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

Abstract

To provide a reactive silicon group-containing polyoxyalkylene derivative that, even when an amine-based compound is used as a curing catalyst, has superior curability even and yields a cured product having superior yellowing resistance and heat resistance.SOLUTION: The present invention provides a reactive silicon group-containing polyoxyalkylene derivative in which one or both terminals of a polyoxyalkylene chain are blocked with a group represented by the following structural formula (1). (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; R3 each independently represents a C1-10 aliphatic saturated hydrocarbon group or a C6-10 aryl group; n is an integer of 2 to 12; and the line with a wavy line represents a bond).SELECTED DRAWING: None

Description

Technical Field

[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. More specifically, the present invention relates to a polyoxyalkylene derivative having an organic silicon group capable of reacting to form a siloxane bond as a reactive silicon group-containing group, a method for producing the same, a curable composition, and a cured product.

Background Art

[0002] Since a reactive silicon group, particularly an alkoxysilyl group, has the property of hydrolytic condensation in the presence of moisture, a polymer having this reactive silicon group can be used as a curable composition that crosslinks and cures in the presence of moisture or humidity. Among these polymers, those having a polyoxyalkylene group as the main chain are generally known as modified silicones. In addition, a curable composition using this has the characteristic of being liquid at room temperature and becoming a rubber elastic body by curing, and is widely used as a coating agent, an adhesive, a building sealant, etc. by utilizing this characteristic.

[0003] Regarding the method for producing a polymer having a reactive silicon group at the molecular chain end, many proposals have been made, and some are already industrially produced. For example, polyoxypropylene derivatives having alkoxysilyl groups bonded to both ends of the molecular chain are known, and a room temperature curable composition using such a polymer as a main agent (base polymer) is 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 curability. Therefore, although the addition of a catalyst such as an organotin compound is generally indispensable to ensure sufficient curability at room temperature, there are concerns about the toxicity of organotin compounds to the human body and the environment.

[0004] In addition, Patent Document 3 discloses an alkoxysilyl-terminated polymer obtained by reacting a polymer having a hydroxyl group at the terminal with isocyanatosilane or the like in order to improve reactivity. However, although the compound of Patent Document 3 is excellent in reactivity, on the other hand, since it contains a urethane or urea bond in the molecule, coloring over time is remarkable, and yellowing resistance and heat resistance are insufficient. Further, when producing the terminal-blocked polymer, the use of highly toxic low-boiling isocyanatosilane, and furthermore, the problem is regarded that the same low-boiling isocyanatosilane can be generated by thermal decomposition of the urethane or urea bond at high temperature.

[0005] In addition, Patent Document 4 discloses that by using a polyoxyalkylene derivative having a sulfide-methylene bond as a linking group between the terminal alkoxysilyl group and the polyoxyalkylene main chain, even when an amine-based compound is used as a curing catalyst instead of an organotin compound, it is excellent in fast curability, excellent in yellowing resistance, and does not use isocyanatosilane, thus providing a cured product that can be low-toxic. However, although the compound of Patent Document 4 is excellent in reactivity when an amine catalyst is used, on the other hand, the problem is regarded that the cured product softens due to cleavage of the sulfide-methylene-silicon bond at high temperature.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

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

Means for Solving the Problems

[0008] As a result of intensive studies to solve the above problems, the present inventors have found that a polyoxyalkylene derivative having an organoxymethyl group as a reactive silicon group and a silyl group having two organoxy groups bonded thereto at the terminals has good curability even when an amine compound is used as a curing catalyst, and gives a cured product excellent in yellowing resistance and heat resistance, and thus completed the present invention.

[0009] That is, the present invention provides: 1. A reactive silicon group-containing polyoxyalkylene derivative in which one or both terminals of a polyoxyalkylene chain are blocked with a group represented by the following structural formula (1):

Chemical Formula

Chemical Formula

Advantages of the Invention

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

BEST MODE FOR CARRYING OUT THE INVENTION

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

[0012]

Chemical formula

[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, 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. R 1 、R 2 and R 3 As the aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, any of linear, cyclic, and branched forms may be used. 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; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. R 1 、R 2 and R 3 Specific examples of the aryl group having 6 to 10 carbon atoms include phenyl, tolyl, xylyl, α-naphthyl, and β-naphthyl groups. In addition, some or all of the hydrogen atoms of these groups may be substituted with halogen atoms such as F, Cl, Br, or cyano groups. Specific examples thereof include 3-chloropropyl group, 3,3,3-trifluoropropyl group, 2-cyanoethyl group, etc.

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

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

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

[0017] Therefore, as the reactive silicon group-containing polyoxyalkylene derivative of the present invention, those represented by the following structural formula (2) are preferable.

[0018]

Chemical formula

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

[0020]

Chemical formula

[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. Note that R 5When there are a plurality of them (p is 2 or more), each R 5 may be the same or different from each other.

[0022] R 5 As the divalent hydrocarbon group of, a linear or branched alkylene group having 1 to 14 carbon atoms is preferable, and examples thereof include methylene, ethylene, propylene, trimethylene, tetramethylene, isobutylene, pentamethylene, hexamethylene, heptamethylene, octamethylene groups and the like. Among these, as R 5 a linear or branched alkylene group having 2 to 4 carbon atoms such as methylene, ethylene, trimethylene, propylene, tetramethylene, isobutylene group is particularly preferable.

[0023] That is, specific examples of the repeating unit (-OR 5 -) in the above formula (3) include oxyalkylene groups such as -OCH2-, -OCH2CH2-, -OCH2CH2CH2-, -OCH(CH3)CH2-, -OCH2CH2CH2CH2-, -OCH(CH2CH3)CH2-, -OC(CH3)2CH2-.

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

[0025] The main chain skeleton of the oxyalkylene group-containing organosilicon compound of the present invention may be composed of one kind of repeating unit or may be composed of two or more kinds of repeating units. In particular, when used in materials such as coating agents, adhesives, and sealants, it is preferable to contain an oxypropylene (-OCH(CH3)CH2-) unit from the viewpoint of durability.

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

[0027] Also, the viscosity of the reactive silicon group-containing polyoxyalkylene derivative of the present invention is not particularly limited. However, considering improving workability by setting the viscosity of the curable composition containing the compound within an appropriate range and imparting sufficient curability, 10 to 100,000 mPa·s is preferable, 50 to 50,000 mPa·s is more preferable, and 100 to 10,000 mPa·s is even more preferable. Here, the viscosity is a measured value at 25 °C using a B-type rotational viscometer.

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

[0029]

Chemical formula

[0030] Specific examples of the disiloxane compound represented by the above 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]

Chemical formula

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

[0033]

Chemical formula

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

[0035]

Chemical formula

[0036] In formula (5), R 6 is an alkenyl group having 2 to 12 carbon atoms. As the alkenyl group having 2 to 12 carbon atoms, a linear or branched alkenyl group having 2 to 8 carbon atoms is preferable. 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, 2-methyl-2-butenyl, 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 groups and the like. Among these, a vinyl group or an allyl group is preferable, and a vinyl group is more preferable.

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

[0038]

Chemical formula

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

[0040] The reaction ratio of the alkenyl group-containing polyoxyalkylene derivative and the disiloxane compound represented by the above formula (4) suppresses by-products during the hydrosilylation reaction and improves the storage stability and properties of the resulting polyoxyalkylene compound. Considering this, with respect to one alkenyl group in the alkenyl group-containing polyoxyalkylene derivative, the ratio of the hydrosilyl group of the disiloxane compound represented by the above formula (4) to be 0.8 to 2.5 is preferable, and the ratio of 0.9 to 2.0 is more preferable.

[0041] The platinum group metal catalyst used in the above hydrosilylation reaction is not particularly limited. Specific examples thereof 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, tetrakis triphenylphosphine platinum, dichlorobis triphenylphosphine platinum, dichlorobis acetonitrile platinum, dichlorobis benzonitrile platinum, dichlorocyclooctadiene platinum, etc., and supported catalysts such as platinum-carbon, platinum-alumina, platinum-silica, etc. Among these, from the viewpoint of selectivity during hydrosilylation, a zero-valent platinum complex is preferable, and a toluene or xylene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex is more preferable.

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

[0043] The above hydrosilylation reaction can be carried out without a solvent, but it can be carried out in an organic solvent such as toluene, isopropyl alcohol, methanol, etc. as necessary within a range that does not inhibit the reaction.

[0044] The reaction temperature in the above 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 using a solvent, it is preferable to carry out the reaction in the range of 0°C to the boiling point of the solvent. The reaction time is not particularly limited and is usually about 1 to 60 hours, but preferably 1 to 24 hours.

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

[0046] The curing catalyst (B) is a component that promotes the reaction in which the hydrolyzable group contained in the (A) polyoxyalkylene derivative containing a reactive silicon group is hydrolytically condensed with moisture in the air, and promotes the curing of the composition, and is added to cure efficiently. The curing catalyst is not particularly limited as long as it is a curing catalyst used for curing general moisture condensation curing type compositions. Specific examples thereof 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 divaldate; titanate and titanium chelate compounds such as tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrakis(2-ethylhexoxy)titanium, dipropoxybis(acetylacetonato)titanium, titanium diisopropoxybis(ethylacetoacetate), and titanium isopropoxyoctylene glycol, and partial hydrolyzates 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 alcoholate, aluminum acylate, salts of aluminum acylate, aluminosiloxy compounds, and aluminum chelate compounds; aminoalkyl group-substituted alkoxysilanes such as 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]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, and N-phenyl-3-aminopropyltrimethoxysilane; amine compounds such as hexylamine and dodecylamine phosphate and salts thereof; quaternary ammonium salts such as benzyltriethylammonium acetate; lower fatty acid salts of alkali metals such as potassium acetate, sodium acetate, and lithium oxalate;Dialkylhydroxylamines such as dimethylhydroxylamine and diethylhydroxylamine; silanes and siloxanes containing a guanidino group such as 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, 2-[3-(tris(trimethylsiloxy)silyl)propyl]-1,1,3,3-tetramethylguanidine; silanes and siloxanes containing a phosphazene base such as N,N,N’,N’,N'',N''-hexamethyl-N'''-[3-(trimethoxysilyl)propyl]-phosphorimidic triamide, etc. These may be used alone or in combination of two or more kinds.

[0047] Among these, dioctyltin dilaurate, dioctyltin dibutyrate, tetra-isopropoxytitanium, 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, 2-[3-(trimethoxysilyl)propyl]-1,1,3,3-tetramethylguanidine are preferred because they are more reactive. Further, from the viewpoint of the curability of the composition, dioctyltin dilaurate, dioctyltin dibutyrate, 3-aminopropyltrimethoxysilane, 2-[3-(trimethoxysilyl)propyl]-1,1,3,3-tetramethylguanidine are more preferred. Considering the non-inclusion of organotin compounds and lower toxicity, 3-aminopropyltrimethoxysilane and 2-[3-(trimethoxysilyl)propyl]-1,1,3,3-tetramethylguanidine are even more preferred. From the viewpoint of the curability of the composition, 2-[3-(trimethoxysilyl)propyl]-1,1,3,3-tetramethylguanidine is particularly preferred.

[0048] Although the addition amount of the curing catalyst is not particularly limited, considering adjusting the curing rate to an appropriate range to improve workability, 0.01 to 15 parts by mass, preferably 0.1 to 5 parts by mass, is preferable with respect to 100 parts by mass of the reactive silicon group-containing organopolysiloxane (A).

[0049] Furthermore, the composition of the present invention preferably has a solvent-free form that substantially does not contain an organic solvent (which is often harmful to the human body and flammable), but a solvent can also be added and used from the viewpoints of its 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 can dissolve the component (A). Specific examples thereof 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 can be used alone or in combination of two or more.

[0050] In addition, various additives such as an adhesion improver, inorganic and organic ultraviolet absorbers, a storage stability improver, a plasticizer, a filler, a pigment, and a fragrance can be added to the composition of the present invention according to the purpose of use.

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

[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, phenolic resin, polyimide resin, polycarbonate resins such as polycarbonates and polycarbonate blends, acrylic resins such as poly(methyl methacrylate), polyester resins such as poly(ethylene terephthalate), poly(butylene terephthalate), and unsaturated polyester resins, polyamide resin, acrylonitrile-styrene copolymer resin, styrene-acrylonitrile-butadiene copolymer resin, polyvinyl chloride resin, polystyrene resin, blend of polystyrene and polyphenylene ether, cellulose acetate butyrate, and polyethylene resin; metal substrates such as iron plate, copper plate, and steel plate; paint-coated surface; glass; ceramic; concrete; slate board; textile; inorganic fillers such as wood, stone, tile, (hollow) silica, titania, zirconia, and alumina; and glass fiber products such as glass cloth, glass tape, glass mat, and glass paper including glass fiber.

[0053] When the composition of the present invention comes into contact with moisture in the atmosphere, the hydrolysis and condensation reaction of the (A) polyoxyalkylene derivative containing a reactive silicon group proceeds. As an index of the moisture in the atmosphere, any humidity of 10 to 100%RH may be used. Generally, the higher the humidity, the faster the hydrolysis proceeds, so moisture may be added to the atmosphere if desired. The curing reaction temperature and time can be appropriately changed according to factors such as the substrate used, moisture concentration, catalyst concentration, and type of hydrolyzable group. The curing reaction temperature is usually preferably about 10°C to 40°C from the viewpoint of workability, etc., but in order to accelerate the curing reaction, it may be heated and cured within a range not exceeding the heat resistance temperature of the substrate used. The curing reaction time is usually about 1 minute to 1 week from the viewpoint of workability, etc.

Example

[0054] Hereinafter, the present invention will be described more specifically 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 the measured value at 25°C by a B-type rotational viscometer, and the molecular weight and degree of polymerization (the number of repeating units of 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

Chemical formula

[0056] To a 300 mL separable flask equipped with a stirrer, a reflux condenser, and a thermometer, 200 g of trimethoxy(methoxymethyl)silane and 40.4 g of 1,1,3,3-tetramethyldisiloxane were added, and 1.2 g of concentrated sulfuric acid (98% by mass) was added dropwise while stirring at 7°C. After the addition was completed, the mixture was stirred at 25°C for 5 hours. Then, 6 g of Kyoward (registered trademark) 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and after stirring for 1 hour, the reaction solution was taken out by filtration, and the reaction solution was distilled (distillation temperature 90°C, vacuum degree 17 kPa) to obtain a disiloxane compound a. 11H-NMR (CDCl3): δ 4.46 - 4.61 ppm (s, 1H, -SiH), 3.41 - 3.34 ppm (s, 9H, -Si(OCH3)2, -OCH3), 3.15 - 3.13 ppm (s, 2H, -CH2-), 0.00 - 0.02 ppm (s, 6H, -SiCH3)

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

Chemical formula

[0058] 268 g of triethoxy(ethoxymethyl)silane and 40.4 g of 1,1,3,3-tetramethyldisiloxane were added to a 300 mL separable flask equipped with a stirrer, a reflux condenser, and a thermometer. While stirring at 7°C, 1.2 g of concentrated sulfuric acid (98% by mass) was added dropwise. After the addition was complete, the mixture was stirred at 25°C for 5 hours. Then, 6 g of Kyoward (registered trademark) 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred for 1 hour. After that, the reaction solution was taken out by filtration, and the reaction solution was distilled (distillation temperature: 90°C, vacuum degree: 17 kPa) to obtain the disiloxane compound b. 1 1H-NMR (CDCl3): δ 4.46 - 4.61 ppm (s, 1H, -SiH), 3.85 - 3.63 ppm (m, 6H, -OCH2-), 1.41 - 1.34 ppm (m, 9H, -CH3), 0.00 - 0.02 ppm (s, 6H, -SiCH3)

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

Chemical formula

[0060] Into a 300 mL separable flask equipped with a stirrer, a reflux condenser, and a thermometer, 200 g of trimethoxy(methoxymethyl)silane and 115 g of 1,1,3,3-tetraphenyldisiloxane were added. While stirring at 7 °C, 1.2 g of concentrated sulfuric acid (98% by mass) was added dropwise. After the addition was complete, the mixture was stirred at 25 °C for 5 hours. Then, 6 g of Kyoward (registered trademark) 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred for 1 hour. After that, the reaction solution was taken out by filtration, and the reaction solution was distilled (distillation temperature 90 °C, vacuum degree 17 kPa) to obtain the disiloxane compound c. 1 1H-NMR (CDCl3): δ 7.58 - 7.32 ppm (m, 10H, -SiC6H5), 4.46 - 4.61 ppm (s, 1H, -SiH), 3.41 - 3.34 ppm (s, 9H, -Si(OCH3)2, -OCH3), 3.15 - 3.13 ppm (s, 2H, -CH2-)

[0061] [2] Synthesis of reactive silicon group-containing polyoxyalkylene derivative [Example 1-1] Synthesis of reactive silicon group-containing polyoxyalkylene derivative A-1 Into a 200 mL separable flask equipped with a stirrer, a reflux condenser, and a thermometer, 100 g of polypropylene glycol with allyl groups at both ends having a number average molecular weight of 5,100 (functional group conversion of terminal allyl groups: 0.07 mol) and a toluene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (50 ppm by mass as platinum) were placed and heated to 60 °C. Into this, 27 g (functional group amount of hydrosilyl group: 0.11 mol) of the disiloxane compound a obtained in Synthesis Example 1 was added and stirred at 60 °C for 2 hours. 1 It was confirmed by 1H-NMR measurement that the peak derived from the allyl group of the raw material completely disappeared and the peak derived from the target product was detected, and the reaction was terminated. After the reaction was completed, the solvent was distilled off at 100 °C and a vacuum degree of 1.3 kPa for 3 hours to obtain a reactive silicon group-containing polyoxyalkylene derivative A-1. The obtained reactive silicon group-containing polyoxyalkylene derivative A-1 was a pale yellow transparent liquid, having 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 Into a 200 mL separable flask equipped with a stirrer, a reflux condenser and a thermometer, 100 g of an allyl group-containing polypropylene glycol having a number average molecular weight of 7,800 (0.039 mol in terms of the functional group of the terminal allyl group) and a toluene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (50 ppm by mass as platinum) were placed and heated to 60 °C. 15 g of the disiloxane compound a obtained in Synthesis Example 1 (0.06 mol of the functional group amount of the hydrosilyl group) was added thereto, and the mixture was stirred at 60 °C for 2 hours. 1 By 1H-NMR measurement, it was confirmed that the peak derived from the allyl group of the raw material completely disappeared and the peak derived from the target product was detected, and the reaction was terminated. After the reaction was completed, the solvent was distilled off at 100 °C and a vacuum degree of 1.3 kPa for 3 hours to obtain a reactive silicon group-containing polyoxyalkylene derivative A-2. The obtained reactive silicon group-containing polyoxyalkylene derivative A-2 was a pale yellow transparent liquid, having 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 Into a 200 mL separable flask equipped with a stirrer, a reflux condenser and a thermometer, 1280 g of an allyl group-containing polypropylene glycol having a number average molecular weight of 12,000 (0.2 mol in terms of the functional group of the terminal allyl group) and a toluene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (50 ppm by mass as platinum) were placed and heated to 60 °C. 75 g of the disiloxane compound a obtained in Synthesis Example 1 (0.3 mol of the functional group amount of the hydrosilyl group) was added thereto, and the mixture was stirred at 60 °C for 2 hours. 1 By 1H-NMR measurement, it was confirmed that the peak derived from the allyl group of the raw material completely disappeared and the peak derived from the target product was detected, and the reaction was terminated. After the reaction was completed, the solvent was distilled off at 100 °C and a vacuum degree of 1.3 kPa for 3 hours to obtain a reactive silicon group-containing polyoxyalkylene derivative A-3. The obtained reactive silicon group-containing polyoxyalkylene derivative A-3 was a pale yellow transparent liquid, having a number average molecular weight of 13,000 and a viscosity of 8,000 mPa·s.

[0064] [Examples 1-4] Synthesis of reactive silicon group-containing polyoxyalkylene derivative A-4 Into a 200 mL separable flask equipped with a stirrer, a reflux condenser, and a thermometer, 1280 g of an allyl group-containing polypropylene glycol with a number average molecular weight of 12,000 (0.2 mol in terms of the functional group of the terminal allyl group) and a toluene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (50 ppm by mass as platinum) were added, and the mixture was heated to 60°C. 90 g of the disiloxane compound b obtained in Synthesis Example 2 (0.3 mol of the functional group amount of the hydrosilyl group) was added thereto, and the mixture was stirred at 60°C for 2 hours. 1 It was confirmed by 1H-NMR measurement that the peak derived from the allyl group of the raw material completely disappeared and the peak derived from the target product was detected, and the reaction was terminated. After the reaction was completed, the solvent was distilled off at 100°C and a vacuum degree of 1.3 kPa for 3 hours to obtain a reactive silicon group-containing polyoxyalkylene derivative A-4. The obtained reactive silicon group-containing polyoxyalkylene derivative A-4 was a pale yellow transparent liquid, having a number average molecular weight of 13,000 and a viscosity of 7,900 mPa·s.

[0065] [Examples 1-5] Synthesis of reactive silicon group-containing polyoxyalkylene derivative A-5 Into a 200 mL separable flask equipped with a stirrer, a reflux condenser, and a thermometer, 1280 g of an allyl group-containing polypropylene glycol with a number average molecular weight of 12,000 (0.2 mol in terms of the functional group of the terminal allyl group) and a toluene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (50 ppm by mass as platinum) were added, and the mixture was heated to 60°C. 97 g of the disiloxane compound c obtained in Synthesis Example 3 (0.3 mol of the functional group amount of the hydrosilyl group) was added thereto, and the mixture was stirred at 60°C for 2 hours. 1 It was confirmed by 1H-NMR measurement that the peak derived from the allyl group of the raw material completely disappeared and the peak derived from the target product was detected, and the reaction was terminated. After the reaction was completed, the solvent was distilled off at 100°C and a vacuum degree of 1.3 kPa for 3 hours to obtain a reactive silicon group-containing polyoxyalkylene derivative A-5. The obtained reactive silicon group-containing polyoxyalkylene derivative A-5 was a pale yellow transparent liquid, having 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, a reflux condenser, and a thermometer, 100 g of a polypropylene glycol having allyl groups at both ends with a number average molecular weight of 7,800 (0.039 mol in terms of the functional group of the terminal allyl group) and a toluene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (50 mass ppm as platinum) were placed and heated to 60 °C. 6 g of methyldimethoxysilane (0.06 mol of the functional group amount of the hydrosilyl group) was introduced therein, and the mixture was stirred at 60 °C for 2 hours. 1 By 1H-NMR measurement, it was confirmed that the peak derived from the allyl group of the raw material completely disappeared and the peak derived from the target product was detected, and the reaction was terminated. After the reaction was completed, the solvent was distilled off at 100 °C and a vacuum degree of 1.3 kPa for 3 hours to obtain a reactive silicon group-containing polyoxyalkylene derivative A'-6. The obtained reactive silicon group-containing polyoxyalkylene derivative A'-6 was a pale yellow transparent liquid, having 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, a reflux condenser, and a thermometer, 100 g of a polypropylene glycol having allyl groups at both ends with a number average molecular weight of 7,800 (0.039 mol in terms of the functional group of the terminal allyl group) and 6.6 g of mercaptomethyltrimethoxysilane (0.039 mol of the functional group amount of the mercapto group) were placed and heated to 90 °C. 0.1 g of 2,2'-azobis-2-methylbutyronitrile was introduced therein, and the mixture was stirred at 90 °C for 3 hours. 1 By 1H-NMR measurement, it was confirmed that the peaks derived from the allyl group and the mercapto group of the raw material completely disappeared and the peak derived from the target product was detected, and the reaction was terminated. The obtained reactive silicon group-containing polyoxyalkylene derivative A'-7 was a pale yellow transparent liquid, having 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, a reflux condenser, and a thermometer, 100 g of a polypropylene glycol having hydroxyl groups at both ends with a number average molecular weight of 7,600 (0.040 mol in terms of the functional group of the terminal hydroxyl group) and 7.1 g of isocyanatomethyltrimethoxysilane (0.040 mol in terms of the functional group amount of the isocyanate group) were placed and heated to 80°C. 0.1 g of dioctyltin dilaurate was added thereto, and the mixture was stirred at 80°C for 3 hours. It was confirmed by IR measurement that the absorption peak derived from the isocyanate group of the raw material completely disappeared and the absorption peak derived from the urethane bond was detected, and the reaction was terminated. The obtained reactive silicon group-containing polyoxyalkylene derivative A'-8 was a pale yellow transparent liquid, having 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 Into a 200 mL separable flask equipped with a stirrer, a reflux condenser, and a thermometer, 100 g of a polypropylene glycol having hydroxyl groups at both ends with a number average molecular weight of 7,600 (0.040 mol in terms of the functional group of the terminal hydroxyl group) and 6.1 g of tetramethoxysilane (0.040 mol) were placed and stirred at 80°C for 3 hours. It was confirmed by IR measurement that the absorption peak derived from the hydroxyl group of the raw material completely disappeared, and the reaction was terminated. The obtained reactive silicon group-containing polyoxyalkylene derivative A'-9 was a colorless transparent liquid, having a number average molecular weight of 22,000 and a viscosity of 6,800 mPa·s.

[0070] [3] Preparation of Composition and Cured Film [Example 2-1] 100 parts by mass of the reactive silicon group-containing polyoxyalkylene derivative A-1 obtained in Example 1-1 and 0.5 part by mass of a curing catalyst B-1 (2-[3-(trimethoxysilyl)propyl]-1,1,3,3-tetramethylguanidine) were uniformly mixed using a stirrer under moisture shielding to prepare a composition. The resulting composition was applied to a glass plate using a bar coater No. 14 under air at 25°C and 50% RH, and dried and cured for 1 day under air at 25°C and 50% RH to produce a cured film.

[0071] [Examples 2-2 to 2-5 and Comparative Examples 2-1 to 2-4] In Example 2-1, except that the reactive silicon group-containing polyoxyalkylene derivative A-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, a composition and a cured film were produced in the same manner as in Example 2-1.

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

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

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

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

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

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

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

[0079] For the cured films prepared in Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-8 above, the following physical properties were evaluated. The results are shown in Tables 1 and 2. [Touch-dry time] A test piece obtained by applying the composition to a glass plate by the above coating method was left in air at 25°C and 50% RH. As moisture curing progressed, the time until the coating film no longer adhered to the finger when the coated surface was pressed with the finger was measured. A smaller value indicates better curability. [Yellowing resistance] A test piece having a cured film formed on a glass plate by the above coating method was irradiated with ultraviolet rays for 2 weeks (integrated irradiation dose: 26,000 mJ / cm 3 ) using a germicidal lamp in air at 25°C and 50% RH. The degree of yellowing of the cured film at that time was evaluated as ΔYI (degree of yellowing = change width of yellowness YI) using a color difference meter based on JIS K 7373. A smaller value indicates better yellowing resistance. When ΔYI was less than 0.5, it was evaluated as "○" as having excellent yellowing resistance. When ΔYI was 0.5 or more, it was evaluated as "×". 〔Heat resistance〕 For the test piece in which the cured film was formed on the glass plate by the above coating method, it was left standing in a dryer at 150 ° C for 2 weeks. Then, those in which no fingerprint was left on the coating film even when the surface of the coating film was pressed with a finger were evaluated as "○". Those in which a fingerprint was left on the coating film when the surface of the coating film was pressed with a finger were evaluated as "×".

[0080]

Table 1

[0081]

Table 2

[0082] As shown in Table 1, it can be seen that the cured films 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 are excellent in curability, yellowing resistance, and heat resistance. On the other hand, as shown in Table 2, in Comparative Examples 2-1, 2-5, and 2-6 using the reactive silicon group-containing polyoxyalkylene derivative A'-6 having no group represented by the above structural formula (1), and in Comparative Example 2-4 using the reactive silicon group-containing polyoxyalkylene derivative A'-9, the curability is inferior, and in Comparative Examples 2-2, 2-7, and 2-8 using the reactive silicon group-containing polyoxyalkylene derivative A'-7 having a sulfide-methylene-silicon bond, the heat resistance is low, and in Comparative Example 2-3 using the reactive silicon group-containing polyoxyalkylene derivative A'-8 having a urethane bond, it can be seen that the yellowing resistance is inferior.

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). 【Chemical 1】 (wherein, 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. A method for producing a reactive silicon group-containing polyoxyalkylene derivative according to Claim 1, comprising 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). 【Chemical 2】 (wherein R 1 , R 2 and R 3 represent the same meaning as described above.)

4. The 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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