably 2 to 3, and more preferably 2.

[0023] In the present invention, the cycloalkyl group means a cyclic monovalent hydrocarbon group. More specifically, examples thereof include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like. Examples of the number of carbon atoms of the cycloalkyl group include 3 to 6, and 3 is preferable.

[0024] In the present invention, examples of the aryl group include phenyl group, naphthyl group, biphenyl group and the like. Examples of the number of carbon atoms of the aryl group include 6 to 12, and 6 is preferable.

[0025] The active energy ray-curable silicone composition of the present invention contains an organopolysiloxane having a thiol group as component A. As component A, (a) R 1 SiO 3 / 2 units (wherein R 1 represents a thiolalkyl group) and (b) R 2 2SiO 2 / 2 units (wherein R 2 represents an alkyl group), and an organopolysiloxane in which the molar ratio of (a) to (b) is in the range of 1:0 to 20 is preferable.

[0026] In the present invention, the number of carbon atoms of the thiolalkyl group represented by R 1 is preferably, for example, 1 to 6, more preferably 2 to 4, and even more preferably 3. There are a plurality of R 1 in component A, and these R 1 may be the same or different.

[0027] In the present invention, the number of carbon atoms of the alkyl group represented by R 2 is, for example, preferably 1 to 6, more preferably 1 to 3, and even more preferably 1. Although there are a plurality of R 2 in the A component, these R 2 may be the same or different.

[0028] The molar ratio of the (a) unit to the (b) unit in the A component is in the range of 1:0 to 20, preferably 1:3 to 18, and more preferably 1:6 to 15.

[0029] In the present invention, the content (mol%) of the constitutional units contained in each component can be measured by 29Si NMR.

[0030] Also, even if all of the constitutional units contained in the A component are (a) R 1 SiO 3 / 2 units and (b) R 2 2SiO 2 / 2 units, they may contain constitutional units other than these. As constitutional units other than (a) R 1 SiO 3 / 2 units and (b) R 2 2SiO 2 / 2 units, for example, as groups other than the mercaptoalkyl group of the (a) unit, alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, etc., cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc., aryl groups such as phenyl group, naphthyl group, biphenyl group, etc. are bonded to silicon atoms, and as groups other than the alkyl group of the (b) unit, cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc., aryl groups such as phenyl group, naphthyl group, biphenyl group, etc. are bonded to silicon atoms, units represented by R 1 m R 3 3― m SiO 1 / 2 (m is 0 to 3), among which R 3Examples include units that do not have an unsaturated hydrocarbon group (such as an alkenyl group or an alkynyl group). In such an embodiment, with respect to the total amount of the constituent units contained in Component A, (a) R 1 SiO 3 / 2 units and (b) R 2 2SiO 2 / 2 The total amount of the units is not particularly limited. For example, 90 mol% or more is preferable, 95 mol% or more is more preferable, and 99 mol% or more is even more preferable.

[0031] The number of mercapto groups per unit weight in Component A is not particularly limited. For example, 0.6 to 5 mmol / g is preferable, 0.7 to 3 mmol / g is more preferable, and 0.8 to 1.75 mmol / g is even more preferable.

[0032] In the present invention, Component A is, for example, (a) R 1 SiO 3 / 2 A chlorosilane or alkoxysilane corresponding to the unit is R 1 R 4 3Si(R 4 is an alkoxy group having 1 to 3 carbon atoms or Cl), and (b) R 2 2SiO 2 / 2 A chlorosilane or alkoxysilane corresponding to the unit is R 2 2R 4 2Si, and optionally (a) R 1 SiO 3 / 2 units and (b) R 2 2SiO 2 / 2 It can be produced by hydrolyzing and condensing a raw material containing a chlorosilane or alkoxysilane corresponding to a constituent unit other than the unit. R 1 R 4 3Si and R 2 2R 4 The usage ratio of 2Si is not limited. For example, with respect to 1 mol of R 1 R 4 3Si, 0 to 20 mol of R 2 2R 4 2Si is preferable, 3 to 18 mol is more preferable, and 6 to 15 mol is even more preferable. Also, R in the raw material monomer 1 R4 3Si and R 2 2R 4 Although the ratio of the total amount of 2Si is not particularly limited, for example, 90% or more is preferable, 95 mol% or more is more preferable, and 99 mol% or more is even more preferable. The temperature during hydrolysis is not particularly limited, for example, 25 to 75 °C is preferable, and 65 to 70 °C is more preferable. The hydrolysis time is also not particularly limited, for example, 1 to 24 hours is preferable, and 1 to 12 hours is more preferable. Hydrolysis may be carried out in the presence of a catalyst. In such an embodiment, examples of the catalyst include acid catalysts such as hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidic ion exchange resins, and various Lewis acids, etc.

[0033] Although the temperature during the condensation reaction is not particularly limited, for example, 100 to 180 °C is preferable, and 100 to 150 °C is more preferable. The condensation reaction time is also not particularly limited, for example, 1 to 24 hours is preferable, and 3 to 12 hours is more preferable. The condensation reaction may be carried out in the presence of a catalyst. In such an embodiment, examples of the catalyst include nitrogen-containing compounds such as ammonia, primary amines, secondary amines, tertiary amines, and pyridine; basic ion exchange resins; hydroxides such as potassium hydroxide; carbonates such as potassium carbonate; carboxylates such as sodium acetate; and base catalysts such as various Lewis bases, etc.

[0034] The reaction solvent in these reactions is not particularly limited. For example, it can include benzene, toluene, xylene, or similar aromatic hydrocarbons; hexane, heptane, isooctane, or similar linear or partially branched saturated hydrocarbons, cyclohexane, or similar aliphatic hydrocarbons, or a mixed solvent thereof, etc.

[0035] The active energy ray-curable silicone composition of the present invention contains an organopolysiloxane having an alkenyl group as component B. As component B, (c)R 3 n SiO (4-n) / 2 units (wherein R 3Each independently represents a monovalent hydrocarbon group having 1 to 10 carbon atoms. n represents an integer of 1 to 3.) and (d) SiO 4 / 2 unit, and the (c) unit is R 3 Preferably, an organopolysiloxane or the like contains an alkenyl group as, and the molar ratio of the (c) unit to the (d) unit is in the range of 0.5 to 1.5 to 1.

[0036] In the present invention, as the monovalent hydrocarbon group represented by R 3 an alkyl group, an alkenyl group, etc. are preferable. In the B component, there are a plurality of R 3 Although there are a plurality of these R 3 they may be the same or different. When the monovalent hydrocarbon group represented by R 3 is an alkyl group, examples of the number of carbon atoms thereof include 1 to 6, preferably 1 to 3, and more preferably 1. When the monovalent hydrocarbon group represented by R 3 is an alkenyl group, examples of the number of carbon atoms thereof include 2 to 6, preferably 2 to 3, and more preferably 2. The proportion of the (c) unit containing an alkenyl group is preferably, for example, 8 mol% or more, more preferably 10 mol% or more, and still more preferably 12 mol% or more.

[0037] Further, in order to obtain a cured product of an active energy ray-curable silicone composition having high hardness, the proportion of the (c) unit in the B component having n = 2 is preferably 10 mol% or less, more preferably 5 mol% or less, and still more preferably 1 mol% or less with respect to the total of the constituent units of the B component.

[0038] The molar ratio of the (c) unit to the (d) unit in the B component is in the range of 0.5 to 1.5:1, preferably 0.6 to 1.1:2, and more preferably 0.7 to 1:1.

[0039] Also, even if all of the constituent units contained in the B component are (c)R 3 n SiO (4 - n) / 2 unit and (d)SiO 4 / 2 unit, other constituent units may be included. (c)R3 (4-n) SiO 1 / 2 Unit and (d)SiO 4 / 2 As the structural units other than the unit, for example, as the groups other than the monovalent hydrocarbon group of the (c) unit, there are units in which a halogen-substituted hydrocarbon group (for example, chloromethyl group, chlorophenyl group, 3,3,3-trifluoropropyl group, etc.) is bonded to a silicon atom. In such an embodiment, (c)R with respect to the total amount of the structural units contained in the B component 3 n SiO (4-n) / 2 Unit and (d)SiO 4 / 2 The total amount of the unit and the (d)SiO unit is not particularly limited, but for example, 90 mol% or more is preferable, 95 mol% or more is more preferable, and 99 mol% or more is even more preferable.

[0040] The number of vinyl groups per unit weight in the B component is not particularly limited, but for example, 0.6 to 5 mmol / g is preferable, 0.65 to 3 mmol / g is more preferable, and 0.7 to 2 mmol / g is even more preferable.

[0041] In the present invention, the B component is, for example, (c)R 3 n SiO (4-n) / 2 Chlorosilane or alkoxysilane corresponding to the unit is R 3 n R 4 (4-n) Si, and (d)SiO 4 / 2 Chlorosilane or alkoxysilane corresponding to the unit is R 4 4Si, and optionally (c)R 3 n SiO (4-n) / 2 Unit and (d)SiO 4 / 2 It can be produced by hydrolyzing and condensing a raw material containing chlorosilane or alkoxysilane corresponding to the structural units other than the unit and the (d)SiO unit. R 3 n R 4 (4-n) Si and R 4 The usage ratio of 4Si is not limited, but for example, R 3 n R4 (4-n) For 1 mol of Si, 4 0.5 to 1.5 mol of R 3 n R 4 (4-n) Si and R 4 The total amount ratio of 4Si is not particularly limited. For example, 90% or more is preferable, 95 mol% or more is more preferable, and 99 mol% or more is even more preferable. The temperature during hydrolysis is not particularly limited. For example, 25 to 85°C is preferable, and 65 to 80°C is more preferable. The hydrolysis time is also not particularly limited. For example, 1 to 24 hours is preferable, and 1 to 12 hours is more preferable. Hydrolysis may be carried out in the presence of a catalyst. In such an embodiment, examples of the catalyst include acid catalysts such as hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidic ion exchange resins, and various Lewis acids.

[0042] The temperature during the condensation reaction is not particularly limited. For example, 100 to 180°C is preferable, and 100 to 150°C is more preferable. The condensation reaction time is also not particularly limited. For example, 1 to 24 hours is preferable, and 1 to 12 hours is more preferable. The condensation reaction may be carried out in the presence of a catalyst. In such an embodiment, examples of the catalyst include nitrogen-containing compounds such as ammonia, primary amines, secondary amines, tertiary amines, and pyridine; basic ion exchange resins; hydroxides such as potassium hydroxide; carbonates such as potassium carbonate; carboxylates such as sodium acetate; and base catalysts such as various Lewis bases.

[0043] The reaction solvent in these reactions is not particularly limited. For example, it can include benzene, toluene, xylene, or similar aromatic hydrocarbons; hexane, heptane, isooctane, or similar linear or partially branched saturated hydrocarbons, cyclohexane, or similar aliphatic hydrocarbons, or a mixed solvent thereof.

[0044] Examples of the active energy ray reaction initiator as the C component include active energy ray radical generators, such as benzyl or its dialkyl acetal compounds, acetophenone compounds, benzoin or its alkyl ether compounds, benzophenone compounds, thioxanthone compounds, phosphine oxide compounds, etc., but are not limited thereto. Specifically, 2,2 - diethoxyacetophenone, 2,2 - dimethoxy - 1,2 - diphenylethane - 1 - one, 1 - hydroxy - cyclohexyl - phenyl - ketone, 2 - hydroxy - 2 - methyl - 1 - phenyl - propan - 1 - one, 2 - hydroxy - 1 - {4 - [4 - (2 - hydroxy - 2 - methyl - propionyl) - benzyl] - phenyl} - 2 - methyl - propan - 1 - one, phenylglyoxylic acid methyl ester, 2 - methyl - 1 - [4 - (methylthio)phenyl] - 2 - morpholinopropan - 1 - one, 2 - benzyl - 2 - dimethylamino - 1 - (4 - morpholinophenyl) - 1 - butanone, bis(2,4,6 - trimethylbenzoyl) - phenylphosphine oxide, 2,4,6 - trimethylbenzoyl - diphenyl - phosphine oxide, etc., but are not limited thereto. These active energy ray reaction initiators can be used alone or in combination of two or more.

[0045] The active energy ray - curable silicone composition of the present invention contains 0.01 to 20 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably 0.1 to 2 parts by mass of the C component with respect to a total of 100 parts by mass of the A component and the B component.

[0046] Although the blending ratio of Component A and Component B in the active energy ray-curable silicone composition of the present invention is not limited, for example, with respect to the number of thiol groups of 1 in Component A in the composition, the number of alkenyl groups of Component B can be blended in the range of 0.25 to 2, preferably 0.35 to 1.7, more preferably 0.5 to 1.5. Further, although the blending ratio of Component A in the active energy ray-curable silicone composition of the present invention is not limited, for example, it can be blended in the range of 20 to 70% by mass, preferably 25 to 60% by mass, more preferably 30 to 55% by mass.

[0047] The active energy ray-curable silicone composition of the present invention may optionally contain components other than Component A, Component B, and Component C as long as the effects of the invention are not impaired.

[0048] For example, a polymerization inhibitor may be blended to improve storage stability. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, t-butylcatechol, phenothiazine, dibutylhydroxytoluene, p-benzoquinone, etc. These polymerization inhibitors can be used alone or in combination of two or more. When using a polymerization inhibitor, the blending amount is not particularly limited, but for example, it can be used in the range of 0.001 to 0.5 parts by mass with respect to 100 parts by mass in total of Component A and Component B.

[0049] A solvent may be blended to adjust the viscosity. Examples of the solvent include aromatic solvents such as toluene and xylene; aliphatic solvents such as hexane, octane, and isoparaffin; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and isobutyl acetate; ether solvents such as diisopropyl ether and 1,4-dioxane, etc. These solvents can be used alone or in combination of two or more.

[0050] A photosensitizer may be blended to initiate the reaction using active energy rays in a wavelength range where the active energy ray initiator cannot initiate the reaction. Examples of photosensitizers include various compounds such as heterocyclic and condensed ring aromatic hydrocarbons, organic dyes, and aromatic ketones. These photosensitizers can be used alone or in combination of two or more.

[0051] In addition, examples include ultraviolet absorbers, colorants, flame retardants, conductive agents, heat conductors, metals, fillers, silane coupling agents, antioxidants, defoaming agents, leveling agents, thermal radical generators, and the like.

[0052] The viscosity of the active energy ray-curable silicone composition of the present invention is not particularly limited, but from the viewpoint of ease of handling, the viscosity at 23°C is preferably 100,000 mPa·s or less, more preferably 50,000 mPa·s or less, and even more preferably 20,000 mPa·s or less. The lower limit of the viscosity of the active energy ray-curable silicone composition of the present invention is not limited, and examples include 100 mPa·s or more, 500 mPa·s or more, 1,000 mPa·s or more, 1,500 mPa·s or more, etc. at 23°C. In the present invention, the viscosity of the active energy ray-curable silicone composition can be measured using a rotational viscometer in accordance with JIS K-7117-1.

[0053] In a preferred embodiment, the wavelength of the active energy ray for curing the active energy ray-curable silicone is not particularly limited as long as it is a wavelength at which the curing reaction is initiated by an active energy ray reaction initiator in the active energy ray-curable silicone composition or other additives such as a separately added photosensitizer. Examples of the active energy ray include ultraviolet rays, electron beams, X-rays, visible light, infrared rays, high-frequency rays, and the like. Among these, ultraviolet rays having a wavelength of 300 nm to 410 nm are preferable from an economic viewpoint. Also, the light source is not particularly limited, and examples include UV-LEDs, ultraviolet lasers, mercury lamps, xenon lamps, halogen lamps, fluorescent lamps, and the like. Active energy rays obtained by converting the wavelength of the active energy rays emitted from the light source to a wavelength at which the curing reaction is initiated by techniques such as photon upconversion may also be used. The irradiation dose of the active energy ray is not particularly limited as long as it does not impair the physical properties of the cured product, but 1 to 10,000 mJ / cm 2 is preferable, and 1 to 1,000 mJ / cm 2 is more preferable. The temperature during irradiation is not particularly limited, but 0 to 80°C is preferable, and 20 to 60°C is more preferable.

[0054] In the present invention, the use of the active energy ray-curable silicone composition is not limited, but since it is less susceptible to oxygen inhibition and has a small curing shrinkage, it can be used in the fields of coating and molding. For example, as the coating, after applying the active energy ray-curable silicone composition of the present invention to an object using, for example, dipping, a bar coater, spraying, a spin coater, etc., a method of curing by irradiating with active energy rays can be mentioned. As for molding, three-dimensional objects can be molded by injection molding or stereolithography. For example, in stereolithography, DLP (Digital Light Processing) type, LCD (Liquid Crystal Display) type, SLA (Stereolithography Apparatus) method, inkjet type, and the like can be mentioned.

[0055] In the present invention, the term "active energy ray-curable silicone composition" includes both a liquid active energy ray-curable silicone composition and a cured product obtained by irradiating with active energy rays. Therefore, in one embodiment, the present invention provides a cured product of an active energy ray-curable silicone composition.

[0056] In such an embodiment, the cured product of the active energy ray-curable silicone composition preferably has a hardness of 10 to 65, more preferably 15 to 55, as measured by a durometer type D in accordance with JIS K 6253.

[0057] The active energy ray-curable silicone composition of the present invention can be used in various applications, for example, it can be used in bioimplants, coatings, medical devices, models, microfluidic channels, sensors, molding materials, molds, adhesives, electronic devices, in-vehicle parts, cell culture scaffolds, optical devices, etc.

Examples

[0058] Component A Synthesis Example 1 (TSHD6) In a 300 mL separable flask equipped with a moisture determination receiver, a reflux condenser for cooling, and a thermometer, 100 g of dimethyldimethoxysilane and 27.31 g of 3-mercaptopropyltrimethoxysilane were mixed to form a 70% xylene solution, and 45.48 g of 0.4% hydrochloric acid was added dropwise. Hydrolysis was carried out while heating and stirring at 70 °C for 90 minutes. After completion of the reaction, the aqueous phase was separated, neutralized with sodium hydrogen carbonate, and then dehydrated by heating at 100 °C to 125 °C. After completion of dehydration, 0.58 g of a 1% potassium hydroxide aqueous solution was added, and a condensation reaction was carried out by heating and stirring at 140 to 145 °C for 5 hours. After neutralization with phosphoric acid, filtration was carried out, and then the remaining xylene was removed by heating under reduced pressure to obtain 58.90 g of a polymethylsiloxane (A-1) containing a mercaptopropyl group. The {HS(CH2)3SiO 3 / 2} units and {(CH3)2SiO 2 / 2The content of the unit (mol%) was measured by 29Si NMR (the same applies to the following synthesis examples). The number of mercapto groups per unit weight was determined from the content of {HS(CH2)3SiO 3 / 2} units and {( CH3)2SiO 2 / 2} units in the obtained polymethylsiloxane.

[0059] Average structural formula: [{HS(CH2)3SiO 3 / 2}{( CH3)2SiO 2 / 2}6] n Number of mercapto groups per unit weight: 1.75 mmol / g.

[0060] Synthesis Example 2 (TSHD9) The reaction was carried out under the same conditions except that the amount of 3-mercaptopropyltrimethoxysilane in Synthesis Example 1 was changed to 18.15 g. 50.78 g of a polymethylsiloxane (A-2) containing a mercaptopropyl group was obtained. Average structural formula: [{HS(CH2)3SiO 3 / 2}{( CH3)2SiO 2 / 2}9] n Number of mercapto groups per unit weight: 1.26 mmol / g.

[0061] Synthesis Example 3 (TSHD12) The reaction was carried out under the same conditions except that the amount of 3-mercaptopropyltrimethoxysilane in Synthesis Example 1 was changed to 13.67 g. 48.19 g of a polymethylsiloxane (A-3) containing a mercaptopropyl group was obtained. Average structural formula: [{HS(CH2)3SiO 3 / 2}{( CH3)2SiO 2 / 2} 12 n Number of mercapto groups per unit weight: 0.98 mmol / g.

[0062] Synthesis Example 4 (TSHD15) The reaction was carried out under the same conditions except that the amount of 3-mercaptopropyltrimethoxysilane in Synthesis Example 1 was changed to 10.89 g. 46.75 g of a polymethylsiloxane (A-4) containing a mercaptopropyl group was obtained. Average structural formula: [{HS(CH2)3SiO 3 / 2 ​}{(CH3)2SiO 2 / 2} 15 n Number of mercapto groups per unit weight: 0.80 mmol / g.

[0063] Synthesis Example 5 (TSHD21) The reaction was carried out under the same conditions except that the amount of 3-mercaptopropyltrimethoxysilane in Synthesis Example 1 was changed to 7.78 g. 40.35 g of polymethylsiloxane (A-5) containing mercaptopropyl groups was obtained. Average structural formula: [{HS(CH2)3SiO 3 / 2}{(CH3)2SiO 2 / 2} 21 n Number of mercapto groups per unit weight: 0.59 mmol / g.

[0064] Component B: Demethylated product of VQX-221 manufactured by Gelest. Number of vinyl groups per unit weight: 0.74 Component C: Active energy ray polymerization initiator. A mixture of 2-hydroxymethyl-1-phenylpropan-1-one (Tokyo Chemical Industry) and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (Tokyo Chemical Industry) (weight ratio 7 / 3) Other components: Polymerization inhibitor p-methoxyphenol (Wako Pure Chemical Industries).

[0065] Examples 1 to 5 and Comparative Example 1 The above components (A) to (D) were mixed in the compositions shown in Table 1 to prepare each silicone composition described in Table 1. Components A and B were prepared so that the thiol / vinyl ratio was 1 / 1 (mol ratio) in Examples 1 to 4 and Comparative Example 1, and the thiol / vinyl ratio was 1.3 / 1 (mol ratio) in Example 5. The viscosity of the compositions in Table 1 was measured at 23 °C using a rotational viscometer conforming to JIS K-7117-1, with spindle number 6 and a rotational speed of 20 rpm.

[0066] ​​Each composition was poured into a frame (25 mm × 60 mm) and formed into a sheet with a thickness of 2 mm. Using an ultraviolet curing light (SPEED-HD395-400) manufactured by Seeforce Co., Ltd., the composition was irradiated with light having a wavelength of 395 - 400 nm at room temperature (about 23°C) for 2 minutes to be cured. The hardness (durometer type D) of the cured product was measured in accordance with JIS K 6253.

[0067]

Table 1

Claims

1. An active energy ray-curable silicone composition containing the following Component A, Component B, and Component C, Component A: An organopolysiloxane represented by the following average structural formula {HS(CH ２ ) ３ SiO ３／２}{(CH ３ ) ２ SiO ２／２} ６～１５ Component B: An organopolysiloxane having an alkenyl group Component C: An active energy ray reaction initiator Based on a total of 100 parts by mass of Component A and Component B, it contains 0.01 to 20 parts by mass of Component C, and the organopolysiloxane of the said Component B is (c) R 3 n SiO (4-n) / 2 units (wherein R 3 independently of one another represents a monovalent hydrocarbon group having 1 to 10 carbon atoms. n is an integer from 1 to 3) and (d) SiO 4 / 2 units, the said (c) units contain an alkenyl group as R 3 and contains an organopolysiloxane in which the molar ratio of the (c) units to the (d) units is in the range of 0.5 to 1.5:1, The total amount of (c) R units and (d) SiO units relative to the total amount of constituent units contained in component B is 90 mol% or more, 3 n SiO (4-n) / 2 units and (d) SiO 4 / 2 units is 90 mol% or more, (c) R in Component B 3 n SiO (4-n) / 2 An active energy ray-curable silicone composition in which the proportion of those having n = 2 in the unit is 10 mol% or less with respect to the total of the structural units of Component B.

2. The active energy ray-curable silicone composition according to Claim 1, wherein the proportion of those in which n in the Component B is 2 is 5 mol% or less with respect to the whole of the constitutional units of the Component B.

3. A cured product of the active energy ray-curable silicone composition according to Claim 1.

4. A cured product of an active energy ray-curable silicone composition containing the following Component A, Component B, and Component C, Component A: An organopolysiloxane represented by the following average structural formula {HS(CH ２ ) ３ SiO ３／２}{(CH ３ ) ２ SiO ２／２}6-15 Component B: (c) R 3 n SiO (4-n) / 2 unit (wherein R 3 independently represents a monovalent hydrocarbon group having 1 to 10 carbon atoms. n is an integer of 1 to 3) and (d) SiO 4 / 2 unit, and the (c) unit contains an alkenyl group as R 3 and the molar ratio of the (c) unit to the (d) unit is in the range of 0.5 to 1.5:1 Organopolysiloxane Component C: An active energy ray reaction initiator The cured product contains 0.01 to 20 parts by mass of Component C with respect to 100 parts by mass in total of Component A and Component B, and has a hardness measured by a durometer type D according to JIS K 6253 of 18 to 50.

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