Silicone compound, method for producing the same, and curable composition

Abstract

An organic silicon compound represented by the following formula (1). (R 1 is an alkyl group, an alkenyl group, an aryl group or an acyl group, R 2 is an alkyl group or an aryl group, R 3 is a hydrogen atom or a methyl group, A 1 is a single bond or an alkylene group, A 2 , A 3 , A 4 is a methylene group or an oxygen atom, however, A 2 , A 3 and A 4 one or more of A to A are oxygen atoms, and n is an integer of 1 to 3.)

Description

Technical Field

[0001] This invention relates to organosilicon compounds, methods of manufacturing the same, and curable compositions thereof, and more specifically, to organosilicon compounds having hydrolyzable silyl groups and polymerizable groups within the molecule, methods of manufacturing the same, curable compositions comprising the compound, and articles having a coating composed of a cured product of the composition. Background Technology

[0002] Silane coupling agents are compounds that simultaneously possess a portion that is reactive to inorganic substances (hydrolyzable groups that are bonded to Si atoms) and a portion that can impart various functions such as reactivity, solubility, and free radical polymerization to organic substances within a single molecule. They function as adhesives at the interface between inorganic and organic substances and as resin modifiers for inorganic-organic composite materials, and are therefore widely used as composite resin modifiers.

[0003] Among them, silane coupling agents with polymerizable groups are used as resin modifiers for (meth)acrylic resins and as adhesive aids for pressure-sensitive adhesives based on (meth)acrylic polymers.

[0004] However, primer compositions using existing silane coupling agents with polymerizable groups and adhesive compositions containing silane coupling agents with polymerizable groups do not provide sufficient adhesion to various substrates, which is the problem.

[0005] On the other hand, as polymerizable compounds capable of forming compositions that provide excellent adhesion to various substrates, compounds having an allyl ether site and an acryloyl group within the same molecule have been reported (Patent Documents 1 and 2). These compounds exhibit cyclization polymerization via a free radical polymerization mechanism, and compositions containing these compounds exhibit superior curing properties and post-curing physical properties compared to compositions containing existing polymerizable compounds.

[0006] As polymerizable silane coupling agents, silane coupling agents with an acryloyl group or a methacryloyl group with a methyl α-substituent are known, but examples of silane coupling agents with different α-substituents are rare. In particular, there are no reported examples of silane coupling agents exhibiting cyclization polymerization that have an alkenyl ether site and an acryloyl group within the same molecule.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 2011-074068

[0010] Patent Document 2: Japanese Patent Application Publication No. 2011-137123 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] The present invention was made in view of the above-mentioned circumstances, and its object is to provide an organosilicon compound that can form a cured product with excellent adhesion to a substrate by being added to a curable composition, a method for manufacturing the same, a curable composition containing the compound, a coating agent, an adhesive, and a cured article.

[0013] Methods for solving problems

[0014] To achieve the above objectives, the inventors conducted in-depth research and discovered an organosilicon compound having a hydrolyzable silyl group, an alkenyl ether site, and an acryloyl group within one molecule, as well as a method for manufacturing the same. Furthermore, they discovered that curable compositions containing this organosilicon compound can form cured products with excellent adhesion to substrates, thus making them suitable as coating agents and adhesives. This led to the completion of the present invention.

[0015] Therefore, the present invention provides the following organosilicon compounds, methods for their manufacture, curable compositions, coating agents, adhesives and articles.

[0016] [1] Organosilicon compounds represented by the following formula (1),

[0017] [Chemistry 1]

[0018]

[0019] In the formula, R 1 Each group is independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an acyl group having 1 to 20 carbon atoms.

[0020] R 2 Each is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.

[0021] R 3 It can be a hydrogen atom or a methyl group.

[0022] A 1 It is a single bond or an unsubstituted or substituted divalent hydrocarbon group with 1 to 20 carbon atoms.

[0023] A 2 A 3 A 4 Each is an unsubstituted or substituted methylene or oxygen atom, wherein A 2 A 3 and A 4 One or more of them are oxygen atoms, and the oxygen atoms are not adjacent to each other.

[0024] n is an integer from 1 to 3.

[0025] [2]. According to the organosilicon compound described in [1], wherein A 1 It is an alkylene group having 1 to 10 carbon atoms.

[0026] [3]. The organosilicon compound according to [1] or [2], wherein, A 2 and the A 4 The A is a methylene group. 3 It is an oxygen atom.

[0027] [4]. A method for manufacturing an organosilicon compound according to any one of [1] to [3], wherein an organosilicon compound containing a halogen group represented by the following formula (3) is reacted with a metal salt compound represented by the following formula (4),

[0028] [Chemistry 2]

[0029]

[0030] In the formula, R 1 R 2 R 3 A 1 A 2 A 3 A 4 The same applies to n as above, where X is a chlorine atom, bromine atom, or iodine atom, and M is an alkali metal.

[0031] [5]. A curable composition comprising an organosilicon compound according to any one of [1] to [3].

[0032] [6]. A coating agent comprising the curable composition according to [5].

[0033] [7]. An adhesive comprising the curable composition according to [5].

[0034] [8]. A cured product obtained by curing the curing composition according to [5].

[0035] [9]. Article having a coating layer cured according to the coating agent described in [6].

[0036]

[10] . An article having an adhesive layer cured according to the adhesive described in [7].

[0037] The effects of the invention

[0038] According to the present invention, an organosilicon compound having a hydrolyzable silyl group, an alkenyl ether site, and an acryloyl group within one molecule is provided. Curable compositions comprising this organosilicon compound exhibit excellent adhesion to various substrates, thus making them suitable for various applications such as coatings and adhesives. Detailed Implementation

[0039] The present invention will now be described in detail. It should be noted that in the present invention, "silane coupling agent" is included in "organosilicon compound".

[0040] [Organosilicon compounds]

[0041] The organosilicon compounds of the present invention are represented by the following formula (1).

[0042] [Chemistry 3]

[0043]

[0044] R 1 Each is independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an acyl group having 1 to 20 carbon atoms.

[0045] Specific examples include linear, branched, or cyclic alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-octyl, and cyclohexyl; alkenyl groups such as vinyl, allyl, and propenyl; aryl groups such as phenyl, tolyl, xylyl, and naphthyl; and acyl groups such as formyl, acetyl, and propionyl. Among these, alkyl groups with 1 to 8 carbon atoms are preferred, more preferably 1 to 6, and methyl and ethyl groups are even more preferred.

[0046] R 2 Each is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.

[0047] Specific examples include linear, branched, or cyclic alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-octyl, and cyclohexyl; and aryl groups such as phenyl, tolyl, xylyl, and naphthyl. Among these, alkyl groups and phenyl groups with 1 to 8 carbon atoms are preferred, more preferably 1 to 6 carbon atoms, and methyl, ethyl, and phenyl groups are even more preferred.

[0048] R 3 It can be a hydrogen atom or a methyl group.

[0049] A 1 It is a single bond or an unsubstituted or substituted divalent hydrocarbon group with 1 to 20 carbon atoms, as A 1The divalent hydrocarbon group can be linear, branched, or cyclic. Specific examples include alkylene groups with 1 to 20 carbon atoms, preferably 1 to 6; cycloalkylene groups with 3 to 20 carbon atoms; alkenylene groups with 2 to 10 carbon atoms; arylene groups with 6 to 10 carbon atoms; and arylalkylene groups with 7 to 10 carbon atoms. Specifically, examples include alkylene groups such as methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, and octamethylene; cycloalkylene groups such as cyclohexylene; alkenylene groups such as vinylene and propenylene; arylene groups such as phenylene, tolylene, xylene, and naphthylene; and arylalkylene groups such as benzylene, phenylethylene, and phenylpropylene.

[0050] A 2 A 3 A 4 Each is independently an unsubstituted or substituted methylene or oxygen atom; however, A 2 A 3 and A 4 One or more of the atoms in the group are oxygen atoms, and these oxygen atoms are not adjacent to each other. Examples of substituted methylene groups include methylmethylene and dimethylmethylene.

[0051] n is an integer from 1 to 3.

[0052] The organosilicon compound of the present invention is preferably represented by the following formula (2).

[0053] [Chemistry 4]

[0054]

[0055] (where R is in the formula) 1 R 2 R 3 A 2 A 3 A 4 And n is the same as above, where m represents an integer from 1 to 10.

[0056] A 2 A 3 A 4 Among them, A is preferred. 2 and A 4 It is methylene and A 3 It is an oxygen atom.

[0057] m is an integer from 1 to 10, preferably an integer from 2 to 10, and more preferably an integer from 2 to 6.

[0058] Therefore, the organosilicon compound of the present invention is more preferably represented by the following formula (5).

[0059] [Chemistry 5]

[0060]

[0061] (where R is in the formula) 1 R 2 (m and n are the same as above.)

[0062] Specific examples of such organosilicon compounds can be cited as examples represented by the following formulas (6) to (9).

[0063] [Chemistry 6]

[0064]

[0065] (In the formula, Me represents methyl and Et represents ethyl.)

[0066] The kinematic viscosity of the organosilicon compound of the present invention is not particularly limited, but is preferably 0.1 to 1000 mm. 2 / s, preferably 0.5~100mm 2 / s, more preferably 1 to 10 mm 2 / s. It should be noted that the kinematic viscosity is a value determined based on JIS Z 8803.

[0067] The organosilicon compounds of the present invention can be obtained, for example, by reacting an organosilicon compound containing a halogen group represented by the following formula (3) with a metal salt compound represented by the following formula (4).

[0068] [Chemistry 7]

[0069]

[0070] (where R is in the formula) 1 R 2 R 3 A 1 A 2 A 3 A 4 And n is the same as above, X is a chlorine atom, bromine atom, or iodine atom, and M is an alkali metal.

[0071] Examples of alkali metals that are M include sodium and potassium.

[0072] Specific examples of organosilicon compounds containing halogen groups represented by the above formula (3) include 3-chloropropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyldimethylmethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropylmethyldiethoxysilane, and 3-chloropropyldimethylethoxysilane.

[0073] Specific examples of metal salt compounds represented by the above formula (4) include sodium 2-(allyloxymethyl)acrylate and potassium 2-(allyloxymethyl)acrylate.

[0074] The organosilicon compound containing a halogen group, represented by formula (3) above, and the metal salt compound represented by formula (4) above, are preferably reacted in a molar ratio of organosilicon compound containing a halogen group: metal salt compound = 1.0:0.3 to 1.0:3.0, especially 1:0.8 to 1:1.2.

[0075] In the manufacture of the organosilicon compound of the present invention, it is preferable to add a polymerization inhibitor, and more preferably, a gas containing molecular oxygen is allowed to coexist with the polymerization inhibitor. As the aforementioned gas containing molecular oxygen, air or oxygen diluted with an inert gas such as nitrogen is typically used and blown into the processing equipment.

[0076] As the aforementioned polymerization inhibitors, polymerization inhibitors for free radical polymerizable monomers can be used, such as phenolic polymerization inhibitors like hydroquinone, methylhydroquinone, trimethylhydroquinone, tert-butylhydroquinone, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, 6-tert-butyl-2,4-xylenol, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methoxyphenol, and 2,2'-methylenebis(4-methyl-6-tert-butylphenol); copper salts of organic acids; and phenothiazines. Among these, phenolic polymerization inhibitors are preferred in terms of low coloring and polymerization resistance. From the perspectives of availability and economy, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, 6-tert-butyl-2,4-xylenol, and 2,6-di-tert-butylphenol are particularly preferred.

[0077] These polymerization inhibitors can be used alone or in combination of two or more.

[0078] There is no particular limitation on the amount of polymerization inhibitor added. It is approximately 100 to 100,000 ppm, based on the mass of the metal salt compound represented by the above formula (4).

[0079] In the manufacture of the organosilicon compound of the present invention, a catalyst such as a phase transfer catalyst may be used as needed. Specific examples of phase transfer catalysts include quaternary phosphonium salts and quaternary ammonium salts.

[0080] Examples of quaternary phosphonium salts include tetraethylphosphonium chloride, tetraethylphosphonium bromide, tetraethylphosphonium iodide, tetrabutylphosphonium bromide, triphenylbenzylphosphonium bromide, and tetraphenylphosphonium bromide.

[0081] Examples of quaternary ammonium salts include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylbenzylammonium hydroxide, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, trimethylbenzylammonium bromide, triethylbenzylammonium bromide, trimethylphenylammonium bromide, triethylbenzylammonium chloride, tetramethylammonium chloride, trioctylmethylammonium chloride, tributylbenzylammonium chloride, trimethylbenzylammonium chloride, N-laurylpyridinium chloride, N-benzylmethylpyridinium chloride, N-lauryl-4-methylpyridinium chloride, N-laurylmethylpyridinium chloride, trioctylmethylammonium chloride, tetramethylammonium iodide, tetra-n-butylammonium iodide, and tetrabutylammonium hydrogen sulfate.

[0082] There is no particular limitation on the amount of catalyst used. From the perspective of reactivity and productivity, the catalyst is preferably 0.1 to 10.0% by mass, more preferably 1.0 to 5.0% by mass, and particularly preferably 2.0 to 4.0% by mass, relative to the organosilicon compound containing a halogen group represented by the above formula (3).

[0083] When manufacturing the organosilicon compounds of the present invention, solvents may be used as needed, and there are no particular limitations as long as the solvent is non-reactive to the halogen-containing organosilicon compounds and metal salt compounds used as raw materials.

[0084] Specifically, examples include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, and decane; ether solvents such as diethyl ether and tetrahydrofuran; and aromatic hydrocarbon solvents such as benzene, toluene, and xylene. One of these solvents can be used alone, or two or more can be mixed.

[0085] There is no particular limitation on the reaction temperature in the above reaction, and it can be carried out from 0°C to heating, preferably 0 to 200°C. In order to obtain a suitable reaction rate, it is preferable to carry out the reaction under heating. From this point of view, the reaction temperature is more preferably 40 to 110°C, and even more preferably 40 to 90°C.

[0086] In addition, there is no particular limitation on the reaction time. It is usually around 1 to 30 hours, preferably 1 to 20 hours, and more preferably 1 to 10 hours.

[0087] The alkali metal halides generated during the manufacture of the organosilicon compounds of the present invention can be separated from the target organosilicon compounds using known methods such as filtration. The organosilicon compounds of the present invention can be further purified using known methods such as vacuum distillation and liquid chromatography.

[0088] [Curing composition]

[0089] The curable composition of the present invention contains an organosilicon compound represented by the above formula (1).

[0090] The organosilicon compounds of the present invention, when added to a curable composition, can improve the adhesion of the cured product obtained by curing the composition to various substrates. Therefore, the curable compositions of the present invention can be used as coating compositions and adhesive compositions.

[0091] In curable compositions, coating compositions, and adhesive compositions (hereinafter collectively referred to as compositions) containing the organosilicon compounds of the present invention, the content of the aforementioned organosilicon compounds is not particularly limited, but is preferably about 0.1 to 50% by mass, more preferably 0.5 to 30% by mass. Furthermore, in the case where the composition contains a solvent, the aforementioned content means excluding the non-volatile components of the solvent.

[0092] The compositions of the present invention preferably contain an organic resin as the main agent (base resin).

[0093] As organic resins, there are no particular limitations. Specific examples include epoxy resins, phenolic resins, polycarbonate and polycarbonate blends, acrylic resins, polyester resins, polyamide resins, polyimide resins, polyurethane resins, polybutadiene resins, styrene-butadiene copolymer resins, acrylonitrile-styrene copolymer resins, styrene-acrylonitrile-butadiene copolymer resins, polyvinyl chloride resins, polystyrene resins, polyphenylene ether resins, polyphenylene ether resins containing polymerizable reactive groups, blends of polystyrene and polyphenylene ether, cellulose acetate butyrate resins, etc.

[0094] Furthermore, suitable curing agents can be formulated according to the organic resin used. For example, when using epoxy resin, curing agents such as imidazole compounds can be formulated, and when using polyphenylene ether resin containing polymerizable reactive groups, curing agents such as peroxides can be formulated.

[0095] Furthermore, in the composition of the present invention, in order to promote the hydrolytic condensation reaction of the hydrolyzable groups contained in the above-mentioned organosilicon compound by utilizing moisture in the air, and to promote the curing of the composition, a curing catalyst is preferably mixed in.

[0096] As a curing catalyst, there are no particular limitations as long as it is a curing catalyst used in the curing of general moisture condensation curing compositions. Specific examples include alkyltin compounds such as dibutyltin oxide and dioctyltin oxide; alkyltin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctanoate, dioctyltin dioctanoate, and dioctyltin ditert-tert-carbonate; titanates such as tetraisopropoxytitanium, tetra-n-butoxytitanium, tetra-tert-butoxytitanium, tetra(2-ethylhexyloxy)titanium, dipropoxybis(acetylacetone)titanium, diisopropoxybis(ethyl acetoacetate)titanium, and isopropoxyoctyl glycoltitanium, and titanium chelates. Compounds and their partial hydrolysates; zinc naphthenate, zinc stearate, zinc 2-ethyloctanoate, iron 2-ethylhexanoate, cobalt 2-ethylhexanoate, manganese 2-ethylhexanoate, cobalt naphthenate, aluminum hydroxide, aluminum alkoxides, aluminum acylates, salts of aluminum acylates, aluminum siloxane compounds, aluminum chelates, and other organometallic compounds; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltrieth ... N,β-(aminoethyl)γ-aminopropylmethyldimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, bis[3-(triethoxysilyl)propyl]amine, N,N'-bis[3-(trimethoxysilyl)propyl]ethane-1,2-diamine, N,N'-bis[3-(triethoxysilyl)propyl]ethane-1,2-diamine, N-phenyl-3-aminopropyltrimethoxysilane and other aminoalkyl-substituted alkoxysilanes; amine compounds and their salts such as hexylamine, dodecylamine phosphate, tetramethylguanidine; quaternary ammonium salts such as benzyltriethylammonium acetate; potassium acetate, sodium acetate, etc. Lower fatty acid salts of alkali metals such as lithium oxalate; dialkyl hydroxyamines such as dimethyl hydroxyamine and diethyl hydroxyamine; silanes and siloxanes containing guanidine groups such as tetramethylguanidinepropyltrimethoxysilane, tetramethylguanidinepropylmethyldimethoxysilane, tetramethylguanidinepropyltriethoxysilane, tetramethylguanidinepropylmethyldiethoxysilane, and tetramethylguanidinepropyltri(trimethylsiloxy)silane; silanes and siloxanes containing phosphazene salts such as N,N,N',N',N”,N”-hexamethyl-N”’-[3-(trimethoxysilyl)propyl]-iminophosphotriamide, etc. These can be used alone or in combination of two or more.

[0097] There is no particular limitation on the amount of curing catalyst added. If it is considered to adjust the curing speed to an appropriate range and improve workability, the amount is preferably 0.01 to 15 parts by weight, more preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of the main agent (base resin) component.

[0098] Compositions containing the organosilicon compounds and resins of the present invention, particularly resins having free radical polymerizable groups, can be cured by initiating free radical polymerization through heating and / or irradiation by active energy lines such as electromagnetic waves or electron beams. Curing can be achieved more effectively by using free radical initiators in combination.

[0099] As free radical initiators, there are thermal free radical initiators that generate free radicals through heating and photofree radical initiators that generate free radicals through irradiation with active energy lines. Typically, one substance used as a free radical initiator can be used alone, or two or more can be used in combination. Furthermore, depending on the requirements, one or more commonly used free radical polymerization accelerators, photosensitizers, etc., can be added alone or in combination.

[0100] As the aforementioned thermal free radical initiator, organic peroxide-based initiators, azo-based initiators, etc. are preferred. Specifically, the following free radical initiators can be listed as examples.

[0101] Examples of organic peroxide initiators include methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, acetoacetate peroxide, 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)-2-methylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)cyclododecane, 1,1-bis(tert-butylperoxy)butane, 2,2-bis(4,4-di-tert-butylperoxycyclohexyl)propane, hydroperoxide terpenes, dicumyl hydroperoxide, and hydroperoxide 1,1... 3,3-Tetramethylbutyl, cumene hydroperoxide, tert-hexyl hydroperoxide, tert-butyl hydroperoxide, α,α'-bis(tert-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, tert-butylcumyl peroxide, ditert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearyl peroxide, succinic acid peroxide, m-toluylbenzoyl peroxide, benzoyl peroxide, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, peroxy Di-2-ethoxyhexyl dicarbonate, di-3-methoxybutyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di(3-methyl-3-methoxybutyl) peroxydicarbonate, α,α'-bis(neodecanoylperoxy)diisopropylbenzene, cumyl peroxyneodecanate, 1,1,3,3'-tetramethylbutyl peroxyneodecanate, 1-cyclohexyl-1-methylethyl peroxyneodecanate, tert-hexyl peroxyneodecanate, tert-butyl peroxyneodecanate, tert-hexyl peroxynepentanoate, tert-butyl peroxynepentanoate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexanoate, 1-cyclohexyl-1-methylethyl peroxy-2-ethylhexanoate, peroxy-2-ethylhexanoate Tert-hexyl ester, tert-butyl peroxy-2-ethylhexanoate, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxyisobutyrate, tert-butyl peroxymaleate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy-2-ethylhexyl monocarbonate, tert-butyl peracetic acid, tert-butyl peroxy-m-toluylbenzoate, tert-butyl peroxybenzoate, bis(tert-butylperoxy)phthalate, 2,5-dimethyl-2,5-bis(m-toluylperoxy)hexane, tert-hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, tert-butyl peroxyallyl monocarbonate, tert-butyl peroxytrimethylsilyl peroxide, 3,3',4'4'-Tetra(tert-butylperoxycarbonyl)benzophenone, 2,3-dimethyl-2,3-diphenylbutane, etc.

[0102] Examples of azo initiators include 2-phenylazo-4-methoxy-2,4-dimethylpentanonitrile, 1-[(1-cyano-1-methylethyl)azo]formamide, 1,1'-azobis(cyclohexane-1-carboxylonitrile), 2,2'-azobis(2-methylbutanonitrile), 2,2'-azobisisobutanonitrile, 2,2'-azobis(2,4-dimethylpentanonitrile), 2,2'-azobis(2,4-dimethyl-4-methoxypentanonitrile), 2,2'-azobis(2-methylpropanediamine) dihydrochloride, 2,2'-azobis(2-methyl-N-phenylpropanediamine) dihydrochloride, and 2,2'-azobis[N-(4-chlorophenyl)-2-methylpropanediamine] 2,2'-Azobis[N-(4-hydrophenyl)-2-methylpropanediamine] dihydrochloride, 2,2'-Azobis[2-methyl-N-(phenylmethyl)propanediamine] dihydrochloride, 2,2'-Azobis[2-methyl-N-(2-propenyl)propanediamine] dihydrochloride, 2,2'-Azobis[N-(2-hydroxyethyl)-2-methylpropanediamine] dihydrochloride, 2,2'-Azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-Azobis[2-(4,5,6,7-tetrahydro-1H-1,3-diazaziate] 2,2'-Azobis[2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane] dihydrochloride, 2,2'-Azobis[2-(5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl)propane] dihydrochloride, 2,2'-Azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane} dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane], 2,2'-Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxy ...{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxy-2-yl]propane} dihydrochloride, 2,2'-Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxy-2-yl]propane} dihydrochloride, 2,2'-Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-methyl-N-[1,1-bis(hydroxymethyl)-2-yl]propane} dihydrochloride, 2,2'-Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2- [2,2'-Azobis[2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide], 2,2'-Azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-Azobis(2-methylpropionamide), 2,2'-Azobis(2,4,4-trimethylpentane), 2,2'-Azobis(2-methylpropane), dimethyl-2,2-Azobis(2-methylpropionate), 4,4'-Azobis(4-cyanopentanoic acid), 2,2'-Azobis[2-(hydroxymethyl)propionitrile], etc.

[0103] Furthermore, free radical polymerization accelerators that can be used in conjunction with the aforementioned thermal free radical initiators are acceptable. As long as the free radical polymerization accelerator promotes the decomposition of the aforementioned thermal free radical initiator (initiating the generation of free radicals), any commonly used free radical polymerization accelerator can be used; there are no particular limitations. Examples include organic salts, inorganic salts, oxides, or metal complexes of metals such as cobalt, copper, tin, zinc, manganese, iron, zirconium, chromium, vanadium, calcium, potassium, cerium, and samarium; primary, secondary, and tertiary amine compounds; quaternary ammonium salts; thiourea compounds; and ketone compounds. Specifically, examples include cobalt octanoate, cobalt naphthenate, zinc octanoate, zinc naphthenate, zirconium octanoate, zirconium naphthenate, copper octanoate, copper naphthenate, manganese octanoate, manganese naphthenate, dimethylaniline, triethanolamine, triethylbenzylammonium chloride, di(2-hydroxyethyl)-p-toluidine, ethylidene thiourea, acetylacetone, and methyl acetoacetate.

[0104] As the aforementioned photoradical initiators, preferred are alkylphenyl ketone compounds, benzophenone compounds, benzoin compounds, thioxanone compounds, halomethylated triazine compounds, halomethylated oxadiazole compounds, biimidazole compounds, oxime ester compounds, dicene compounds, benzoate compounds, acridine compounds, etc. Specifically, the following photoradical initiators can be listed as examples.

[0105] 2,2-Diethoxyacetophenone, 2,2-Dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanoyl)benzyl]phenyl}-2-methylpropane-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinophenyl) ... Alkylphenyl ketones such as [-1-butanone]-[- ... Halomethylated triazine compounds such as chloromethyl)-homo-triazine and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-homo-triazine; halomethylated oxadiazole compounds such as 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4-oxadiazole, 4-oxadiazole, and 2-trichloromethyl-5-furanyl-1,3,4-oxadiazole; halomethylated oxadiazole compounds such as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole and 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole. Biimidazole compounds such as 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole; oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyl oxime)], acetone, and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime); diacene compounds such as bis(n5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)-phenyl)titanium; benzoate ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; and acridine compounds such as 9-phenylacridine.

[0106] Furthermore, by using photosensitizers and free radical polymerization accelerators in conjunction with the aforementioned photoradical initiators, sensitivity and curability can be improved. Commonly used substances can be used as such photosensitizers and free radical polymerization accelerators, and there are no particular limitations. Preferred are pigment compounds, dialkylaminobenzene compounds, and thiol hydrogen donors, such as thiocyanate pigments, coumarin pigments, 3-ketocoumarin compounds, and metamethylene pigments; dialkylaminobenzene compounds such as ethyl 4-dimethylaminobenzoate and 2-ethylhexyl 4-dimethylaminobenzoate; and thiol hydrogen donors such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzimidazole.

[0107] The total amount of the aforementioned free radical initiator can be appropriately set according to the purpose and application, and is not particularly limited. From the perspective of balancing curability, adverse effects of decomposition products, and economy, it is preferably 0.01 to 30 parts by mass relative to 100 parts by mass of the organosilicon compound of the present invention. More preferably, it is 0.05 to 20 parts by mass, and even more preferably, it is 0.1 to 15 parts by mass.

[0108] The total amount of the above-mentioned free radical polymerization accelerator and photosensitizer can be appropriately set according to the purpose and use, and is not particularly limited. From the perspective of balancing curability and economy, it is preferably 0.001 to 20% by mass relative to 100% by mass of the organosilicon compound of the present invention. More preferably, it is 0.005 to 10% by mass, and even more preferably, it is 0.01 to 10% by mass.

[0109] Furthermore, other components may be added to the curable composition of the present invention without prejudice to the purpose of the invention. These other components are not particularly limited, and examples include desiccants that promote the decomposition of peroxides, other curing accelerators, solvents, reactive diluents, stabilizers, adhesive resins, colorants, dispersants, fillers, adhesion promoters, release agents, leveling agents, antistatic agents, etc.

[0110] There are no particular limitations on solvents. Examples include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as pentane, hexane, heptane, and decane; ethers such as diethyl ether and tetrahydrofuran; esters such as ethyl acetate and butyl acetate; and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. One of these can be used alone, or two or more can be used in combination.

[0111] When these solvents are added, the amount is preferably 1 to 50 parts by weight, more preferably 5 to 20 parts by weight, relative to 100 parts by weight of the main component (base resin).

[0112] By applying the coating composition of the present invention described above to the surface of a solid substrate and allowing it to cure, a coating layer can be formed, thereby obtaining a coated solid substrate.

[0113] In addition, by applying the adhesive composition of the present invention to the surface of a solid substrate, and then stacking other solid substrates on it, the composition of the present invention is cured to form an adhesive layer, thereby obtaining an adhesive laminate.

[0114] There are no particular limitations on the coating method for each composition. As specific examples, it is possible to appropriately select and use known methods such as spraying, spin coating, dip coating, roller coating, brush coating, bar coating, and flow coating.

[0115] As a solid substrate, there are no particular limitations. Specific examples include epoxy resin, phenolic resin, polyimide resin, polycarbonate resins and polycarbonate blends, acrylic resins such as poly(methyl methacrylate), polyethylene terephthalate, polybutylene terephthalate, unsaturated polyester resins, polyamide resins, acrylonitrile-styrene copolymer resins, styrene-acrylonitrile-butadiene copolymer resins, polyvinyl chloride resins, polystyrene resins, blends of polystyrene and polyphenylene ether, cellulose acetate butyrate resins, polyethylene resins, and other organic resin substrates; metal substrates such as iron plates, copper plates, and steel plates; coated surfaces; glass; ceramics; concrete; stone slabs; fabrics; wood, stone, tiles; inorganic fillers such as (hollow) silica, titanium dioxide, zirconium oxide, and alumina; glass fiber products such as glass cloth, glass tape, glass pads, and glass paper, and glass plates, etc. There are no particular limitations on the shape of the substrate.

[0116] [Primer Composition]

[0117] Compositions containing the organosilicon compounds of the present invention can improve adhesion to substrates, and are therefore suitable as primer compositions for coating various substrates.

[0118] Various additives can be added to the primer composition of the present invention as needed.

[0119] Specific examples of additives include diluents, curing catalysts, physical property modifiers that adjust the tensile properties of the cured film, storage stability improvers, free radical polymerization inhibitors, metal passivators, ozone deterioration inhibitors, lubricants, and pigments.

[0120] There are no particular limitations on the diluent solvent, and examples include water; alcohols such as methanol, ethanol, and isopropanol; aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as pentane, hexane, heptane, and decane; ethers such as diethyl ether, tetrahydrofuran, and 1,4-dioxane; esters such as ethyl acetate and butyl acetate; and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. One solvent can be used alone, or two or more can be used in combination. Furthermore, when using a diluent solvent, the concentration of the above-mentioned organosilicon compound is preferably 0.1–10% by mass, more preferably 0.5–5% by mass.

[0121] There are no particular limitations on the application method of the primer composition, and the same method as that used for the curing composition can be used. After the primer composition is applied to a solid substrate to form a primer film, a laminate with a cured film can be obtained by further applying a coating agent, paint, etc., onto the primer film.

[0122] There are no particular limitations on the solid substrate used; the same solid substrate as that described for the curable composition can be used.

[0123] As a coating agent applied to a primer film, it is possible to appropriately select from conventionally known coating agents, such as acrylic coating agents, epoxy coating agents, polyurethane coating agents, silicone coating agents, and urethane acrylate coating agents.

[0124] Example

[0125] The following examples and comparative examples illustrate the invention in more detail, but the invention is not limited to these examples.

[0126] Furthermore, in the following examples, kinematic viscosity, specific gravity, and refractive index are values ​​measured at 25°C, and parts are by mass. In this case, kinematic viscosity is measured based on JIS Z 8803. Specific gravity is measured based on JIS Z 8804. Refractive index is measured based on JIS K0062. Nuclear magnetic resonance spectroscopy (NMR spectroscopy) 1 ¹H-NMR determination was performed using a BRUKER AVANCE III / ULTRASHIELD 400 in dichloroform. Gas chromatography (GC) analysis was performed under the following conditions.

[0127] GC device: Agilent Technologies 6890N

[0128] Detector: Flame Ionization Detector (FID)

[0129] Column: HP-5J-413 (30m long × 0.32mm inner diameter, 0.25μm film thickness)

[0130] Column temperature: 50℃ → 10℃ / minute → 300℃ (hold for 10 minutes)

[0131] Measurement time: 35.0 minutes in total

[0132] Inlet temperature: 250℃

[0133] Detector temperature: 300℃

[0134] Carrier gas: He

[0135] Carrier gas flow rate: 1.0 mL / min

[0136] [1] Synthesis of organosilicon compounds

[0137] [Example 1-1] Synthesis of organosilicon compound 1

[0138] In a 1L detachable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 100.0 g (0.55 mol) of potassium 2-(allyloxymethyl)acrylate, 100 g of toluene, 0.3 g of 2,6-di-tert-butyl-p-cresol, and 3.1 g of tetrabutylammonium bromide were added dropwise over 1 hour at an internal temperature of 95–105 °C. The mixture was then stirred at 100 °C for 3 hours. Gas chromatography analysis confirmed the disappearance of 3-chloropropyltrimethoxysilane. The resulting solution was purified by distillation at 5 mmHg and 160 °C to obtain a kinematic viscosity of 4.57 mmHg. 2 120g of a colorless, transparent liquid (organosilicon compound 1) with a density of 1.060 g / s, a specific gravity of 1.060, and a refractive index of 1.4442.

[0139] pass 1 H-NMR analysis confirmed that the obtained organosilicon compound 1 has the structure represented by the above formula (6).

[0140] 1 H-NMR (CDCl3, 400MHz) δ: 0.56-0.67 (m, 2H), 1.66-1.80 (m, 2H), 3.53 (s, 9H), 3.92-4.00 (d , 2H), 4.02-4.08(m, 2H), 4.16(s, 2H), 5.07-5.28(d, 2H), 5.77-5.91(d, 2H), 6.28(s, 1H).

[0141] [Examples 1-2] Synthesis of organosilicon compound 2

[0142] In a 1L detachable beaker equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 100.0 g (0.55 mol) of potassium 2-(allyloxymethyl)acrylate, 100 g of toluene, 0.3 g of 2,6-di-tert-butyl-p-cresol, and 3.1 g of tetrabutylammonium bromide were added dropwise over 1 hour at an internal temperature of 95–105 °C. The mixture was then stirred at 100 °C for 3 hours. Gas chromatography analysis confirmed the disappearance of 3-chloropropylmethyldimethoxysilane. The resulting solution was purified by distillation at 5 mmHg and 158 °C to obtain a kinematic viscosity of 4.66 mmHg. 2 110g of a colorless, transparent liquid (organosilicon compound 2) with a density of 1.024 g / s, a specific gravity of 1.024, and a refractive index of 1.4483.

[0143] pass 1 H-NMR analysis confirmed that the obtained organosilicon compound 2 has the structure represented by the above formula (7).

[0144] 1 H-NMR (CDCl3, 400MHz) δ: 0.09 (s, 3H), 0.56-0.67 (m, 2H), 1.66-1.80 (m, 2H), 3.53 (s, 6H), 3.92- 4.00(d, 2H), 4.02-4.08(m, 2H), 4.16(s, 2H), 5.07-5.28(d, 2H), 5.77-5.91(d, 2H), 6.28(s, 1H)

[0145] [2] Preparation of primer composition and cured film (cured article)

[0146] [Examples 2-1, 2-2, Comparative Examples 2-1, 2-2]

[0147] The components were mixed in the proportions (parts by mass) shown in Table 1 to prepare a primer composition. The obtained primer composition was flow-coated onto a glass substrate at 25°C and 50% RH in air, and dried at 80°C for 5 minutes to obtain a primer film.

[0148] The topcoat composition was applied to the aforementioned primer film at 25°C and 50% RH in air using a rod coater No. 20. The topcoat composition used was a product made by mixing 3% by mass of Omnirad 184 (manufactured by IGM Resins BV) with Lucidia 17-813 (urethane acrylate resin, manufactured by DIC Co., Ltd.). After drying at 80°C for 10 minutes, it was subjected to UV irradiation (74 mW / cm²). 2 Thus, a laminate with a cured film was obtained.

[0149] The obtained cured film was evaluated by measuring its pencil hardness and adhesion using the following method. The results are shown in Table 1.

[0150] [Pencil Hardness (Surface Hardness)]

[0151] The test was performed using a 750g load, according to JIS K5600-5-4.

[0152] [Seamlessness]

[0153] Checkerboard peel test: conducted according to JIS K 5400.

[0154] After boiling test, the test piece was immersed in hot water at 100°C for 2 hours and then a checkerboard peel test was performed.

[0155] The evaluation results shown in Table 1 represent the number of checkerboard grids remaining after stripping out 100 grids.

[0156] [Table 1]

[0157]

[0158] · Organosilicon compound 3: 3-(methacryloyloxy)propyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0159] ·AOMA: Methyl 2-(allyloxymethyl)acrylate (Nippon Shokubai Co., Ltd.)

[0160] The results of the above examples and comparative examples confirm that the modified surfaces formed using the organosilicon compounds of Examples 1-1 and 1-2 exhibit excellent adhesion to the acrylate resin.

[0161] [3] Preparation of curable compositions and curable films (cured articles)

[0162] [Examples 3-1, 3-2, Comparative Examples 3-1, 3-2]

[0163] The components were mixed in the proportions (parts by weight) shown in Table 2 to prepare a UV-curable polyurethane resin composition. The obtained UV-curable polyurethane resin composition was applied to a glass plate using a rod applicator No. 12 at 25°C and 50% RH in air, and cured and dried for one week at 25°C and 50% RH in air. Subsequently, it was subjected to UV irradiation (74 mW / cm²). 2 Thus, a cured film was obtained.

[0164] The obtained cured film was evaluated by measuring its pencil hardness and adhesion using the following method. The results are shown in Table 2.

[0165] Pencil hardness (surface hardness)

[0166] The test was performed using a 750g load, according to JIS K5600-5-4.

[0167] [Seamlessness]

[0168] Checkerboard peel test: conducted according to JIS K 5400.

[0169] The evaluation results shown in Table 2 represent the number of checkerboard grids remaining after stripping from 100 grids.

[0170] [Table 2]

[0171]

[0172] • UV-curable polyurethane resin: Lucidity 17-813 (manufactured by DIC Corporation)

[0173] • Curing catalyst: DX-9740 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0174] • Photoradical initiator: Omnirad184 (made by IGM Resins BV)

[0175] · Organosilicon compound 3: 3-(methacryloyloxy)propyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0176] ·AOMA: Methyl 2-(allyloxymethyl)acrylate (Nippon Shokubai Co., Ltd.)

[0177] The results of the above examples and comparative examples confirm that the polyurethane resin compositions with added organosilicon compounds of Examples 1-1 and 1-2 exhibit excellent adhesion to glass substrates.

Claims

1. An organosilicon compound represented by the following formula (1), [Chemical Formula 1] wherein R 1 each independently is an alkyl group having 1 to 10 carbons, an alkenyl group having 2 to 10 carbons, an aryl group having 6 to 10 carbons, or an acyl group having 1 to 20 carbons, R 2 each independently is an alkyl group having a carbon number of 1 to 10 or an aryl group having a carbon number of 6 to 10, R 3 is a hydrogen atom or a methyl group, A 1 is a single bond or an unsubstituted or substituted divalent hydrocarbon group having a carbon number of 1 to 20, A 2 , A 3 , A 4 each independently is unsubstituted or substituted methylene or an oxygen atom, wherein, A 2 , A 3 and A 4 one or more of the groups A, A, A, A, A, A, A, A, A, A, A, A, A, A, A, A, A, A, A, A, A, A, A, A, A, A, A, A, A n is an integer of 1 to 3.

2. The organosilicon compound of claim 1, wherein, The A 1 is an alkylene group having 1 to 10 carbon atoms.

3. The organosilicon compound according to claim 1 or 2, wherein, said A 2 and said A 4 is methylene, said A 3 is an oxygen atom.

4. The method for producing a silicone compound according to any one of claims 1 to 3, wherein an organosilicon compound containing a halogen group represented by the following formula (3) is reacted with a metal salt compound represented by the following formula (4), [Chemical Formula 2] wherein R 1 , R 2 , R 3 , A 1 , A 2 , A 3 , A 4 and n are the same as described above, X is a chlorine atom, a bromine atom or an iodine atom, and M is an alkali metal.

5. A curable composition comprising the organosilicon compound according to any one of claims 1 to 3.

6. A coating agent comprising the curable composition according to claim 5.

7. An adhesive comprising the curable composition according to claim 5.

8. A cured product cured from the curable composition according to claim 5.

9. An article having a coating layer cured from the coating agent according to claim 6.

10. An article having an adhesive layer cured from the adhesive according to claim 7.

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