Reactive silicon group-containing polyoxyalkylene derivative, production method therefor, curable composition, and cured product

Abstract

This reactive silicon group-containing polyoxyalkylene derivative in which one or both terminals of a polyoxyalkylene chain are blocked with a group represented by structural formula (1) has good curability even if an amine-based compound is used as a curing catalyst, and gives a cured product having excellent yellowing resistance and heat resistance. (In the formula, R1 and R2 each independently represent a hydrogen atom, a C1-10 aliphatic saturated hydrocarbon group or a C6-10 aryl group, each R3 independently represents a C1-10 aliphatic saturated hydrocarbon group or a C6-10 aryl group, and n is an integer of 2-12. The wavy line represents a bond.)

Description

Reactive silicon group-containing polyoxyalkylene derivative, its production method, curable composition and cured product

[0001] The present invention relates to a reactive silicon group-containing polyoxyalkylene derivative, a method for producing the same, a curable composition, and a cured product thereof. More specifically, the present invention relates to a polyoxyalkylene derivative having, as the reactive silicon group-containing group, an organosilicon group that can react to form a siloxane bond, a method for producing the same, a curable composition, and a cured product thereof.

[0002] Reactive silicon group, especially alkoxysilyl group, has the property of hydrolysis condensation in the presence of water, so polymers having this reactive silicon group can be used as curable compositions that crosslink and cure in the presence of water or humidity.Among these polymers, those whose main chain is a polyoxyalkylene group are generally known as modified silicones.In addition, the curable compositions using this have the characteristic of being liquid at room temperature and becoming rubber elastic bodies after curing, and utilizing this characteristic, they are widely used in coating agents, adhesives, construction sealants, etc.

[0003] Numerous methods have been proposed for producing polymers having reactive silicon groups at molecular chain terminals, and some have already been industrially produced.For example, polyoxypropylene derivatives having alkoxysilyl groups bonded to both molecular chain terminals are known, and room temperature curable compositions using such polymers as base polymers are known (Patent Documents 1 and 2).However, the room temperature curable compositions disclosed in Patent Documents 1 and 2 have low reactivity with moisture in the air and insufficient curing properties.Therefore, in order to ensure sufficient curing properties at room temperature, it is generally necessary to add a catalyst such as an organotin compound, but organotin compounds are toxic to the human body and the environment.

[0004] Furthermore, Patent Document 3 discloses an alkoxysilyl end-blocked polymer obtained by reacting a polymer having a hydroxyl group at the end with an isocyanate silane or the like to improve reactivity. However, although the compound of Patent Document 3 has excellent reactivity, it contains a urethane or urea bond in the molecule, which causes significant discoloration over time and insufficient yellowing resistance and heat resistance. Furthermore, the use of a highly toxic low-boiling point isocyanate silane in the production of the end-blocked polymer, and the possibility of similar low-boiling point isocyanate silane being generated by thermal decomposition of the urethane or urea bond at high temperatures, are considered problematic.

[0005] Furthermore, Patent Document 4 discloses that by using a polyoxyalkylene derivative having a sulfide-methylene bond as the linking group between the terminal alkoxysilyl group and the polyoxyalkylene main chain, a cured product can be obtained that exhibits excellent fast curing speed and yellowing resistance even when an amine compound is used as the curing catalyst instead of an organotin compound, and that does not use isocyanate silane, which can result in low toxicity. However, although the compound of Patent Document 4 exhibits excellent reactivity when an amine catalyst is used, there is a problem in that the cured product softens due to cleavage of the sulfide-methylene-silicon bond at high temperatures.

[0006] Japanese Patent Application Laid-Open No. 2004-099908 Japanese Patent Application Laid-Open No. 2010-209205 Japanese Patent Application Laid-Open No. 2004-518801 Japanese Patent Application Laid-Open No. 2017-141450

[0007] The present invention has been made in view of the above circumstances, and aims to provide a reactive silicon group-containing polyoxyalkylene derivative that exhibits good curability even when an amine compound is used as a curing catalyst, and that gives a cured product that is excellent in yellowing resistance and heat resistance, and a method for producing the same.

[0008] As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have found that a polyoxyalkylene derivative whose terminals are capped with an organoxymethyl group and a silyl group to which two organoxy groups are bonded as reactive silicon groups exhibits good curability even when an amine compound is used as a curing catalyst, and gives a cured product that is excellent in yellowing resistance and heat resistance, thereby completing the present invention.

[0009] That is, the present invention provides: 1. a reactive silicon group-containing polyoxyalkylene derivative in which one or both ends of the polyoxyalkylene chain are blocked with a group represented by the following structural formula (1); (In the formula, R 1 and R 2 each independently represents a hydrogen atom, an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms; R 3 each independently represents an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and n is an integer from 2 to 12. A wavy line represents a bond.) 2. A reactive silicon group-containing polyoxyalkylene derivative of 1 having a number average molecular weight of 200 to 50,000; 3. A method for producing a reactive silicon group-containing polyoxyalkylene derivative of 1, which comprises reacting an alkenyl group-containing polyoxyalkylene derivative in which one or both ends of the polyoxyalkylene chain are blocked with an alkenyl group having 2 to 12 carbon atoms with a disiloxane compound represented by the following formula (4): (In the formula, R 1 , R 2 and R 3have the same meanings as above.) 4. A method for producing the reactive silicon group-containing polyoxyalkylene derivative of 3 having a number average molecular weight of 200 to 50,000, 5. A curable composition containing (A) the reactive silicon group-containing polyoxyalkylene derivative of 1 and (B) a curing catalyst, 6. The curable composition of 5 in which the (B) curing catalyst is an amine-based compound, 7. A cured product obtained by curing the curable composition of 5 or 6, 8. A coating composition containing (A) the reactive silicon group-containing polyoxyalkylene derivative of 1 and (B) a curing catalyst, 9. The coating composition of 8 in which the (B) curing catalyst is an amine-based compound, 10. An article having a coating layer obtained by curing the coating composition of 8 or 9, 11. An adhesive composition containing (A) the reactive silicon group-containing polyoxyalkylene derivative of 1 and (B) a curing catalyst, 12. The adhesive composition of 11 in which the (B) curing catalyst is an amine-based compound, 13. 13. An article having an adhesive layer formed by curing the adhesive composition of 11 or 12.

[0010] The reactive silicon group-containing polyoxyalkylene derivative of the present invention has an organoxymethyl group and a silyl group that two organoxy groups are bonded to as specific reactive silicon groups at the molecular end, so even when using an amine compound as a curing catalyst instead of an organotin compound, it has good curing property, and gives a cured product that is excellent in yellowing resistance and heat resistance.The reactive silicon group-containing polyoxyalkylene derivative of the present invention that has such properties can be suitably used as the main component (base polymer) of coating agents, adhesives, sealants, etc.

[0011] The present invention will be described in detail below. The reactive silicon group-containing polyoxyalkylene derivative of the present invention is a polyoxyalkylene derivative in which one or both ends of the polyoxyalkylene chain are blocked with a group represented by the following structural formula (1).

[0012]

[0013] In formula (1), R 1 and R 2 each independently represents a hydrogen atom, an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms; R3 R each independently represents an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. 1 , R 2 and R 3 The aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms may be linear, cyclic, or branched, and specific examples thereof include linear or branched alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. 1 , R 2 and R 3 Specific examples of the aryl group having 6 to 10 carbon atoms include phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, etc. Some or all of the hydrogen atoms in these groups may be substituted with halogen atoms such as F, Cl, Br, etc., or cyano groups, etc. Specific examples thereof include 3-chloropropyl, 3,3,3-trifluoropropyl, 2-cyanoethyl, etc.

[0014] Among these, R 1 , R 2 and R 3 As the alkyl group, a methyl group, an ethyl group, or a phenyl group is preferred, and from the viewpoints of curability, productivity, and cost, a methyl group is more preferred.

[0015] In formula (1), n ​​is an integer of 2 to 12, preferably 2 to 8, more preferably 2 or 3, and even more preferably 2, from the viewpoint of reactivity.

[0016] The reactive silicon group-containing polyoxyalkylene derivative of the present invention is not particularly limited as long as it is a compound having a group represented by the above formula (1) at one or both ends of the polyoxyalkylene skeleton. However, from the viewpoint of curability and the mechanical properties of the resulting cured product, it is preferable that the reactive silicon group-containing polyoxyalkylene derivative has a group represented by the above formula (1) at both ends of the polyoxyalkylene skeleton.

[0017] Therefore, the reactive silicon group-containing polyoxyalkylene derivative of the present invention is preferably one represented by the following structural formula (2).

[0018] (In the formula, R 1 , R 2 , R 3 and n have the same meaning as above.)

[0019] In formula (2), Z represents a polyoxyalkylene structure represented by the following formula (3).

[0020] (In the formula, the wavy line represents a bond.)

[0021] In formula (3), R 5 represents a divalent hydrocarbon group having 1 to 14 carbon atoms, and p is an integer of 1 or more. 5 If there are multiple p (p is 2 or more), each R 5 may be the same or different.

[0022] R 5 The divalent hydrocarbon group is preferably a linear or branched alkylene group having 1 to 14 carbon atoms, such as methylene, ethylene, propylene, trimethylene, tetramethylene, isobutylene, pentamethylene, hexamethylene, heptamethylene, and octamethylene. 5 As the alkyl group, a straight or branched alkylene group having 2 to 4 carbon atoms such as methylene, ethylene, trimethylene, propylene, tetramethylene, or isobutylene is particularly preferred.

[0023] That is, the repeating unit (-OR 5 Specific examples of -) include oxyalkylene groups such as -OCH2-, -OCH2CH2-, -OCH2CH2CH2-, -OCH2CH2CH2-, -OCH(CH3)CH2-, -OCH2CH2CH2CH2-, -OCH(CH2CH3)CH2-, and -OC(CH3)2CH2-.

[0024] In formula (3), p is a number of 1 or more, and from the viewpoint of the mechanical properties of the resulting cured product and the workability of the composition, it is preferably 5 to 700, more preferably 10 to 500, and even more preferably 20 to 300.

[0025] The main chain skeleton of the oxyalkylene group-containing organosilicon compound of the present invention may consist of one type of repeating unit, or two or more types of repeating units. In particular, when used in materials such as coating agents, adhesives, and sealants, it is preferable to include oxypropylene (—OCH(CH)CH—) units from the standpoint of durability.

[0026] The number average molecular weight of the oxyalkylene group-containing organosilicon compound of the present invention is not particularly limited, but in consideration of improving workability and imparting sufficient curability by maintaining the viscosity and other properties of the curable composition containing the compound within an appropriate range, the number average molecular weight is preferably 200 to 50,000, more preferably 1,000 to 20,000. Note that the number average molecular weight in the present invention is a polystyrene-equivalent value determined by gel permeation chromatography (GPC) analysis (the same applies hereinafter).

[0027] The viscosity of the reactive silicon group-containing polyoxyalkylene derivative of the present invention is not particularly limited, but in consideration of improving workability and imparting sufficient curability by maintaining the viscosity of the curable composition containing the compound within an appropriate range, it is preferably 10 to 100,000 mPa s, more preferably 50 to 50,000 mPa s, and even more preferably 100 to 10,000 mPa s. Here, the viscosity is measured at 25°C using a Brookfield type rotational viscometer.

[0028] The reactive silicon group-containing polyoxyalkylene derivative of the present invention can be obtained by subjecting a polyoxyalkylene having one or both molecular chain terminals blocked with an alkenyl group having 2 to 12 carbon atoms (hereinafter also referred to as an "alkenyl group-containing polyoxyalkylene derivative") to a hydrosilylation reaction with a disiloxane compound represented by formula (4) in the presence of a platinum group metal catalyst in air or an inert gas such as nitrogen.

[0029] (In the formula, R 1 , R 2 and R 3 has the same meaning as above.)

[0030] Specific examples of the disiloxane compound represented by formula (4) include, but are not limited to, those represented by the following structural formulas: Among these, the disiloxane compound represented by formula (6) is preferred.

[0031]

[0032] The disiloxane compound represented by formula (4) above can be obtained, for example, by subjecting an organoxysilane represented by formula (7) below and a disiloxane compound represented by formula (8) below to an equilibration reaction in the presence of an acid and water.

[0033] (In the formula, R 1 , R 2 and R 3 has the same meaning as above.)

[0034] The alkenyl group-containing polyoxyalkylene derivative is not particularly limited as long as it is a compound having an alkenyl group having 2 to 12 carbon atoms at one or both ends of a polyoxyalkylene skeleton. From the viewpoint of curability and the mechanical properties of the resulting cured product, however, a compound having an alkenyl group having 2 to 12 carbon atoms at both ends of a polyoxyalkylene skeleton, represented by the following formula (5), is preferred:

[0035] (In the formula, R 5 and p have the same meaning as above.

[0036] In formula (5), R 6is an alkenyl group having 2 to 12 carbon atoms. The alkenyl group having 2 to 12 carbon atoms is preferably a linear or branched alkenyl group having 2 to 8 carbon atoms. Specific examples thereof include vinyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-2-propenyl, 3-methyl-2-butenyl, and 2-methyl-2-butenyl. nyl, 1-ethyl-2-propenyl, 2-ethyl-2-propenyl, 1-methyl-4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-heptenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 5-heptenyl, 6-heptenyl, 1-methyl-6-heptenyl, 1-octenyl, 2-octenyl, 3-octenyl, 4-octenyl, 5-octenyl, 6-octenyl, 7-octenyl, etc. Among these, a vinyl group or an allyl group is preferred, and a vinyl group is more preferred.

[0037] Specific examples of the alkenyl group-containing polyoxyalkylene derivative include, but are not limited to, those represented by the following structural formulas.

[0038] (In the formula, p has the same meaning as above.)

[0039] The number average molecular weight of the alkenyl group-containing polyoxyalkylene derivative is not particularly limited, but in consideration of improving workability by setting the viscosity and the like of a curable composition containing the compound in an appropriate range and imparting sufficient curability, the number average molecular weight is preferably 200 to 50,000, and more preferably 1,000 to 20,000.

[0040] Regarding the reaction ratio of the alkenyl group-containing polyoxyalkylene derivative with the disiloxane compound represented by formula (4), in consideration of suppressing by-products during the hydrosilylation reaction and improving the storage stability and properties of the resulting polyoxyalkylene compound, the ratio of hydrosilyl groups of the disiloxane compound represented by formula (4) to one alkenyl group in the alkenyl group-containing polyoxyalkylene derivative is preferably 0.8 to 2.5, and more preferably 0.9 to 2.0.

[0041] The platinum group metal catalyst used in the hydrosilylation reaction is not particularly limited, and specific examples include chloroplatinic acid, an alcohol solution of chloroplatinic acid, a toluene or xylene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, tetrakistriphenylphosphine platinum, dichlorobistriphenylphosphine platinum, dichlorobisacetonitrile platinum, dichlorobisbenzonitrile platinum, dichlorocyclooctadiene platinum, and supported catalysts such as platinum-carbon, platinum-alumina, and platinum-silica. Among these, zero-valent platinum complexes are preferred in terms of selectivity during hydrosilylation, and a toluene or xylene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex is more preferred.

[0042] The amount of platinum group metal catalyst used is not particularly limited, but from the standpoints of reactivity, productivity, and the like, it is preferably 0.1 to 1,000 ppm, and more preferably 0.3 to 100 ppm, calculated as the mass of platinum group metal, relative to the total mass of the alkenyl group-containing organopolysiloxane and the disiloxane compound represented by formula (4) above.

[0043] The hydrosilylation reaction can be carried out without a solvent, but can also be carried out in an organic solvent such as toluene, isopropyl alcohol, or methanol, as needed, as long as the reaction is not inhibited.

[0044] The reaction temperature for the hydrosilylation reaction is not particularly limited, but is preferably 0 to 200°C, more preferably 40 to 110°C, and even more preferably 60 to 100°C. When a solvent is used, the reaction is preferably carried out at a temperature ranging from 0°C to the boiling point of the solvent. The reaction time is not particularly limited, but is usually about 1 to 60 hours, preferably 1 to 24 hours.

[0045] The curable composition of the present invention (hereinafter referred to as the composition) contains at least the reactive silicon group-containing polyoxyalkylene derivative (A) and the curing catalyst (B). Because the composition of the present invention contains the reactive silicon group-containing polyoxyalkylene derivative of the present invention, it has excellent curability and provides a cured product that is resistant to yellowing and heat resistance.

[0046] The curing catalyst (B) is a component that promotes the hydrolysis and condensation reaction of the hydrolyzable groups contained in the reactive silicon group-containing polyoxyalkylene derivative (A) with moisture in the air, thereby promoting the curing of the composition, and is added to achieve efficient curing. The curing catalyst is not particularly limited as long as it is a curing catalyst that is commonly used for curing 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 dioctoate, dioctyltin dioctoate, and dioctyltin diversatate; tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrakis(2-ethylhexoxy)titanium, dipropoxybis(acetylacetonato)titanium, titanium diisopropoxybis(ethylacetoacetate), titanium titanate esters and titanium chelate compounds, such as zinc isopropoxyoctylene glycol, and partial hydrolysates thereof; organometallic compounds, such as zinc naphthenate, zinc stearate, zinc 2-ethyloctoate, iron 2-ethylhexoate, cobalt 2-ethylhexoate, manganese 2-ethylhexoate, cobalt naphthenate, aluminum trihydroxide, aluminum alcoholates, aluminum acylates, salts of aluminum acylate, aluminosiloxy compounds, and aluminum chelate compounds;3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane, bis[3-(trimethoxysilyl)propyl] Amines, aminoalkyl group-substituted alkoxysilanes such as 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, and N-phenyl-3-aminopropyltrimethoxysilane; amine compounds and salts thereof such as hexylamine and dodecylamine phosphate; quaternary ammonium salts such as benzyltriethylammonium acetate; potassium acetate lower fatty acid salts of alkali metals such as sodium acetate and lithium oxalate; dialkylhydroxylamines such as dimethylhydroxylamine and diethylhydroxylamine; 2-[3-(trimethoxysilyl)propyl]-1,1,3,3-tetramethylguanidine, 2-[3-(methyldimethoxysilyl)propyl]-1,1,3,3-tetramethylguanidine, 2-[3-(triethoxysilyl)propyl]-1,1,3,3-tetramethylguanidine, 2-[3-(methyldiethoxysilyl)propyl]-1,1,3,3-tetramethylguanidine, silanes and siloxanes containing a guanidino group, such as N-[3-(tris(trimethylsiloxy)silyl)propyl]-1,1,3,3-tetramethylguanidine and 2-[3-(tris(trimethylsiloxy)silyl)propyl]-1,1,3,3-tetramethylguanidine; and silanes and siloxanes containing a phosphazene base, such as N,N,N',N',N'',N''-hexamethyl-N'''-[3-(trimethoxysilyl)propyl]-phosphorimidic triamide, which may be used alone or in combination of two or more kinds.

[0047] Among these, dioctyltin dilaurate, dioctyltin diversatate, tetraisopropoxytitanium, tetra n-butoxytitanium, titanium diisopropoxybis(ethylacetoacetate), 3-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, N,N'-bis[3-(trimethoxysilyl)propyl]ethane-1,2-diamine, and 2-[3-(trimethoxysilyl)propyl]-1,1,3,3-tetramethylguanidine are preferred because of their excellent reactivity, and further, From the viewpoint of the curability of the composition, dioctyltin dilaurate, dioctyltin diversatate, 3-aminopropyltrimethoxysilane, and 2-[3-(trimethoxysilyl)propyl]-1,1,3,3-tetramethylguanidine are more preferred, and from the viewpoint of not containing an organotin compound and being less toxic, 3-aminopropyltrimethoxysilane and 2-[3-(trimethoxysilyl)propyl]-1,1,3,3-tetramethylguanidine are even more preferred, and from the viewpoint of the curability of the composition, 2-[3-(trimethoxysilyl)propyl]-1,1,3,3-tetramethylguanidine is particularly preferred.

[0048] The amount of curing catalyst added is not particularly limited, but in order to adjust the curing rate within an appropriate range and improve workability, it is preferably 0.01 to 15 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of (A) the reactive silicon group-containing organopolysiloxane.

[0049] Furthermore, the composition of the present invention is preferably a solvent-free form that does not substantially contain organic solvents (which are often harmful to humans and flammable), but a solvent may be added depending on the intended use and workability. Here, "substantially" means that the solvent contained in the composition is 1% by mass or less, particularly 0.1% by mass or less. The solvent is not particularly limited as long as it dissolves the component (A). Specific examples include hydrocarbon solvents such as pentane, hexane, heptane, octane, decane, and cyclohexane; aromatic solvents such as benzene, toluene, and xylene; amide solvents such as formamide, N,N-dimethylformamide, pyrrolidone, and N-methylpyrrolidone; ester solvents such as ethyl acetate, butyl acetate, γ-butyrolactone, and propylene glycol-1-monomethyl ether-2-acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and ether solvents such as diethyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, and 1,4-dioxane. These may be used alone or in combination of two or more.

[0050] Depending on the intended use, various additives such as adhesion improvers, inorganic and organic ultraviolet absorbers, storage stability improvers, plasticizers, fillers, pigments, and fragrances may be added to the composition of the present invention.

[0051] A coated solid substrate can be obtained by applying the composition of the present invention described above to the surface of a solid substrate and curing it to form a coating layer, and an adhesive laminate can be obtained by applying the adhesive composition of the present invention to the surface of a solid substrate, laminating another solid substrate thereon, and then curing the composition to form an adhesive layer. The method for applying the composition is not particularly limited, and specific examples thereof can be appropriately selected from known methods such as spray coating, spin coating, dip coating, roller coating, brush coating, bar coating, and flow coating.

[0052] The material and shape of the solid substrate are not particularly limited, and specific examples thereof include organic resin substrates such as epoxy resin, phenol resin, polyimide resin, polycarbonate resin such as polycarbonates and polycarbonate blends, acrylic resin such as poly(methyl methacrylate), polyester resin such as poly(ethylene terephthalate), poly(butylene terephthalate), unsaturated polyester resin, polyamide resin, acrylonitrile-styrene copolymer resin, styrene-acrylonitrile-butadiene copolymer resin, polyvinyl chloride resin, polystyrene resin, blends of polystyrene and polyphenylene ether, cellulose acetate butyrate, and polyethylene resin; metal substrates such as iron plate, copper plate, and steel plate; painted surfaces; glass; ceramic; concrete; slate; textile; wood, stone, roof tile, (hollow) inorganic fillers such as silica, titania, zirconia, and alumina; and glass fiber products such as glass fiber, glass cloth, glass tape, glass mat, and glass paper.

[0053] When the composition of the present invention comes into contact with moisture in the atmosphere, the hydrolysis and condensation reaction of the reactive silicon group-containing polyoxyalkylene derivative (A) proceeds. The moisture content of the atmosphere can be measured using any humidity between 10 and 100% RH. Generally, the higher the humidity, the faster the hydrolysis proceeds, so moisture can be added to the atmosphere if desired. The curing reaction temperature and time can be appropriately adjusted depending on factors such as the substrate used, moisture concentration, catalyst concentration, and type of hydrolyzable group. From the standpoint of workability, the curing reaction temperature is typically preferably about 10°C to 40°C. However, to accelerate the curing reaction, the composition may be heated to a temperature not exceeding the heat resistance temperature of the substrate used. The curing reaction time is typically about 1 minute to 1 week, from the standpoint of workability, etc.

[0054] The present invention will be described in more detail below with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to these Examples. In the following, the viscosity is measured at 25°C using a B-type rotational viscometer, and the molecular weight and degree of polymerization (the number of repeating oxyalkylene units) are the number-average molecular weight and number-average degree of polymerization in terms of polystyrene determined by GPC (gel permeation chromatography) measurement.

[0055] [1] Synthesis of disiloxane compound [Synthesis Example 1] Synthesis of disiloxane compound a

[0056] A 300 mL separable flask equipped with a stirrer, reflux condenser, and thermometer was charged with 200 g of trimethoxy(methoxymethyl)silane and 40.4 g of 1,1,3,3-tetramethyldisiloxane, and 1.2 g of concentrated sulfuric acid (98% by mass) was added dropwise with stirring at 7°C. After completion of the dropwise addition, the mixture was stirred for 5 hours at 25°C. Thereafter, 6 g of Kyoward (registered trademark) 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and after stirring for 1 hour, the reaction liquid was removed by filtration and distilled (distillation temperature 90°C, vacuum degree 17 kPa) to obtain disiloxane compound a. 1 H-NMR (CDCl3): δ4.46-4.61ppm (s, 1H, -SiH), 3.41-3.34ppm (s, 9H, -Si(OC H3)2, -OCH3), 3.15-3.13ppm (s, 2H, -CH2-), 0.00-0.02ppm (s, 6H, -SiCH3)

[0057] [Synthesis Example 2] Synthesis of disiloxane compound b

[0058] A 300 mL separable flask equipped with a stirrer, reflux condenser, and thermometer was charged with 268 g of triethoxy(ethoxymethyl)silane and 40.4 g of 1,1,3,3-tetramethyldisiloxane, and 1.2 g of concentrated sulfuric acid (98% by mass) was added dropwise with stirring at 7°C. After completion of the dropwise addition, the mixture was stirred for 5 hours at 25°C. Thereafter, 6 g of Kyoward (registered trademark) 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and after stirring for 1 hour, the reaction liquid was removed by filtration and distilled (distillation temperature 90°C, vacuum degree 17 kPa) to obtain disiloxane compound b.1 H-NMR (CDCl3): δ4.46-4.61ppm (s, 1H, -SiH), 3.85-3.63ppm (m, 6H, -OCH2-), 1.41-1.34ppm (m, 9H, -CH3), 0.00-0.02ppm (s, 6H, -SiCH3)

[0059] [Synthesis Example 3] Synthesis of disiloxane compound c

[0060] A 300 mL separable flask equipped with a stirrer, reflux condenser, and thermometer was charged with 200 g of trimethoxy(methoxymethyl)silane and 115 g of 1,1,3,3-tetraphenyldisiloxane, and 1.2 g of concentrated sulfuric acid (98% by mass) was added dropwise with stirring at 7°C. After completion of the dropwise addition, the mixture was stirred for 5 hours at 25°C. Thereafter, 6 g of Kyoward (registered trademark) 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and after stirring for 1 hour, the reaction liquid was removed by filtration and distilled (distillation temperature 90°C, vacuum degree 17 kPa) to obtain disiloxane compound c. 1 H-NMR (CDCl3): δ7.58-7.32ppm (m, 10H, -SiC6H5), 4.46-4.61ppm (s, 1H, -Si H), 3.41 to 3.34 ppm (s, 9H, -Si(OCH3)2, -OCH3), 3.15 to 3.13 ppm (s, 2H, -CH2-)

[0061] [2] Synthesis of reactive silicon group-containing polyoxyalkylene derivatives [Example 1-1] Synthesis of reactive silicon group-containing polyoxyalkylene derivative A-1 In a 200 mL separable flask equipped with a stirrer, reflux condenser, and thermometer, 100 g of polypropylene glycol containing allyl groups at both ends and having a number average molecular weight of 5,100 (0.07 mol in terms of functional groups of the terminal allyl groups) and a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (50 ppm by mass as platinum) were placed and heated to 60° C. 27 g of the disiloxane compound a obtained in Synthesis Example 1 (0.11 mol of hydrosilyl functional groups) was added and the mixture was stirred at 60° C. for 2 hours. 1The reaction was terminated when H-NMR analysis confirmed that the peaks derived from the allyl groups in the raw material had completely disappeared and that peaks derived from the target product had been detected. After the reaction was completed, the solvent was distilled off at 100°C and a vacuum of 1.3 kPa for 3 hours to obtain reactive silicon group-containing polyoxyalkylene derivative A-1. The resulting reactive silicon group-containing polyoxyalkylene derivative A-1 was a pale yellow, transparent liquid with a number average molecular weight of 6,000 and a viscosity of 500 mPa s.

[0062] Example 1-2 Synthesis of Reactive Silicon Group-Containing Polyoxyalkylene Derivative A-2 100 g of polypropylene glycol containing allyl groups at both ends and having a number average molecular weight of 7,800 (0.039 mol in terms of functional groups in the terminal allyl groups) and a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (50 ppm by mass as platinum) were placed in a 200 mL separable flask equipped with a stirrer, reflux condenser, and thermometer, and heated to 60° C. 15 g of the disiloxane compound a obtained in Synthesis Example 1 (0.06 mol of hydrosilyl functional groups) were then added, and the mixture was stirred at 60° C. for 2 hours. 1 The reaction was terminated when H-NMR analysis confirmed that the peaks derived from the allyl groups in the raw material had completely disappeared and that peaks derived from the target product had been detected. After completion of the reaction, the solvent was distilled off at 100°C and a vacuum of 1.3 kPa for 3 hours to obtain reactive silicon group-containing polyoxyalkylene derivative A-2. The resulting reactive silicon group-containing polyoxyalkylene derivative A-2 was a pale yellow, transparent liquid with a number average molecular weight of 8,600 and a viscosity of 2,800 mPa s.

[0063] Example 1-3 Synthesis of Reactive Silicon Group-Containing Polyoxyalkylene Derivative A-3 A 200 mL separable flask equipped with a stirrer, reflux condenser, and thermometer was charged with 1,280 g of polypropylene glycol containing allyl groups at both ends and having a number average molecular weight of 12,000 (0.2 mol in terms of functional groups in the terminal allyl groups) and a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (50 ppm by mass as platinum), and heated to 60° C. 75 g of the disiloxane compound a obtained in Synthesis Example 1 (0.3 mol of hydrosilyl functional groups) was then added, and the mixture was stirred at 60° C. for 2 hours. 1The reaction was terminated when H-NMR analysis confirmed that the peaks derived from the allyl groups of the raw material had completely disappeared and that peaks derived from the target product had been detected. After completion of the reaction, the solvent was distilled off at 100°C and a vacuum of 1.3 kPa for 3 hours to obtain reactive silicon group-containing polyoxyalkylene derivative A-3. The resulting reactive silicon group-containing polyoxyalkylene derivative A-3 was a pale yellow, transparent liquid with a number average molecular weight of 13,000 and a viscosity of 8,000 mPa s.

[0064] Example 1-4 Synthesis of Reactive Silicon Group-Containing Polyoxyalkylene Derivative A-4 A 200 mL separable flask equipped with a stirrer, reflux condenser, and thermometer was charged with 1,280 g of polypropylene glycol containing allyl groups at both ends and having a number average molecular weight of 12,000 (0.2 mol in terms of functional groups in the terminal allyl groups) and a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (50 ppm by mass as platinum), and heated to 60° C. 90 g of the disiloxane compound b obtained in Synthesis Example 2 (0.3 mol of hydrosilyl functional groups) was then added, and the mixture was stirred at 60° C. for 2 hours. 1 The reaction was terminated when H-NMR analysis confirmed that the peaks derived from the allyl groups in the raw material had completely disappeared and that the peaks derived from the target product had been detected. After the reaction was completed, the solvent was distilled off at 100°C and a vacuum of 1.3 kPa for 3 hours to obtain reactive silicon group-containing polyoxyalkylene derivative A-4. The resulting reactive silicon group-containing polyoxyalkylene derivative A-4 was a pale yellow, transparent liquid with a number average molecular weight of 13,000 and a viscosity of 7,900 mPa s.

[0065] Example 1-5 Synthesis of Reactive Silicon Group-Containing Polyoxyalkylene Derivative A-5 A 200 mL separable flask equipped with a stirrer, reflux condenser, and thermometer was charged with 1,280 g of polypropylene glycol containing allyl groups at both ends and having a number average molecular weight of 12,000 (0.2 mol in terms of functional groups in the terminal allyl groups) and a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (50 ppm by mass as platinum), and heated to 60° C. 97 g of the disiloxane compound c obtained in Synthesis Example 3 (0.3 mol of hydrosilyl functional groups) was then added, and the mixture was stirred at 60° C. for 2 hours. 1The reaction was terminated when H-NMR measurement confirmed that the peaks derived from the allyl groups of the raw material had completely disappeared and that peaks derived from the target product had been detected. After completion of the reaction, the solvent was distilled off at 100°C and a vacuum of 1.3 kPa for 3 hours to obtain reactive silicon group-containing polyoxyalkylene derivative A-5. The resulting reactive silicon group-containing polyoxyalkylene derivative A-5 was a pale yellow, transparent liquid with a number average molecular weight of 13,200 and a viscosity of 8,200 mPa s.

[0066] Comparative Example 1-1 Synthesis of Reactive Silicon Group-Containing Polyoxyalkylene Derivative A'-6 Into a 200 mL separable flask equipped with a stirrer, reflux condenser, and thermometer, 100 g of polypropylene glycol containing allyl groups at both ends and having a number average molecular weight of 7,800 (0.039 mol in terms of functional groups in the terminal allyl groups) and a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (50 ppm by mass as platinum) were placed and heated to 60° C. 6 g of methyldimethoxysilane (0.06 mol of hydrosilyl functional groups) was then added, and the mixture was stirred at 60° C. for 2 hours. 1 The reaction was terminated when H-NMR analysis confirmed that the peaks derived from the allyl groups in the raw material had completely disappeared and that peaks derived from the target product had been detected. After the reaction was completed, the solvent was distilled off at 100°C and a vacuum of 1.3 kPa for 3 hours to obtain reactive silicon group-containing polyoxyalkylene derivative A'-6. The resulting reactive silicon group-containing polyoxyalkylene derivative A'-6 was a pale yellow, transparent liquid with a number average molecular weight of 8,400 and a viscosity of 2,700 mPa s.

[0067] Comparative Example 1-2 Synthesis of Reactive Silicon Group-Containing Polyoxyalkylene Derivative A'-7 Into a 200 mL separable flask equipped with a stirrer, reflux condenser, and thermometer, 100 g of polypropylene glycol containing allyl groups at both ends and having a number average molecular weight of 7,800 (0.039 mol in terms of functional groups of terminal allyl groups) and 6.6 g of mercaptomethyltrimethoxysilane (0.039 mol of functional group amount of mercapto groups) were placed and heated to 90° C. 0.1 g of 2,2′-azobis-2-methylbutyronitrile was added, and the mixture was stirred at 90° C. for 3 hours. 1The reaction was terminated when H-NMR analysis confirmed that the peaks derived from the allyl and mercapto groups of the raw material had completely disappeared and that the peaks derived from the target compound had been detected. The resulting reactive silicon group-containing polyoxyalkylene derivative A'-7 was a pale yellow, transparent liquid with a number average molecular weight of 8,100 and a viscosity of 3,300 mPa s.

[0068] Comparative Example 1-3 Synthesis of Reactive Silicon Group-Containing Polyoxyalkylene Derivative A'-8 Into a 200 mL separable flask equipped with a stirrer, reflux condenser, and thermometer, 100 g of polypropylene glycol containing hydroxyl groups at both ends and having a number average molecular weight of 7,600 (0.040 mol equivalent to the functional group of the terminal hydroxyl group) and 7.1 g of isocyanate methyltrimethoxysilane (0.040 mol of functional group amount of isocyanate group) were placed and heated to 80°C. 0.1 g of dioctyltin dilaurate was added thereto and stirred at 80°C for 3 hours. IR measurement confirmed that the absorption peak derived from the isocyanate group of the raw material had completely disappeared and that an absorption peak derived from the urethane bond had been detected, marking the end of the reaction. The resulting reactive silicon group-containing polyoxyalkylene derivative A'-8 was a pale yellow, transparent liquid with a number average molecular weight of 8,000 and a viscosity of 3,700 mPa·s.

[0069] Comparative Example 1-4 Synthesis of Reactive Silicon Group-Containing Polyoxyalkylene Derivative A'-9 100 g of polypropylene glycol having hydroxyl groups at both ends and a number average molecular weight of 7,600 (0.040 mol in terms of functional groups of the terminal hydroxyl groups) and 6.1 g (0.040 mol) of tetramethoxysilane were placed in a 200 mL separable flask equipped with a stirrer, reflux condenser, and thermometer, and stirred at 80°C for 3 hours. The reaction was terminated when IR measurement confirmed that the absorption peak derived from the hydroxyl groups of the raw material had completely disappeared. The resulting reactive silicon group-containing polyoxyalkylene derivative A'-9 was a colorless, transparent liquid with a number average molecular weight of 22,000 and a viscosity of 6,800 mPa·s.

[0070] [3] Preparation of Composition and Cured Coating [Example 2-1] A composition was prepared by uniformly mixing 100 parts by mass of the reactive silicon group-containing polyoxyalkylene derivative A-1 obtained in Example 1-1 above and 0.5 parts by mass of curing catalyst B-1 (2-[3-(trimethoxysilyl)propyl]-1,1,3,3-tetramethylguanidine) using a stirrer while keeping moisture out. The resulting composition was applied to a glass plate using a No. 14 bar coater in air at 25°C and 50% RH, and then dried and cured for one day in air at 25°C and 50% RH to produce a cured coating.

[0071] Examples 2-2 to 2-5 and Comparative Examples 2-1 to 2-4 Compositions and cured coatings were prepared in the same manner as in Example 2-1, except that the reactive silicon group-containing polyoxyalkylene derivative A-1 in Example 2-1 was changed to the reactive silicon group-containing polyoxyalkylene derivatives A-2 to A-5 obtained in Examples 1-2 to 1-5 and the reactive silicon group-containing polyoxyalkylene derivatives A'-6 to A'-9 obtained in Comparative Examples 1-1 to 1-4, respectively.

[0072] Example 2-6 A composition and a cured coating were prepared in the same manner as in Example 2-1, except that the curing catalyst B-1 in Example 2-1 was changed to 5 parts by mass of curing catalyst B-2 (3-aminopropyltrimethoxysilane).

[0073] Example 2-7 A composition and a cured coating were prepared in the same manner as in Example 2-1, except that the curing catalyst B-1 in Example 2-1 was changed to 5 parts by mass of curing catalyst B-3 (dioctyltin diversatate).

[0074] Example 2-8 A composition and a cured coating were prepared in the same manner as in Example 2-1, except that the curing catalyst B-1 in Example 2-1 was changed to 2 parts by mass of curing catalyst B-4 (titanium diisopropoxybis(ethylacetoacetate)).

[0075] Comparative Example 2-5 A composition and a cured coating were prepared in the same manner as in Comparative Example 2-1, except that the curing catalyst B-1 in Comparative Example 2-1 was changed to 5 parts by mass of curing catalyst B-2 (3-aminopropyltrimethoxysilane).

[0076] Comparative Example 2-6 A composition and a cured coating were prepared in the same manner as in Comparative Example 2-1, except that the curing catalyst B-1 in Comparative Example 2-1 was changed to 5 parts by mass of curing catalyst B-3 (dioctyltin diversatate).

[0077] Comparative Example 2-7 A composition and a cured coating were prepared in the same manner as in Comparative Example 2-2, except that the curing catalyst B-1 in Comparative Example 2-2 was changed to 5 parts by mass of curing catalyst B-2 (3-aminopropyltrimethoxysilane).

[0078] Comparative Example 2-8 A composition and a cured coating were prepared in the same manner as in Comparative Example 2-2, except that the curing catalyst B-1 in Comparative Example 2-2 was changed to 5 parts by mass of curing catalyst B-3 (dioctyltin diversatate).

[0079] The cured coatings produced in Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-8 above were evaluated for the following physical properties. The results are shown in Tables 1 and 2. [Tack-free time] Test specimens obtained by applying the composition to glass plates using the above application method were left in an atmosphere of 25°C and 50% RH, and the time until moisture curing progressed and the coating no longer adhered to the finger when pressed with a finger on the coated surface was measured. A smaller value indicates better curability. [Yellowing resistance] Test specimens formed on glass plates using the above application method were irradiated with ultraviolet light (cumulative exposure dose 26,000 mJ / cm) for 2 weeks using a germicidal lamp in an atmosphere of 25°C and 50% RH. 3 ) was performed. The degree of yellowing of the cured coating at this time was evaluated using a color difference meter in accordance with JIS K 7373 as ΔYI (yellowing index = change in yellowness index YI). A smaller value indicates better yellowing resistance. A ΔYI of less than 0.5 was evaluated as excellent yellowing resistance and was rated as "○". A ΔYI of 0.5 or more was evaluated as "×". [Heat Resistance] Test specimens on glass plates on which cured coatings had been formed by the above coating method were left to stand in a dryer at 150°C for two weeks. After that, coatings that did not leave a finger mark when pressed with a finger on the surface were evaluated as "○". Coatings that left a finger mark when pressed with a finger on the surface were evaluated as "×".

[0080]

[0081]

[0082] As shown in Table 1, the cured coatings prepared in Examples 2-1 to 2-8 using the reactive silicon group-containing polyoxyalkylene derivatives A-1 to A-5 obtained in Examples 1-1 to 1-5 were found to have excellent curability, yellowing resistance, and heat resistance. On the other hand, as shown in Table 2, Comparative Examples 2-1, 2-5, and 2-6, which used the reactive silicon group-containing polyoxyalkylene derivative A'-6 that does not have a group represented by structural formula (1), and Comparative Example 2-4, which used the reactive silicon group-containing polyoxyalkylene derivative A'-9, were found to have poor curability, Comparative Examples 2-2, 2-7, and 2-8, which used the reactive silicon group-containing polyoxyalkylene derivative A'-7 having a sulfide-methylene-silicon bond, were found to have low heat resistance, and Comparative Example 2-3, which used the reactive silicon group-containing polyoxyalkylene derivative A'-8 having a urethane bond, was found to have poor yellowing resistance.

Claims

1. A reactive silicon group-containing polyoxyalkylene derivative in which one or both ends of the polyoxyalkylene chain are blocked with a group represented by the following structural formula (1). (In the formula, R 1 and R 2 each independently represents a hydrogen atom, an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and R 3 each independently represents an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and n is an integer of 2 to 12. The wavy line represents a bond.) 2. The reactive silicon group-containing polyoxyalkylene derivative according to claim 1, having a number average molecular weight of 200 to 50,000.

3. The method for producing a reactive silicon group-containing polyoxyalkylene derivative according to claim 1, wherein an alkenyl group-containing polyoxyalkylene derivative in which one or both ends of the polyoxyalkylene chain are blocked with an alkenyl group having 2 to 12 carbon atoms is reacted with a disiloxane compound represented by the following formula (4). (In the formula, R 1 , R 2 and R 3 represent the same meaning as described above.) 4. A method for producing a reactive silicon group-containing polyoxyalkylene derivative according to claim 3, having a number average molecular weight of 200 to 50,000.

5. A curable composition containing (A) the reactive silicon group-containing polyoxyalkylene derivative according to claim 1 and (B) a curing catalyst.

6. The curable composition according to claim 5, wherein the (B) curing catalyst is an amine compound.

7. A cured product obtained by curing the curable composition according to claim 5 or 6.

8. A coating agent composition containing (A) the reactive silicon group-containing polyoxyalkylene derivative according to claim 1 and (B) a curing catalyst.

9. The coating agent composition according to claim 8, wherein the (B) curing catalyst is an amine compound.

10. An article having a coating layer obtained by curing the coating agent composition according to claim 8 or 9.

11. An adhesive composition containing (A) the reactive silicon group-containing polyoxyalkylene derivative according to claim 1 and (B) a curing catalyst.

12. The adhesive composition according to claim 11, wherein the (B) curing catalyst is an amine compound.

13. An article having an adhesive layer obtained by curing the adhesive composition according to claim 11 or 12.

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