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WO2025225206A1 - Organosiloxane cyclique contenant un groupe polymérisable par voie radicalaire, son procédé de production et composition durcissable le contenant - Google Patents

Organosiloxane cyclique contenant un groupe polymérisable par voie radicalaire, son procédé de production et composition durcissable le contenant

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Publication number
WO2025225206A1
WO2025225206A1 PCT/JP2025/010045 JP2025010045W WO2025225206A1 WO 2025225206 A1 WO2025225206 A1 WO 2025225206A1 JP 2025010045 W JP2025010045 W JP 2025010045W WO 2025225206 A1 WO2025225206 A1 WO 2025225206A1
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WO
WIPO (PCT)
Prior art keywords
meth
acrylate
group
curable composition
radically polymerizable
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/010045
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English (en)
Japanese (ja)
Inventor
和弘 土田
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Shin Etsu Chemical Co Ltd
Original Assignee
Shin Etsu Chemical Co Ltd
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Application filed by Shin Etsu Chemical Co Ltd filed Critical Shin Etsu Chemical Co Ltd
Publication of WO2025225206A1 publication Critical patent/WO2025225206A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/10—Esters
    • C08F22/12—Esters of phenols or saturated alcohols
    • C08F22/20—Esters containing oxygen in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F30/00—Homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/04—Homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F30/08—Homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon

Definitions

  • the present invention relates to a radically polymerizable group-containing cyclic organosiloxane, a method for producing the same, and a curable composition containing the same.
  • Patent Document 1 proposes a technology for improving the hardness required for hard coats, flexibility to withstand impacts, and weather resistance to long-term outdoor exposure.
  • multifunctional (meth)acrylate compounds containing urethane bonds are prone to aggregation and high viscosity due to intermolecular interactions at the urethane bond sites, and require dilution with organic solvents, posing problems in terms of handling and environmental impact.
  • Patent Documents 2 to 4 propose silicone oligomers in which polymerizable functional groups are introduced via Si-O-C bonds, but the siloxane skeletons in these oligomers are all random structures, consisting of condensates of tetrafunctional siloxane units such as tetrachlorosilane and silicate, making it difficult to control the structure of the main chain.
  • the present invention has been made in consideration of the above circumstances, and aims to provide a radically polymerizable group-containing cyclic siloxane that has low viscosity and produces a cured product with excellent hardness, impact resistance, and adhesion to substrates, and little shrinkage on cure, as well as a method for producing the same and a curable composition containing the same.
  • cyclic organosiloxanes in which radically polymerizable functional groups are introduced into the cyclic siloxane structure via Si-O-C bonds, have low viscosity despite a small functional group equivalent weight, and produce cured products that have excellent hardness, impact resistance, and adhesion to substrates, and exhibit little cure shrinkage, leading to the completion of the present invention.
  • the siloxane units in the parentheses may be arranged in any order.
  • a method for producing a radically polymerizable group-containing cyclic organosiloxane according to 1, comprising dehydrogenating a cyclic hydrogen siloxane represented by the following formula (2) with a compound represented by the following formula (3) in the presence of an amine catalyst: (In the formula, each R1 independently represents a monovalent hydrocarbon group, p is an integer from 2 to 6, q is an integer from 0 to 4, and the sum of p and q is 4 to 6.
  • the siloxane units in the parentheses may be arranged in any order.) (wherein R3 represents a hydrogen atom or a methyl group, and A represents a divalent hydrocarbon group having 1 to 10 carbon atoms.) 4.
  • a curable composition comprising (A) the radical polymerizable group-containing cyclic organosiloxane of 1 and (B) a polymerization initiator; 6.
  • the curable composition of 5 further comprising, as component (C), a polymerizable unsaturated group-containing compound other than component (A); 7.
  • the radically polymerizable group-containing cyclic organosiloxane of the present invention has a structure in which polymerizable unsaturated groups, such as acryloyl groups and methacryloyl groups, are linked to the cyclic siloxane main skeleton via Si-O-C bonds. Therefore, even when the radically polymerizable group equivalent weight is small (functional group density is high), the viscosity is low. Cured products obtained from polymerizable compositions containing the radically polymerizable group-containing cyclic organosiloxane of the present invention exhibit excellent hardness, impact resistance, and adhesion to substrates, and exhibit little cure shrinkage.
  • each R 1 independently represents a monovalent hydrocarbon group
  • each R 2 independently represents a monovalent hydrocarbon group or a hydrogen atom
  • R 3 independently represents a hydrogen atom or a methyl group.
  • Specific examples of the monovalent hydrocarbon group for R1 and R2 may be linear, branched, or cyclic, but preferably have 1 to 20 carbon atoms.
  • alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, cyclohexyl, n-octyl, 2-ethylhexyl, and n-decyl; alkenyl groups such as vinyl, allyl (2-propenyl), 1-propenyl, isopropenyl, and butenyl; aryl groups such as phenyl, tolyl, xylyl, and naphthyl; and aralkyl groups such as benzyl, phenylethyl, and phenylpropyl.
  • alkyl groups having 1 to 20 carbon atoms and aryl groups having 6 to 12 carbon atoms are preferred, alkyl groups having 1 to 10 carbon atoms are more preferred, alkyl groups having 1 to 5 carbon atoms are even more preferred, and methyl groups, ethyl groups, and n-propyl groups are most preferred from the perspective of the marketability of the raw materials used.
  • A is a divalent hydrocarbon group having 1 to 10 carbon atoms.
  • the divalent hydrocarbon group may be linear, branched, or cyclic. Specific examples include linear or branched alkylene groups such as methylene, ethylene, trimethylene, propylene, tetramethylene, isobutylene, dimethylethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decylene (decamethylene); and arylene groups such as 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, toluenediyl, xylenediyl, and naphthalenediyl.
  • divalent saturated hydrocarbon groups having 2 to 4 carbon atoms are preferred, with ethylene, trimethylene, propylene, and tetramethylene groups being more preferred.
  • n is an integer of 2 to 6
  • m is an integer of 0 to 4
  • the sum of n and m is 4 to 6.
  • n is an integer of 2 to 4
  • m is an integer of 0 to 2
  • the sum of n and m is 4. If n is less than 2, the hardness of the cured product will be insufficient, and if n is more than 6, the structure will have an excess of polymerizable functional groups, resulting in an excessively high crosslink density of the cured product, which may result in reduced impact resistance.
  • the kinematic viscosity of the radically polymerizable group-containing cyclic organosiloxane of the present invention is preferably 1 to 1,000 mm 2 /s, more preferably 10 to 100 mm 2 /s, from the viewpoint of handleability.
  • the kinematic viscosity is measured at 25°C using, for example, an Ubbelohde viscometer or a Cannon-Fenske viscometer.
  • the weight-average molecular weight of the radically polymerizable group-containing cyclic organosiloxane of the present invention is preferably 400 to 4,000, in order to impart sufficient hardness and impact resistance to the resulting cured product.
  • the weight-average molecular weight in this invention is a value calculated using standard polystyrene as determined by gel permeation chromatography (GPC).
  • the functional group equivalent weight of the radically polymerizable group in the radically polymerizable group-containing cyclic organosiloxane of the present invention is preferably 200 to 500 g/mol, in order to impart sufficient hardness and impact resistance to the resulting cured product.
  • a functional group equivalent weight of 200 g/mol or more will result in a cured product with excellent hardness, while a functional group equivalent weight of 500 g/mol or less will result in a cured product with excellent flexibility and impact resistance.
  • the radically polymerizable group-containing cyclic organosiloxane of the present invention can be obtained, for example, by dehydrogenating a cyclic hydrogensiloxane represented by the following formula (2) with a compound represented by the following formula (3) in the presence of an amine catalyst.
  • R 1 , R 3 , and A have the same meanings as above, p is an integer of 2 to 6, preferably 2 to 4, q is an integer of 0 to 4, preferably 2 to 4, and the sum of p and q is 4 to 6, preferably 4.
  • the arrangement of the siloxane units in the parentheses may be arbitrary.
  • cyclic hydrogen siloxanes represented by the above formula (2) include 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3-dipropylcyclotetrasiloxane, and 1,3,5,7-tetramethyl-1,5-dipropylcyclotetrasiloxane.
  • compounds represented by the above formula (3) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate.
  • the amine catalyst is not particularly limited, and commercially available products can be used, but amine compounds having no NH group are preferred, and among these, diethylhydroxylamine is more preferred from the standpoints of basicity and availability.
  • Metal complexes such as platinum and palladium complexes can also function as catalysts for this reaction, but are not preferred because they also induce a hydrosilylation reaction between the hydrosilyl group and the olefin moiety of the polymerizable group.
  • the amount of amine catalyst used is preferably 0.001 to 0.1 moles per mole of Si-H groups in the cyclic hydrogensiloxane, and more preferably 0.005 to 0.05 moles.
  • an organic solvent may be used, if necessary.
  • the organic solvent is not particularly limited as long as it can sufficiently dissolve the raw materials without reacting with them, and examples thereof include non-polar hydrocarbon solvents such as hexane, heptane, and cyclohexane; ether solvents such as tetrahydrofuran, 4-methyltetrahydropyran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether monoacetate, and cyclopentyl methyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; and aromatic solvents such as toluene and xylene.
  • ether solvents and aromatic solvents are preferred from the viewpoints of reactivity and solubility.
  • the organic solvents can be used alone or in an appropriate mixture of two or more.
  • the reaction time for the dehydrogenation reaction can be appropriately set depending on the progress of the reaction, but is preferably 1 to 10 hours, more preferably 2 to 7 hours.
  • the reaction temperature may be appropriately changed depending on the boiling points of the raw materials and the solvent used, but is preferably in the range of 40 to 100°C.
  • the curable composition of the present invention comprises (A) the above-described radically polymerizable group-containing cyclic organosiloxane of the present invention and (B) a polymerization initiator.
  • the polymerization initiator of component (B) may be selected appropriately from the viewpoint of compatibility with the curable composition and curability.
  • Specific examples include carbonyl compounds such as benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzil, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, benzil dimethyl ketal, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, methylphenyl glyoxylate, and 2-hydroxy-2-methyl-1-phenylpropan-1-one; tetramethylthiol;
  • sulfur compounds such as uram monosulfide and tetramethylthiuram disulfide
  • phosphate compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, bis(2,4,6-trimethylbenz
  • the content of the polymerization initiator in the composition is preferably 0.1 to 10 parts by mass, more preferably 1 to 8 parts by mass, per 100 parts by mass of the (meth)acrylate compound and binder precursor combined, in order to moderate the curing speed of the resulting coating film, improve the scratch resistance and adhesion to the substrate of the cured coating film, and prevent discoloration and a decrease in weather resistance.
  • the curable composition of the present invention may contain, as necessary, a polymerizable unsaturated group-containing compound other than the component (A) as the component (C).
  • component (C) include monofunctional (meth)acrylates and polyfunctional (meth)acrylates having a polymerizable unsaturated bond, such as urethane (meth)acrylate, epoxy (meth)acrylate, and polyester (meth)acrylate, and may be selected appropriately depending on the performance required of the coating film.
  • monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, morpholyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, and dimethylamino Examples include ethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, tricyclodecane (meth)acrylate, polyethylene
  • acrylate bis(2-(meth)acryloxyethyl)-hydroxyethyl-isocyanurate, trimethylolpropane tri(meth)acrylate, tris(2-(meth)acryloxyethyl)isocyanurate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, epoxy di(meth)acrylate obtained by reacting bisphenol A diepoxy with (meth)acrylic acid, urethane tri(meth)acrylate obtained by reacting 2-hydroxyethyl (meth)acrylate with a trimer of 1,6-hexamethylene diisocyanate; urethane di(meth)acrylate obtained by reacting isophorone
  • the component (C) When the component (C) is used, its content is preferably 1 to 100 parts by mass, and more preferably 5 to 90 parts by mass, per 100 parts by mass of the total of the components (A) and (C), in order to improve the scratch resistance and adhesion to substrates of a cured product obtained from the composition.
  • the component (C) may be used alone or in combination.
  • the curable composition of the present invention may contain an inorganic filler, if necessary.
  • inorganic fillers include fine particles of oxides of Si, Ti, Al, Zn, Zr, In, Sn, Sb, etc., and fine particles of composite oxides thereof. These fine particles may also be coated with silica, alumina, etc.
  • specific examples of metal oxide fine particles include silica, alumina, zirconia, titania, etc., and silica fine particles are preferred. Addition of such metal oxide fine particles can further improve the properties of the cured product, such as abrasion resistance.
  • additives may be added to the curable composition of the present invention as long as they do not impair the effects of the present invention.
  • additives include ultraviolet absorbers, antifouling agents, water repellents, leveling agents, colorants, pigments, antioxidants, anti-yellowing agents, bluing agents, defoamers, thickeners, anti-settling agents, antistatic agents, surfactants, adhesion promoters, infrared absorbers, light stabilizers, and curing catalysts other than the above-mentioned photo- and thermal polymerization initiators.
  • the composition of the present invention is preferably in a solvent-free form that does not substantially contain organic solvents (which are often harmful to the human body and flammable), but a solvent may be added to the composition depending on the intended use and workability.
  • substantially means that the solvent contained in the composition is 1% by mass or less, particularly 0.1% by mass or less.
  • Specific examples of solvents that can be used include the same organic solvents as those used in the production of (A) the above-mentioned radically polymerizable group-containing cyclic organosiloxane of the present invention.
  • the solvent also includes those that are not intentionally added to the curable composition, such as reaction solvents that could not be completely removed by distillation under reduced pressure.
  • the curable composition of the present invention can be cured by heating and/or light to obtain a corresponding cured product, which may be in any form, such as a coating film applied to a substrate and cured, or a self-standing molded product or sealed product.
  • Photocuring is the preferred curing method from the viewpoint of productivity.
  • a high-pressure mercury lamp, metal halide lamp, LED lamp, or the like is used as a light source to irradiate ultraviolet light or electron beams of a wavelength appropriate for the polymerization initiator.
  • the irradiation atmosphere may be air or an inert gas such as nitrogen or argon.
  • When irradiating with ultraviolet light it is preferable to irradiate with about 1 to 1000 mJ/ cm2 , for example.
  • Substrates include, but are not limited to, organic resins such as plastic molded bodies, wood-based products, fibers, ceramics, glass, metals, calcium phosphates such as hydroxyapatite, and composites thereof. It is particularly suitable for use with various plastic materials and calcium phosphates.
  • polycarbonate resin polystyrene resin
  • acrylic resin modified acrylic resin
  • urethane resin urethane resin
  • thiourethane resin polycondensation products of halogenated bisphenol A and ethylene glycol
  • acrylic urethane resin halogenated aryl group-containing acrylic resin
  • sulfur-containing resin polyalkylene terephthalate resin
  • polyimide resin polyamide resin
  • polycycloolefin resin polyphenylene sulfide resin
  • polyphenylene oxide resin polyphenylene oxide resin
  • cellulose resin amorphous polyolefin resin
  • composite resins thereof e.g., amorphous polyolefin resin
  • the surface of these substrates may be treated, specifically, chemically treated, corona discharge treated, flame treated, plasma treated, or treated with an acid or alkaline solution, or a laminate whose surface layer is coated with a resin of a different type from that of the substrate itself may be used.
  • the laminate include a laminate produced by coextrusion or lamination in which an acrylic resin layer or a urethane resin layer is present on the surface layer of a polycarbonate resin substrate, and a laminate in which an acrylic resin layer is present on the surface layer of a polyester resin substrate.
  • the curable composition may be applied directly to the surface of the substrate, or may be applied via a primer layer, an ultraviolet absorbing layer, a printing layer, a recording layer, a heat ray shielding layer, an adhesive layer, an inorganic vapor deposition film layer, or the like, as needed.
  • the coating method can be appropriately selected from known coating methods such as spin coater, comma coater, lip coater, roll coater, die coater, knife coater, blade coater, rod coater, kiss coater, gravure coater, screen coating, dip coating, and cast coating.
  • coating layers such as an adhesive layer, ultraviolet absorbing layer, printing layer, recording layer, heat ray shielding layer, adhesive layer, inorganic vapor deposition film layer, water- and oil-repellent layer, and hydrophilic antifouling layer may be formed on the surface of the cured coating film of the curable composition of the present invention.
  • Methods for producing a self-supporting cured molded product using the curable composition of the present invention include, but are not limited to, methods using a mold, as well as film formation methods using a casting method in which the composition is coated on a film that already has a release layer and then cured.
  • the material of the molding die is not particularly limited as long as it ensures easy releasability from the cured product obtained after curing.
  • metal, glass, plastic, silicone, or a Teflon (registered trademark)-coated die may be used.
  • Teflon (registered trademark)-coated die it is preferable to use a Teflon (registered trademark)-coated die, as this has excellent releasability and can prevent breakage when removing the cured product.
  • Cured products obtained from the curable composition of the present invention can be used in scratch-resistant hard coatings for plastic substrates, optical lens moldings, flexible display materials for electronic materials, optical encapsulants for LED devices, and denture molding materials and dental filling materials for dental and medical use.
  • Example 2 A pale yellow, transparent liquid (A-2) was obtained by the same procedure as in Example 1, except that the 1,3,5,7-tetramethylcyclotetrasiloxane was replaced with a 1:1 (molar) mixture of 1,3,5,7-tetramethyl-1,3-dipropylcyclotetrasiloxane and 1,3,5,7-tetramethyl-1,5-dipropylcyclotetrasiloxane in the same molar ratio.
  • the kinematic viscosity at 25°C of this liquid was 13 mm /s
  • the acrylic group equivalent was 276 g/mol
  • the weight-average molecular weight was 731.
  • the above (A-2) was found to be a mixture of compounds represented by the following formulas (5) and (6).
  • Example 3 A pale yellow, transparent liquid (A-3) was obtained by the same procedure as in Example 1, except that the 2-hydroxyethyl acrylate was replaced by the same molar amount of 4-hydroxybutyl acrylate.
  • the liquid had a kinematic viscosity at 25°C of 42 mm /s, an acrylic group equivalent of 202 g/mol, and a weight-average molecular weight of 1,010.
  • the above (A-3) was found to be the compound represented by the following formula (7).
  • Example 4 A pale yellow, transparent liquid (A-4) was obtained by the same procedure as in Example 2, except that the 2-hydroxyethyl acrylate was replaced by the same molar amount of 4-hydroxybutyl acrylate.
  • the liquid had a kinematic viscosity at 25°C of 16 mm/s, an acrylic group equivalent of 306 g/mol, and a weight-average molecular weight of 755.
  • the above (A-4) was found to be a mixture of compounds represented by the following formulas (8) and (9).
  • Example 5 A pale yellow, transparent liquid (A-5) was obtained by the same procedure as in Example 1, except that the 2-hydroxyethyl acrylate was replaced by the same molar amount of 2-hydroxypropyl methacrylate.
  • the liquid had a kinematic viscosity at 25°C of 65 mm /s, a methacryl group equivalent of 205 g/mol, and a weight-average molecular weight of 986.
  • the above (A-5) was found to be the compound represented by the following formula (10).
  • Example 6 The same procedure as in Example 2 was carried out, except that the 2-hydroxyethyl acrylate was replaced by the same molar amount of 2-hydroxypropyl methacrylate, to obtain a pale yellow, transparent liquid (A-6).
  • the liquid had a kinematic viscosity at 25°C of 16 mm/s, a methacryl group equivalent of 300 g/mol, and a weight-average molecular weight of 731.
  • the above (A-6) was found to be a mixture of compounds represented by the following formulas (11) and (12).
  • PETA pentaerythritol tetraacrylate
  • DPHA dipentaerythritol hexaacrylate
  • HDDA hexanediol diacrylate
  • Photopolymerization initiator ⁇ -hydroxyacetophenone (Omnirad 1173, manufactured by IGB Resin B.V.)
  • the curable compositions in Table 1 were applied to the surfaces of various substrates, such as a polycarbonate (PC) NF-2000 sheet (4 mm thick ⁇ 15 cm long ⁇ 10 cm wide) manufactured by Mitsubishi Engineering-Plastics Corporation, a polyethylene terephthalate (PET) film Cosmoshine A4160 (50 microns thick) manufactured by Toyobo Co., Ltd., and a polished steel plate, using a No. 14 bar coater, and then air-dried for 15 minutes, heated at 80°C for 1 minute, and then irradiated with light at an irradiation dose of 600 mJ/ cm2 using a high-pressure mercury lamp to cure the coating, thereby obtaining test pieces.
  • PC polycarbonate
  • PET polyethylene terephthalate
  • A4160 50 microns thick
  • the coating films obtained in the above Examples and Comparative Examples were evaluated as follows, and the results are shown in Table 2.
  • PC Pencil hardness
  • the coating films obtained by curing the curable compositions of Examples 7 to 13 containing the radically polymerizable group-containing cyclic organosiloxane of the present invention exhibit transparency, adhesion, hardness, and impact resistance, and exhibit little cure shrinkage.
  • Comparative Example 1 using PETA and Comparative Example 2 using DPHA the adhesion was insufficient, and therefore the scratch resistance also tended to deteriorate, the impact resistance was low, and the cure shrinkage was very large.
  • Comparative Example 3 using HDDA the adhesion and cure shrinkage were good, but the hardness was low and the polycarbonate substrate was corroded, resulting in a deterioration in transparency.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'organosiloxane cyclique contenant un groupe polymérisable par voie radicalaire représenté par la formule (1) présente une faible viscosité, et donne un produit durci possédant une excellente dureté, une excellente résistance aux chocs et une excellente adhésion à un substrat et présentant un faible retrait de durcissement. Dans la formule, chaque R1 représente indépendamment un groupe hydrocarbure monovalent ; chaque R2 représente indépendamment un groupe hydrocarbure monovalent ou un atome d'hydrogène ; R3 représente un atome d'hydrogène ou un groupe méthyle ; A représente un groupe hydrocarbure divalent possédant entre 1 et 10 atomes de carbone ; n représente un nombre entier compris entre 2 et 6 ; m représente un nombre entier compris entre 0 et 4 ; et le total de n + m est compris entre 4 et 6. L'agencement des unités de siloxane dans les parenthèses peut être arbitraire.
PCT/JP2025/010045 2024-04-24 2025-03-17 Organosiloxane cyclique contenant un groupe polymérisable par voie radicalaire, son procédé de production et composition durcissable le contenant Pending WO2025225206A1 (fr)

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JP2024070177A JP2025166284A (ja) 2024-04-24 2024-04-24 ラジカル重合性基含有環状オルガノシロキサン、その製造方法およびそれを含む硬化性組成物
JP2024-070177 2024-04-24

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61236786A (ja) * 1985-04-11 1986-10-22 Shin Etsu Chem Co Ltd 環状シロキサンおよびその製造方法
JP2007145884A (ja) * 2005-11-24 2007-06-14 Shin Etsu Chem Co Ltd 多官能（メタ）アクリレート化合物、光硬化性樹脂組成物及び物品
JP2008173564A (ja) * 2007-01-18 2008-07-31 Kao Corp 高分子乳化剤
JP2016141615A (ja) * 2015-01-29 2016-08-08 旭化成株式会社 オルガノポリシロキサン及びそれを含有する熱硬化性樹脂組成物
JP2017149657A (ja) * 2016-02-23 2017-08-31 信越化学工業株式会社 有機ケイ素化合物およびそれを含む硬化性組成物
JP2021109923A (ja) * 2020-01-10 2021-08-02 信越化学工業株式会社 （メタ）アクリル官能性オルガノポリシロキサンの製造方法、硬化性組成物およびインクジェット用インク

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61236786A (ja) * 1985-04-11 1986-10-22 Shin Etsu Chem Co Ltd 環状シロキサンおよびその製造方法
JP2007145884A (ja) * 2005-11-24 2007-06-14 Shin Etsu Chem Co Ltd 多官能（メタ）アクリレート化合物、光硬化性樹脂組成物及び物品
JP2008173564A (ja) * 2007-01-18 2008-07-31 Kao Corp 高分子乳化剤
JP2016141615A (ja) * 2015-01-29 2016-08-08 旭化成株式会社 オルガノポリシロキサン及びそれを含有する熱硬化性樹脂組成物
JP2017149657A (ja) * 2016-02-23 2017-08-31 信越化学工業株式会社 有機ケイ素化合物およびそれを含む硬化性組成物
JP2021109923A (ja) * 2020-01-10 2021-08-02 信越化学工業株式会社 （メタ）アクリル官能性オルガノポリシロキサンの製造方法、硬化性組成物およびインクジェット用インク

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