Epoxy group-containing cyclic organopolysiloxane, curable composition comprising same, and cured product thereof

Abstract

An epoxy group-containing cyclic organopolysiloxane represented by general formula (1) can form a cured product having excellent crack resistance and flexibility. (R1 to R4 each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms in which an oxygen atom can be intervened, Y represents a divalent hydrocarbon group, Z1 and Z2 each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms in which an oxygen atom can be intervened, an epoxy group-containing monovalent organic group in which an oxygen atom can be intervened, an alkoxysilyl alkyl group, or a hydrogen atom, (In the formula, at least one is an epoxy group-containing monovalent organic group in which oxygen atoms can be introduced, n1 and n2 each independently represent an integer of 1-5 and satisfy an integer of n1 + n2 = 3-6, n3 and n4 each independently represent an integer of 1-5 and satisfy an integer of n3 + n4 = 3-6, and m represents an integer of 1-11. > # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a cyclic organopolysiloxane containing an epoxy group, a curable composition containing the same, and a cured product thereof. More specifically, the present invention relates to an organopolysiloxane formed by connecting a cyclic siloxane skeleton containing an epoxy group through a linking group, a curable composition containing the same, and a cured product thereof. Background Art

[0002] Compared with a non-siloxane-based epoxy material having a phenolic resin skeleton, an organopolysiloxane having an epoxy group is excellent in heat-resistant yellowing characteristics and low curing shrinkage. Therefore, a sealing material and a lens molding material using an epoxy-functional polyorganosiloxane have been proposed for use in electronic materials (Patent Documents 1 and 2).

[0003] In addition, regarding an organopolysiloxane having an epoxy group, an application as a coating adhesive that exhibits the heat resistance and weather resistance of a siloxane skeleton has also been proposed (Patent Documents 3 to 6).

[0004] On the other hand, in the cured product of an existing curable epoxy material, there is a drawback that cracking is likely to occur, and sufficient improvement in characteristics has not been achieved in an organopolysiloxane having an epoxy group.

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2005-171021

[0008] Patent Document 2: Japanese Patent Application Laid-Open No. 2019-189874

[0009] Patent Document 3: Japanese Patent Application Laid-Open No. 2015-112599

[0010] Patent Document 4: Japanese Patent Application Laid-Open No. 2019-143161

[0011] Patent Document 5: Japanese Patent Application Laid-Open No. 2019-108541

[0012] Patent Document 6: Japanese Patent Application Laid-Open No. 2012-144678 Summary of the Invention

[0013] Problems to be Solved by the Invention

[0014] In view of the above actual situation, the present invention has been completed, and an object thereof is to provide an organopolysiloxane containing an epoxy group, a curable composition containing the same, and a cured product thereof, which can form a cured product excellent in crack resistance and flexibility.

[0015] Means for Solving the Problems

[0016] The inventors of the present invention have conducted in - depth research to achieve the above - mentioned object, and as a result, it has been found that: an organopolysiloxane having a main skeleton formed by connecting cyclic siloxanes containing epoxy groups through a linking group improves the flexibility and crack resistance of a cured product obtained by the polymerization of epoxy groups, and thus the present invention has been completed.

[0017] That is, the present invention provides:

[0018] 1. A cyclic organopolysiloxane containing an epoxy group, which is represented by the following general formula (1):

[0019] [Chemical formula 1]

[0020]

[0021] (In the formula, R 1 , R 2 , R 3 and R 4 each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms in which an oxygen atom may be interposed,

[0022] Y represents a divalent hydrocarbon group,

[0023] Z 1 and Z 2 each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms in which an oxygen atom may be interposed, a monovalent organic group containing an epoxy group in which an oxygen atom may be interposed, an alkoxysilylalkyl, or a hydrogen atom, and at least one of Z 1 and Z 2 is a monovalent organic group containing an epoxy group in which an oxygen atom may be interposed,

[0024] n1 and n2 each independently represent an integer of 1 to 5 and satisfy the integer of n1 + n2 = 3 to 6,

[0025] n3 and n4 each independently represent an integer of 1 to 5 and satisfy the integer of n3 + n4 = 3 to 6,

[0026] m represents an integer of 1 to 11.)

[0027] 2. The cyclic organopolysiloxane containing an epoxy group according to 1, wherein the R 1 , R 2 , R 3 and R 4 are methyl groups;

[0028] 3. The cyclic organopolysiloxane containing an epoxy group according to 1, wherein the Z 1 and Z 2 are one or more selected from 3 - glycidoxypropyl and 2-(3,4 - epoxycyclohexyl)ethyl;

[0029] 4. The cyclic organopolysiloxane containing epoxy groups according to claim 1, wherein Y is a divalent saturated hydrocarbon group having a polycyclic structure;

[0030] 5. The cyclic organopolysiloxane containing epoxy groups according to claim 4, wherein Y is one or more selected from divalent saturated hydrocarbon groups represented by the following formulas (2a) and (2b),

[0031] [Chemical formula 2]

[0032]

[0033] (In the formula, the asterisk (*) represents the bonding site to the silicon atom, and the spatial configuration of each chiral carbon can be either cis (outer) or trans (inner).)

[0034] 6. The cyclic organopolysiloxane containing epoxy groups according to claim 1, wherein n1 and n4 are 3, and n2 and n3 are 1;

[0035] 7. The cyclic organopolysiloxane containing epoxy groups according to claim 1, wherein the functional group equivalent of the epoxy group is 200 to 400 g / mol;

[0036] 8. A curable composition comprising: (A) 100 parts by mass of the cyclic organopolysiloxane containing epoxy groups according to any one of claims 1 to 7, and (B) 0.01 to 5 parts by mass of a curing agent;

[0037] 9. The curable composition according to claim 8, further comprising (C) 1 to 200 parts by mass of a compound containing epoxy groups other than (A);

[0038] 10. The curable composition according to claim 9, wherein the curing agent is a photoacid generator;

[0039] 11. A cured product obtained by curing the curable composition according to claim 9.

[0040] Effects of the Invention

[0041] According to the present invention, it is possible to provide an organopolysiloxane containing epoxy groups and a curable composition containing the same, which can form a cured product having crack resistance and flexibility. Detailed Description of the Invention

[0042] The present invention will be specifically described below.

[0043] [1] Organopolysiloxane Containing Epoxy Groups

[0044] The cyclic organopolysiloxane containing epoxy groups according to the present invention is represented by the following general formula (1).

[0045] [Chemical formula 3]

[0046]

[0047] In formula (1), R 1 , R 2 , R 3 and R 4 each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms in which an oxygen atom may be inserted.

[0048] As the monovalent hydrocarbon group, it may be linear, branched, or cyclic. Specific examples thereof include 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.

[0049] Among these, an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 12 carbon atoms are preferred, an alkyl group having 1 to 10 carbon atoms is more preferred, an alkyl group having 1 to 5 carbon atoms is further preferred, and methyl is even more preferred.

[0050] Furthermore, in the molecular chain or at the Si-side terminal of the above monovalent hydrocarbon group, an oxygen atom may be inserted, and for example, it may be an alkoxy group having 1 to 20 carbon atoms.

[0051] In formula (1), Y represents a divalent hydrocarbon group. As this group, there is no particular limitation, but a divalent saturated hydrocarbon group having a polycyclic structure is preferred, a group represented by the following formulas (2a), (2b), and (10a) to (10c) is more preferred, and a group represented by formulas (2a) and (2b) is further preferred.

[0052] It should be noted that for the asymmetric divalent hydrocarbon group represented by the following formulas, the left-right direction is as described below and is not limited, and it may be a structure in which each of the following formulas is rotated 180° on the paper surface. In addition, the hydrocarbon group represented by the following formulas may be a group formed by combining each structure.

[0053] [Chemical formula 4]

[0054]

[0055] (In the formula, the asterisk (*) represents the bonding site to the silicon atom, and the spatial configuration of each chiral carbon may be either cis (exo) or trans (endo).)

[0056] In formula (1), Z 1 and Z 2Each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms into which an oxygen atom can intervene, a monovalent organic group containing an epoxy group into which an oxygen atom can intervene, an alkoxysilylalkyl group, or a hydrogen atom, and at least one of them is a monovalent organic group containing an epoxy group into which an oxygen atom can intervene.

[0057] Regarding Z 1 and Z 2 For the monovalent hydrocarbon group, groups similar to those exemplified for the above R 1 to R 4 can be cited.

[0058] As the monovalent organic group containing an epoxy group, as long as it contains an epoxy group, it is not particularly limited, and particularly preferably 3-glycidoxypropyl, 2-(3,4-epoxycyclohexyl)ethyl.

[0059] As the alkoxysilylalkyl group, 2-(trimethoxysilyl)ethyl, 2-(methyldimethoxysilyl)ethyl, 2-(dimethoxymethylsilyl)ethyl, 2-(triethoxysilyl)ethyl, 2-(methyldiethoxysilyl)ethyl, 2-(dimethylethoxysilyl)ethyl, 6-(trimethoxysilyl)hexyl, 8-(trimethoxysilyl)octyl, etc. can be cited.

[0060] In formula (1), n1 and n2 each independently represent an integer of 1 to 5 and satisfy the integer of n1 + n2 = 3 to 6, n3 and n4 each independently represent an integer of 1 to 5 and satisfy the integer of n3 + n4 = 3 to 6, and particularly preferably n1 and n4 are 3, and n2 and n3 are 1.

[0061] In addition, m represents an integer of 1 to 11.

[0062] As the cyclic organopolysiloxane containing an epoxy group represented by the above formula (1), from the viewpoint of easy availability of raw materials and excellent compatibility with general epoxy adhesives, compounds represented by the following (4) to (7) are preferred, but not limited to these. It should be noted that hereinafter, Me means methyl.

[0063] [Chemical formula 5]

[0064]

[0065] [Chemical formula 6]

[0066]

[0067] (In the formula, m1 represents an integer of 2 to 11.)

[0068] [Chemical formula 7]

[0069]

[0070] [Chemical formula 8]

[0071]

[0072] (In the formula, m2 represents an integer from 2 to 11.)

[0073] The cyclic organopolysiloxane compound containing an epoxy group of the present invention is obtained, for example, by subjecting a cyclic organohydrogenpolysiloxane represented by the following formula (3) to an addition reaction with a compound having one addition-reactive carbon-carbon double bond and an epoxy group in one molecule.

[0074] [Chemical formula 9]

[0075]

[0076] In formula (3), R 1 ~R 4 , Y, n1 to n4 and m have the same meanings as described above, and Z 11 , Z 12 each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms in which an oxygen atom may intervene or a hydrogen atom, and at least one of Z 11 , Z 12 is a hydrogen atom.

[0077] Examples of the monovalent hydrocarbon group for Z 11 and Z 12 include the same groups as those exemplified for R 1 ~R 4 above.

[0078] Specific examples of the compound represented by the above formula (3) include, but are not limited to, those represented by the following formula (8).

[0079] [Chemical formula 10]

[0080]

[0081] (In the formula, m3 represents an integer from 1 to 11.)

[0082] The compound having one addition-reactive carbon-carbon double bond and an epoxy group in one molecule is not particularly limited, but allyl glycidyl ether, hexenyl glycidyl ether, octenyl glycidyl ether, vinyl cyclohexene oxide, etc. are preferred, and from the viewpoint of market availability, allyl glycidyl ether and vinyl cyclohexene oxide are more preferred.

[0083] From the viewpoints of the thermal stability and productivity of the obtained cyclic organopolysiloxane having an epoxy group, the amount of the compound used is preferably 1 to 10 moles, more preferably 1.5 to 5 moles, per 1 mole of the hydrogen atom (Si-H group) bonded to a silicon atom in the compound represented by the above formula (3).

[0084] Regarding the catalyst for the addition reaction, a known catalyst generally used for hydrosilylation addition reaction can be used. For example, carbon powder loaded with platinum metal, platinum(IV) chloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and an olefin; platinum group metal catalysts such as palladium-based catalysts and rhodium-based catalysts can be cited.

[0085] Regarding the amount of the catalyst used, if the prevention of side reactions and the coloring of the product are considered, it is preferably 2% by mass or less, more preferably 5 to 5000 ppm, based on the total amount of the compound represented by the above formula (3).

[0086] A solvent can be used in the addition reaction.

[0087] As the solvent, it is preferable to be able to dissolve the compound represented by the above formula (3) and the compound having one addition-reactive carbon-carbon double bond and an epoxy group in one molecule.

[0088] Examples of the solvent that can be used include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, toluene, xylene, and mesitylene; alcohol solvents such as methanol, ethanol, and isopropanol; aprotic polar solvents such as acetonitrile, propionitrile, N,N-dimethylformamide, and N-methylpyrrolidone; halogenated hydrocarbon solvents such as dichloromethane, dichloroethane, and chlorobenzene; ether solvents such as diethyl ether, tetrahydrofuran, dioxane, and dimethoxyethane. These solvents can be used alone or in combination of two or more.

[0089] From the viewpoints of improving productivity due to shortening of the reaction time and preventing side reactions to prevent coloring of the product, the reaction temperature is preferably 20 to 150 °C, more preferably 60 to 100 °C.

[0090] As long as it is the time for sufficiently consuming the raw materials by carrying out the reaction, from the viewpoint of production efficiency, the reaction time is preferably 10 minutes to 24 hours, more preferably 1 to 10 hours, and further preferably 2 to 7 hours.

[0091] The weight-average molecular weight of the cyclic organopolysiloxane containing an epoxy group of the present invention is not particularly limited. However, when considering imparting sufficient hardness and flexural resistance to the cured product obtained by curing the curable composition containing the organopolysiloxane, the weight-average molecular weight is preferably 1,500 to 20,000, more preferably 2,000 to 15,000, and further preferably 3,000 to 10,000. It should be noted that the weight-average molecular weight in the present invention is the standard polystyrene conversion value measured by gel permeation chromatography (GPC).

[0092] The epoxy functional group equivalent of the cyclic organopolysiloxane containing an epoxy group of the present invention is not particularly limited. However, when considering imparting sufficient hardness and flexural resistance to the cured product obtained by curing the curable composition containing the organopolysiloxane, it is preferably 200 to 400 g / mol, more preferably 250 to 350 g / mol.

[0093] [2] Curable composition

[0094] The curable composition of the present invention comprises (A) the above-mentioned cyclic organopolysiloxane containing an epoxy group and (B) a curing agent.

[0095] The curing agent as the component (B) is not particularly limited. However, from the viewpoint of production efficiency, a photoacid generator (photo cationic polymerization initiator) that generates cationic species by irradiation with light to initiate the curing reaction of the cationic curable compound is preferred.

[0096] Examples of the photoacid generator include diazonium salt compounds, iodonium salt compounds, sulfonium salt compounds, phosphonium salt compounds, selenonium salt compounds, oxonium salt compounds, ammonium salt compounds, bromide salt compounds, etc. Among these, in the present invention, a sulfonium salt compound is preferably used in terms of being able to form a cured product with excellent curability.

[0097] Examples of the cation moiety of the sulfonium salt compound include arylsulfonium ions (especially triarylsulfonium ions) such as triphenylsulfonium ion, diphenyl[4-(phenylthio)phenyl]sulfonium ion, tri-p-tolylsulfonium ion, (4-hydroxyphenyl)methylbenzylsulfonium ion, 4-(4-biphenylthio)phenyl-4-biphenylylphenylsulfonium ion, etc.

[0098] Examples of the anion moiety include [(Ar) s B(Phf) 4-s - (In the formula, Ar represents a phenyl group or a biphenyl group. Phf represents a phenyl group in which at least one hydrogen atom is substituted with at least one selected from a perfluoroalkyl group, a perfluoroalkoxy group, and a halogen atom. s is an integer of 0 to 3.), BF4 - 、[(Rf) L PF 6-L ​​- (wherein, Rf represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms, and L is an integer of 0 to 5), AsF6 - , SbF6 - , pentafluoro-hydroxyantimonate, etc.

[0099] As specific examples of the photoacid generator, (4-hydroxyphenyl)methylbenzylsulfonium tetrakis(pentafluorophenyl)borate, 4-(4-biphenylthio)phenyl-4-biphenylylphenylsulfonium tetrakis(pentafluorophenyl)borate, 4-(phenylthio)phenyl diphenylsulfonium phenyltris(pentafluorophenyl)borate, [4-(4-biphenylthio)phenyl]-4-biphenylylphenylsulfonium phenyltris(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium tris(pentafluoroethyl)trifluorophosphate, diphenyl[4-(phenylthio)phenyl]sulfonium tetrakis(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, 4-(4-biphenylthio)phenyl-4-biphenylylphenylsulfonium tris(pentafluoroethyl)trifluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfide phenyltris(pentafluorophenyl)borate, [4-(2-thioxanthonylthio)phenyl]phenyl-2-thioxanthonylsulfonium phenyltris(pentafluorophenyl)borate, 4-(phenylthio)phenyl diphenylsulfonium hexafluoroantimonate, etc. can be used. These can be used under the trade names "CYRACURE UVI-6970", "CYRACURE UVI-6974", "CYRACURE UVI-6990", "CYRACURE UVI-950" (manufactured by Union Carbide Corporation, USA), "IRGACURE 250", "IRGACURE 261", "IRGACURE 264" (manufactured by Ciba Specialty Chemicals), "SP-150", "SP-151", "SP-170", "OPTOMER SP-171" (manufactured by ADEKA Corporation), "CG-24-61" (manufactured by Ciba Specialty Chemicals), "DAICATII" (manufactured by Daicel Corporation), "UVAC1590", "UVAC1591" (manufactured by Daicel-Cytec Company, Ltd.), "CI-2064", "CI-2639", "CI-2624", "CI-2481", "CI-2734", "CI-2855", "CI-2823", "CI-2758", "CIT-1682" (manufactured by Nippon Soda Co., Ltd.), "PI-2074" (manufactured by Rhodia), tetrakis(pentafluorophenylborate)toluoyl cumyl iodonium salt, "FFC509" (manufactured by 3M), "BBI-102", "BBI-101", "BBI-103", "MPI-103", "TPS-103", "MDS-103", "DTS-103", "NAT-103", "NDS-103" (manufactured by Midori Kagaku Co., Ltd.Commercially available products such as those manufactured by Sartomer Co., Ltd. including “CD-1010”, “CD-1011”, “CD-1012”, and those manufactured by San-Apro Ltd. including “CPI-100P”, “CPI-101A”, “CPI-200K”.

[0100] As needed, the curable composition of the present invention may contain an adhesive precursor other than the component (A) as the component (C).

[0101] The adhesive precursor is not particularly limited as long as it can become an adhesive. For example, thermoplastic resin systems such as (meth)acrylic resins and polyurethane resins can be cited; photocurable (meth)acrylic systems composed of functional or polyfunctional (meth)acrylates; photo- or thermosetting epoxy systems composed of monofunctional or polyfunctional epoxides; thermosetting anhydride systems composed of monofunctional or polyfunctional anhydrides; various adhesive precursors such as thermosetting silicone systems using silanols can be cited.

[0102] Among these, from the viewpoints of reactivity, productivity, and durability with the cyclic organopolysiloxane containing an epoxy group, a photo- or thermosetting epoxy-based adhesive precursor composed of a monofunctional or polyfunctional epoxide and a thermosetting anhydride-based adhesive precursor composed of a monofunctional or polyfunctional anhydride are preferred.

[0103] As the epoxy-based adhesive precursor, more preferably, an epoxide having a molecular weight of 100 to 3000, a functional group equivalent of the epoxy group of 100 to 300 g / mol, and having two or more, preferably two epoxy groups in one molecule can be cited. In particular, similar to the component (A), an epoxide represented by the following formula (C1), having a cyclic organopolysiloxane structure and having two or more, preferably 2 to 4 epoxy groups in one molecule is preferred.

[0104] [Chemical formula 11]

[0105]

[0106] (In the formula, R 1 , R 2 , Z 1 , Z 2 , n1 and n2 represent the same meanings as in the above formula (1), and at least two of Z 1 and Z 2 are monovalent organic groups containing an epoxy group into which an oxygen atom can intervene.)

[0107] The blending amount of the component (C) is preferably 1 to 200 parts by mass, more preferably 5 to 100 parts by mass with respect to 100 parts by mass of the component (A).

[0108] In addition, if necessary, the curable composition of the present invention can be diluted with an organic solvent and used. As the organic solvent at this time, components that can sufficiently dissolve the components and do not have reactivity with epoxy groups and curing catalysts are preferred. Specifically, aliphatic and / or aromatic hydrocarbon compounds, ester compounds, ketone compounds, ether compounds, etc. can be cited. Among these, from the viewpoint of market availability, isododecane, toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, etc. are preferred.

[0109] Furthermore, as other optional components, the curable composition of the present invention can contain inorganic fillers such as precipitated silica, wet-process silica, fumed silica, calcined silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate, carbon black, silicon carbide, silicon nitride, boron nitride, etc., and inorganic fillers treated with organosilicon compounds such as organohalosilanes, organoalkoxysilanes, and organosilazanes; organic resin fine powders such as silicone resins, epoxy resins, and fluororesins; conductive metal powders such as silver and copper, etc. fillers, curing aids, solvents (organic solvents, etc.), stabilizers (antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, heavy metal passivators, etc.), flame retardants (phosphorus-based flame retardants, halogen-based flame retardants, inorganic-based flame retardants, etc.), flame retardant aids, reinforcing materials (other fillers, etc.), nucleating agents, coupling agents (silane coupling agents, etc.), lubricants, waxes, plasticizers, release agents, impact modifiers, hue improvers, clarifying agents, rheology modifiers (flow improvers, etc.), processability improvers, colorants (dyes, pigments, etc.), antistatic agents, dispersants, surface modifiers (defoamers, leveling agents, anti-foaming agents, etc.), surface modifiers (slip agents, etc.), matting agents, defoamers, anti-foaming agents, degassing agents, antibacterial agents, preservatives, viscosity modifiers, thickeners, photosensitizers, foaming agents, etc. These additives can be used alone or in combination of two or more.

[0110] By irradiating and / or heating the curable composition of the present invention, it is cured to obtain a corresponding cured product. There is no particular limitation on its form, and it can be a cured coating film on a substrate, or a self-supporting cured molded product or sealant. From the aspect of productivity, the curing method is preferably photocuring.

[0111] When photocuring the curable composition of the present invention, for example, the curable composition is coated on a substrate to form a desired film thickness, and then, if necessary, after the solvent is volatilized, ultraviolet rays, electron beams, etc. are irradiated using a high-pressure mercury lamp, metal halide lamp, LED lamp, etc. The irradiation atmosphere can be in air or in an inert gas such as nitrogen or argon. In the case of irradiating ultraviolet rays, for example, it is preferably set to about 1 to 1000 mJ / cm 2 or so.

[0112] On the other hand, there are no particular limitations on the conditions for heat-curing the curable composition of the present invention. For example, it is preferably 30 to 200°C, more preferably 50 to 190°C. The curing time can be set appropriately.

[0113] The substrate is not particularly limited, and examples thereof include organic resins such as plastic molded bodies, wood-based products, fibers, ceramics, glass, metals, or composites thereof.

[0114] Among these, the curable composition of the present invention can be suitably used for various plastic materials. In particular, it can be suitably used for polycarbonate resins, polystyrene resins, acrylic resins, modified acrylic resins, polyurethane resins, thiourethane resins, condensates of halogenated bisphenol A and ethylene glycol, acrylic polyurethane resins, acrylic resins containing halogenated aryl groups, sulfur-containing resins, polyalkylene terephthalate resins, polyimide resins, polyamide resins, polycycloolefin resins, polyphenylene sulfide resins, polyphenylene ether resins, cellulose resins, amorphous polyolefin resins, and composite resins thereof.

[0115] In addition, products obtained by surface-treating these resin substrates can also be used. Specifically, products subjected to chemical conversion treatment, corona discharge treatment, flame treatment, plasma treatment, acid or alkali solution treatment can be used. In addition, laminates in which the surface layer is coated with a resin different in type from the substrate main body can also be used. Specific examples of the laminate include laminates in which an acrylic resin layer or a polyurethane resin layer exists on the surface layer of a polycarbonate resin substrate manufactured by a co-extrusion method or a lamination method, and laminates in which an acrylic resin layer exists on the surface layer of a polyester resin substrate.

[0116] Furthermore, the curable composition of the present invention can be directly coated on the surface of the substrate, and can also be coated via a primer layer, an ultraviolet absorption layer, a printing layer, a recording layer, an infrared shielding layer, a thermosensitive adhesive layer, an inorganic vapor deposition coating layer, etc. as needed.

[0117] Regarding the coating method, for example, it can be appropriately selected and used from known coating methods such as spin coaters, bevel wheel coaters, lip coaters, roll coaters, die coaters, knife coaters, doctor blade coaters, bar coaters, kiss coaters, gravure coaters, screen coating, dip coating, and casting coating.

[0118] Furthermore, as needed, other coating layers such as an adhesive layer, an ultraviolet absorption layer, a printing layer, a recording layer, an infrared shielding layer, a thermosensitive adhesive layer, an inorganic vapor deposition coating layer, a water and oil repellent layer, and a hydrophilic antifouling layer can be formed on the surface of the cured coating film of the coating composition of the present invention.

[0119] In addition, in addition to the method using a mold, the curable composition of the present invention can be formed into a self-supporting cured molded article by a film forming method based on a casting method in which the composition is coated and cured on a film having a release layer in advance.

[0120] The material of the mold is not particularly limited as long as it ensures the releasability of the cured product obtained after curing. For example, it can be any of metal, glass, plastic, silicone, and a Teflon (registered trademark, the same below)-treated mold. Among them, a Teflon-treated mold is preferably used. The Teflon-treated mold has excellent releasability in the present invention and can suppress the generation of breakage of the cured product when the curable composition is taken out.

[0121] The cured product obtained by using the curable composition of the present invention can have both crack resistance and flexibility, and thus can be applied to abrasion-resistant coatings for plastic substrates, optical lenses, flexible display materials for electronic materials, optical sealing materials such as LED devices, and denture molding materials, tooth filling agents, etc.

[0122] Examples

[0123] Synthesis examples, examples, and comparative examples are listed below to illustrate the present invention more specifically, but the present invention is not limited to these examples. In addition, in the following examples, unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass", respectively. In addition, the devices used in the examples are as described below.

[0124] (1) GPC measurement conditions

[0125] Device: HLC-8320GPC manufactured by Tosoh Corporation

[0126] Elution solvent: Tetrahydrofuran (THF)

[0127] Flow rate: 0.6 mL / min

[0128] Detector: Differential refractive index detector (RI)

[0129] Column: TSK Guardcolumn SuperH-H

[0130] TSKgel SuperHM-N (6.0 mm I.D. × 15 cm × 1)

[0131] TSKgel SuperH2500 (6.0 mm I.D. × 15 cm × 1)

[0132] (All are manufactured by Tosoh Corporation)

[0133] Column temperature: 40 °C

[0134] Sample injection volume: 50 μL (THF solution with a concentration of 2.0 mass%)

[0135] Standard: Monodisperse polystyrene

[0136] (2) Proton nuclear magnetic resonance spectroscopy ( 1 1H-NMR) measurement conditions

[0137] Apparatus: AVANCE III 400 manufactured by BURKER

[0138] Solvent: CDCl3

[0139] Internal standard: Tetramethylsilane (TMS)

[0140] (3) Kinematic viscosity measurement conditions

[0141] Measured using a Canon-Fenske viscometer at 25 °C.

[0142] (4) Viscosity measurement conditions

[0143] Measured using a Type B rotational viscometer at 25 °C.

[0144] [1] Synthesis of cyclic organohydrogen polysiloxane

[0145] [Synthesis Example 1]

[0146] 80 g of toluene and 115.2 g (0.48 mol) of 1,3,5,7-tetramethylcyclotetrasiloxane were added to a 500 mL four-necked flask equipped with a stirring device, a condenser, a dropping funnel, and a thermometer, and heated to 117 °C using an oil bath. 0.05 g of carbon powder loaded with 5% platinum metal was added thereto, and 48 g (0.4 mol) of vinyl norbornene (trade name: V0062, manufactured by Tokyo Chemical Industry Co., Ltd.; an isomer mixture of approximately equimolar amounts of 5-vinylbicyclo[2.2.1]hept-2-ene and 6-vinylbicyclo[2.2.1]hept-2-ene) was dropped therein over 16 minutes while stirring. After the dropping was completed, the mixture was heated and stirred at 125 °C for 16 hours and then cooled to room temperature. Then, the carbon loaded with platinum metal was filtered off, and toluene was distilled off under reduced pressure to obtain a colorless transparent viscous liquid (A-0). The kinematic viscosity of this liquid at 25 °C was 2500 mm 2 / s, and the average amount of SiH contained was 7.2 mmol / g.

[0147] By 1 1H-NMR and GPC measurement and analysis, the viscous liquid (A-0) was confirmed to be a mixture of the compounds shown below.

[0148] · Compounds having 1 tetramethylcyclotetrasiloxane ring: approximately 6 mol% (showing an example of the structural formula represented by the following formula (9).)

[0149] [Chemical Formula 12]

[0150]

[0151] · Compounds having 2 tetramethylcyclotetrasiloxane rings: approximately 25 mol% (showing an example of the structural formula represented by the following formula (10).)

[0152] [Chemical Formula 13]

[0153]

[0154] · Compounds having 3 tetramethylcyclotetrasiloxane rings: approximately 16 mol% (showing an example of the structural formula represented by the following formula (11), where m = 2).

[0155] · Compounds having 4 tetramethylcyclotetrasiloxane rings: approximately 11 mol% (showing an example of the structural formula represented by the following formula (11), where m = 3).

[0156] · Compounds having 5 to 12 cyclotetrasiloxane rings: the remainder (showing an example of the structural formula represented by the following formula (11), where m = 4 to 11).

[0157] [Chemical Formula 14]

[0158]

[0159] [2] Synthesis of cyclic organopolysiloxanes containing epoxy groups

[0160] [Example 1-1]

[0161] In a 1 L detachable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 124 parts (1 mole) of 1,2-epoxy-4-vinylcyclohexane, 121 parts of toluene, 37 parts of isopropanol, 0.12 part of acetonitrile, and 0.0001 mole (in terms of platinum) of a toluene solution of a platinum complex (1,3-divinyltetramethyldisiloxane complex of Pt(0)) were placed and stirred and mixed. Then, when heating was carried out to an internal temperature of 85°C, 116 parts (Si-H; 0.83 mole) of the viscous liquid (A-0) obtained in Synthesis Example 1 were dropped in over 1 hour. A reaction occurred simultaneously with the dropping, generating heat, and the temperature of the reaction solution slowly rose from 85°C. Therefore, adjustment was made so that the temperature of the reaction solution did not exceed 90°C, and the dropping was continued simultaneously. After the dropping was completed, the reaction solution was aged for 6 hours while heating to make the internal temperature 90°C, and then the hydrogen generation amount of the reaction solution was measured, and it was confirmed that no Si-H groups remained. Then, 0.02 part of triphenylphosphine was added, and toluene, isopropanol, acetonitrile, and excess 1,2-epoxy-4-vinylcyclohexane were removed by distillation under reduced pressure (90°C, 5 mmHg), thereby obtaining a pale yellow viscous liquid (A-1) having a viscosity of 2000 Pa·s or more at 25°C and an epoxy equivalent of 295 g / mol. From the results of GPC and 1 1H-NMR measurements, it was confirmed that the viscous liquid (A-1) was a mixture represented by the following formula (12) (m = 1 to 11).

[0162] [Chemical Formula 15]

[0163]

[0164] [Example 1-2]

[0165] In a 1 L detachable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 114 parts (1 mole) of allyl glycidyl ether, 121 parts of toluene, 37 parts of isopropanol, 0.12 part of acetonitrile, and 0.0001 mole (in terms of platinum) of a toluene solution of a platinum complex (1,3-divinyltetramethyldisiloxane complex of Pt(0)) were placed and stirred and mixed. Then, when heated to an internal temperature of 85°C, 116 parts (Si-H; 0.83 mole) of the viscous liquid (A-0) obtained in the synthesis example were dropped in over 1 hour. A reaction occurred during the dropping, generating heat, and the temperature of the reaction solution slowly rose from 85°C. Therefore, the dropping was continued while adjusting so that the temperature of the reaction solution did not exceed 90°C. After the dropping was completed, heating was carried out to make the internal temperature 90°C, and while aging the reaction solution for 6 hours, the hydrogen generation amount of the reaction solution was measured, and it was confirmed that no Si-H groups remained. Then, 0.02 part of triphenylphosphine was added, and toluene, isopropanol, acetonitrile, and excess allyl glycidyl ether were removed by distillation under reduced pressure (90°C, 5 mmHg), thereby obtaining a pale yellow viscous oil (A-2) having a viscosity of 2000 Pa·s or more at 25°C and an epoxy equivalent of 282 g / mol. From the results of GPC and 1 1H-NMR measurements, it was confirmed that the pale yellow highly viscous oil (A-2) was a mixture (m = 1 to 11) represented by the following formula (13).

[0166] [Chemical Formula 16]

[0167]

[0168] [3] Preparation of Curable Composition for Coating and Cured Product

[0169] [Examples 2-1 to 2-3, Comparative Examples 2-1 to 2-4]

[0170] Each component was mixed in the mixing ratio shown in Table 1 to prepare a curable composition for coating.

[0171] [Table 1]

[0172]

[0173] (A-1): Cyclic organopolysiloxane containing an epoxy group obtained in Example 1-1 (A-2): Cyclic organopolysiloxane containing an epoxy group obtained in Example 1-2 (B-1): Non-antimony-based photo cationic polymerization initiator (manufactured by San-Apro Ltd., "CPI-200K")

[0174] (C-1): Cyclic siloxane represented by the following formula (14) (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "X-40-2678", epoxy equivalent: 300)

[0175] (C-2): Cyclic siloxane represented by the following formula (15) (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KR-470", epoxy equivalent: 200)

[0176] (C-3): Dimethylsiloxane having an epoxycyclohexyl structural group in the side chain and a viscosity of 280 mPa·s at 25°C (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "X-40-2715", epoxy equivalent 290)

[0177] (C-4): Hydrocarbon-based difunctional epoxycyclohexyl compound (manufactured by Daicel Corporation, CELLOXIDE 2021P)

[0178] [Chemical formula 17]

[0179]

[0180] After coating the curable compositions for coating obtained in Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-4 on the surface of a polycarbonate NF-2000 sheet (thickness 4 mm × length 15 cm × width 10 cm) manufactured by Mitsubishi Engineering-Plastics Corporation using a bar coater No. 14, air-dried for 15 minutes, and then heated at 80°C for 1 minute, a high-pressure mercury lamp was used to irradiate with a light irradiation dose of 600 mJ / cm 2 to cure the coating film and obtain test pieces.

[0181] For each test piece, the following evaluations were carried out. The results are shown in Table 2.

[0182] (1) Coating film appearance

[0183] The coating film was visually observed to determine the presence or absence of abnormalities.

[0184] ○: No abnormality

[0185] △: Coloration

[0186] ×: Abnormalities such as foreign matter, unevenness, and whitening

[0187] (2) Initial haze

[0188] Using a haze meter NDH5000SP manufactured by Nippon Denshoku Industries Co., Ltd., the haze of the coated sheet was measured as the initial haze.

[0189] (3) Abrasion resistance

[0190] According to ASTM1044, using a Taper wear tester, a wear wheel CS-10F was installed, and the haze after 100 revolutions under a load of 500 g was measured. The difference in haze after the test and before the test was defined as the abrasion resistance.

[0191] (4) Initial adhesion

[0192] According to JIS K5600, 6 cuts were made in the coating film at intervals of 2 mm using a razor blade to make 25 checkerboards. After Cellotape (registered trademark, manufactured by NICHIBAN Co., Ltd.) was fully adhered, the number of grids (X) remaining without peeling off the coating film when it was peeled off sharply in the 90° forward direction was expressed as X / 25.

[0193] (5) Boiling tightness

[0194] The adhesion after immersing the test piece in boiling water for 2 hours was evaluated in the same manner as the above-mentioned initial adhesion.

[0195] (6) Pencil hardness

[0196] The results are shown below, with the pencil scratch test method according to JIS K5600-5-4 being performed with a load of 750 g applied.

[0197] (7) Crack resistance (impact resistance)

[0198] The results are shown below, which were measured using a DuPont impact tester in accordance with the method of the weight drop resistance test described in JIS K5600-5-3.

[0199] [Table 2]

[0200]

[0201] As shown in Table 2, it was found that the coating films composed of the curable compositions for coating of Examples 2-1 to 2-3 achieved transparency, hardness, adhesion, and crack resistance.

[0202] On the other hand, it can be seen that in Comparative Example 2-1, due to insufficient hardness and adhesion, the scratch resistance also tends to deteriorate. In Comparative Example 2-2, although the hardness is excellent, the film lacks flexibility and the crack resistance is insufficient. In Comparative Example 2-3, due to insufficient hardness and flexibility, the scratch resistance tends to deteriorate. In Comparative Example 4, due to corrosion of the polycarbonate substrate used, the initial haze deteriorates, and the hardness and flexibility are also insufficient.

[0203] [4] Preparation of curable composition for sheet molding

[0204] [Examples 3-1, 3-2, Comparative Examples 3-1 to 3-4]

[0205] The respective components were mixed in the mixing ratio shown in Table 3 to prepare a curable composition for sheet molding. The abbreviations in the table are the same as those described above.

[0206] [Table 3]

[0207]

[0208] After casting the compositions obtained in Examples 3-1 and 3-2 and Comparative Examples 3-1 to 3-4 into a Teflon (registered trademark)-treated mold (depth 0.3 mm × length 15 cm × width 10 cm), allowing it to stand for 30 minutes, and irradiating with light having an irradiation dose of 600 mJ / cm 2 , it was cured to obtain a film-like test piece.

[0209] Regarding each test piece, the following evaluations were carried out. The results are shown in Table 4.

[0210] (8) Film appearance

[0211] By visually observing the test piece obtained above, the presence or absence of abnormalities was determined.

[0212] ○: No abnormality

[0213] ×: Abnormality such as cracking

[0214] (9) Film formability

[0215] When taking it out of the mold, it was observed whether it became a self-supporting film and judged as follows.

[0216] ○: No abnormality and can be taken out as a film.

[0217] ×: Brittle and cannot be taken out as a film.

[0218] (10) 90° bendability

[0219] The test piece obtained above was cut into a width of 1 cm to make a strip having a length of 10 cm, a width of 1 cm, and a thickness of 0.3 mm. The two short-side portions were pinched with tweezers, and the state of the film when bent at 90° was observed and judged as follows.

[0220] ○: Can be bent without breakage.

[0221] △: Cracking occurs in part but no breakage.

[0222] ×: Completely broken and cannot be bent.

[0223] (11) Storage modulus, Tanδ(max)

[0224] The test piece obtained above was cut into a width of 1 cm to make a strip having a length of 10 cm, a width of 1 cm, and a thickness of 0.3 mm. Using a viscoelasticity measuring device DMA7100 manufactured by Hitachi High-Technologies Corporation, in an air atmosphere, it was heated from -50°C to 250°C at a heating rate of 10°C / min and measured in a tensile measurement mode.

[0225] [Table 4]

[0226]

[0227] As can be seen from Table 4, the films obtained from the compositions of Examples 3-1 and 3-2 achieved formability, flexibility, and hardness (storage modulus).

[0228] On the other hand, it can be seen that in Comparative Example 3-1, although the formability was good, the hardness (storage modulus) was low, and it was found that Tanδ(max) corresponding to the glass transition temperature decreased. In Comparative Example 3-2, since the cured product was very brittle and the crack resistance was low, a film sufficient for measurement was not obtained. In Comparative Examples 3-3 and 3-4, the flexibility was insufficient, and compared with the examples, the films had poor hardness (storage modulus).

[0229] As described above, the cured product obtained by using the cyclic organopolysiloxane containing an epoxy group of the present invention has both hardness and flexibility, and can be suitably used as a cured molded product used in hard coatings for plastic substrates, lens materials, sealing materials, etc.

Claims

1. A cyclic organopolysiloxane containing an epoxy group, which is represented by the following general formula (1): [Chemical formula 1] In the formula, R 1 , R 2 , R 3 and R 4 each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms in which an oxygen atom may intervene. Y represents a divalent hydrocarbon group, Z 1 and Z 2 each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms in which an oxygen atom can intervene, a monovalent organic group containing an epoxy group in which an oxygen atom can intervene, an alkoxysilylalkyl, or a hydrogen atom, and Z 1 and Z 2 at least one of them is a monovalent organic group containing an epoxy group in which an oxygen atom can intervene, n1 and n2 each independently represent an integer of 1 to 5 and satisfy that n1 + n2 is an integer of 3 to 6, n3 and n4 each independently represent an integer of 1 to 5 and satisfy that n3 + n4 is an integer of 3 to 6, m represents an integer of 1 to 11.

2. The cyclic organopolysiloxane containing an epoxy group according to claim 1, wherein, The R 1 , R 2 , R 3 and R 4 are methyl groups.

3. The cyclic organopolysiloxane containing epoxy groups according to claim 1, wherein, Said Z 1 and Z 2 is one or more selected from 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl.

4. The cyclic organopolysiloxane containing epoxy groups according to claim 1, wherein, The Y is a divalent saturated hydrocarbon group having a polycyclic structure.

5. The cyclic organopolysiloxane containing epoxy groups according to claim 4, wherein, The Y is one or more divalent saturated hydrocarbon groups selected from those represented by the following formulae (2a) and (2b), [Chemical formula 2] In the formula, the asterisk (*) represents the bonding site to the silicon atom, and the spatial configuration of each chiral carbon can be either cis (exo) or trans (endo).

6. The cyclic organopolysiloxane containing epoxy groups according to claim 1, wherein, n1 and n4 are 3, and n2 and n3 are 1.

7. The cyclic organopolysiloxane containing epoxy groups according to claim 1, wherein, The functional group equivalent of the epoxy group is 200 to 400 g / mol.

8. A curable composition, which comprises: (A) 100 parts by mass of the cyclic organopolysiloxane containing an epoxy group according to any one of claims 1 to 7; and (B) 0.01 to 5 parts by mass of a curing agent.

9. The curable composition according to claim 8, which comprises (C) 1 to 200 parts by mass of a compound containing an epoxy group other than (A).

10. The curable composition according to claim 9, wherein, The curing agent is a photoacid generator.

11. A cured product, which is a cured product obtained by curing the curable composition according to claim 9.

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