Polyoxyalkylene derivative containing reactive silicon group, method for producing same, curable composition, and cured product

Abstract

Polyoxyalkylene derivatives containing reactive silicon groups, with single or double ends of the polyoxyalkylene chain capped with groups represented by the following structural formula (1), exhibit good curability even when using amine compounds as curing catalysts, resulting in cured products with excellent resistance to yellowing and heat resistance. Wherein, R... 1 and R 2 Each is independently 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 group independently represents an aliphatic saturated hydrocarbon group with 1 to 10 carbon atoms or an aryl group with 6 to 10 carbon atoms, where n is an integer from 2 to 12. Lines with wavy lines indicate bonding ends.

Description

Technical Field

[0001] This invention relates to polyoxyethylene derivatives containing reactive silicon groups, methods for manufacturing the same, curable compositions and cured products, and more specifically, to polyoxyethylene derivatives having organosilicon groups that can react to form siloxane bonds as groups containing reactive silicon groups, methods for manufacturing the same, curable compositions and cured products. Background Technology

[0002] Reactive silicon groups, especially alkoxysilyl groups, have hydrolytic condensation properties in the presence of moisture. Therefore, polymers with such reactive silicon groups can be used as curable compositions that are crosslinked and cured in the presence of moisture or humidity.

[0003] Among these polymers, those with a polyoxyalkylene backbone are generally used as modified silicones. Furthermore, curable compositions using these polymers are liquid at room temperature and possess the characteristic of becoming rubber elastomers upon curing. Utilizing this characteristic, they are widely used in coatings, adhesives, building sealants, and other applications.

[0004] Numerous schemes have been proposed for the manufacture of polymers with reactive silicon groups at the ends of the molecular chains, and some of these schemes have already been industrially produced.

[0005] For example, polyoxypropylene derivatives with alkoxysilyl groups bonded to both ends of the molecular chain are known, and room temperature curing compositions using such polymers as the main agent (base polymer) are known (Patent Documents 1 and 2).

[0006] However, the room-temperature curing compositions disclosed in Patent Documents 1 and 2 have low reactivity with moisture in the air and insufficient curing. Therefore, in order to ensure sufficient curing at room temperature, it is generally necessary to add catalysts such as organotin compounds. However, there are concerns that organotin compounds may be toxic to humans and the environment.

[0007] In addition, in order to improve reactivity, Patent Document 3 discloses an alkoxysilyl-terminated polymer that reacts a polymer having hydroxyl groups at the end with isocyanate-based silanes.

[0008] However, while the compound in Patent Document 3 exhibits excellent reactivity, it also contains urethane or urea bonds within its molecule, resulting in significant coloration over time and insufficient resistance to yellowing and heat. Furthermore, the use of highly toxic low-boiling-point isocyanate-based silanes in the manufacture of the end-capped polymer raises concerns about the potential for similar low-boiling-point isocyanate-based silanes to be produced due to the thermal decomposition of urethane or urea bonds at high temperatures.

[0009] Furthermore, Patent Document 4 discloses a method that utilizes a polyoxymethylene derivative with a thioether-methylene bond as a linker between the terminal alkoxysilane and the polyoxymethylene backbone. This method achieves excellent rapid curing properties even when using an amine compound as a curing catalyst instead of an organotin compound, and also provides excellent resistance to yellowing. Moreover, it avoids the use of isocyanate-based silanes, thus resulting in a low-toxicity cured product. However, while the compound in Patent Document 4 exhibits excellent reactivity when using an amine catalyst, the softening of the cured product due to the cleavage of the thioether-methylene-silicon bond at high temperatures is considered a problem.

[0010] Existing technical documents

[0011] Patent documents

[0012] Patent Document 1: Japanese Patent Application Publication No. 2004-099908

[0013] Patent Document 2: Japanese Patent Application Publication No. 2010-209205

[0014] Patent Document 3: Japanese Patent Publication No. 2004-518801

[0015] Patent Document 4: Japanese Patent Application Publication No. 2017-141450 Summary of the Invention

[0016] The problem that the invention aims to solve

[0017] The present invention was made in view of the above-mentioned circumstances, and its object is to provide a reactive silicon-based polyoxyethylene derivative and a method thereof that produce a cured product with good curability, excellent resistance to yellowing and heat resistance, even when using amine compounds as curing catalysts.

[0018] Methods for solving problems

[0019] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that: as a reactive silicon-based polyoxyethylene derivative with end capping of methyl and two organic oxygen groups, the polyoxyethylene derivative exhibits good curability even when amine compounds are used as curing catalysts, and produces cured products with excellent resistance to yellowing and heat resistance, thus completing the present invention.

[0020] That is, the present invention provides:

[0021] 1. A polyoxyalkylene derivative containing a reactive silicon group, wherein the single or double ends of the polyoxyalkylene chain are capped with a group represented by the following structural formula (1),

[0022] [Chemistry 1]

[0023]

[0024] 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 group independently represents an aliphatic saturated hydrocarbon group with 1 to 10 carbon atoms or an aryl group with 6 to 10 carbon atoms, where n is an integer from 2 to 12, and the line with a wavy line represents the bonding end.

[0025] 2. The polyoxyethylene derivative containing reactive silicon groups according to claim 1, wherein the number average molecular weight is 200 to 50,000;

[0026] 3. The method for manufacturing a polyoxyalkylene derivative containing a reactive silicon group according to 1, wherein the polyoxyalkylene derivative containing an alkenyl group, wherein the single or double ends of the polyoxyalkylene chain are capped with an alkenyl group having 2 to 12 carbon atoms, is reacted with a disiloxane compound represented by the following formula (4).

[0027] [Chemistry 2]

[0028]

[0029] In the formula, R 1 R 2 and R 3 It means the same as above;

[0030] 4. The method for manufacturing polyoxyethylene derivatives containing reactive silicon groups according to claim 3, characterized in that the number average molecular weight is 200 to 50,000;

[0031] 5. A curable composition comprising (A) a polyoxyethylene derivative containing a reactive silicon group according to claim 1 and (B) a curing catalyst;

[0032] 6. The curable composition according to 5, wherein the (B) curing catalyst is an amine compound;

[0033] 7. A cured product obtained by curing the curable composition according to 5 or 6;

[0034] 8. A coating composition comprising (A) a polyoxyethylene derivative containing a reactive silicon group according to claim 1 and (B) a curing catalyst;

[0035] 9. The coating composition according to 8, wherein the (B) curing catalyst is an amine compound;

[0036] 10. An article having a coating layer cured according to the coating agent composition described in 8 or 9;

[0037] 11. An adhesive composition comprising (A) a polyoxyethylene derivative containing a reactive silicon group according to claim 1 and (B) a curing catalyst;

[0038] 12. The adhesive composition according to 11, wherein the (B) curing catalyst is an amine compound;

[0039] 13. An article having an adhesive layer cured according to the adhesive composition described in 11 or 12.

[0040] The effects of the invention

[0041] The polyoxyethylene derivatives containing reactive silicon groups of the present invention have a specific reactive silicon group consisting of an organooxy methyl group and a silyl group with two organooxy groups at the molecule end. Therefore, even when an amine compound is used as the curing catalyst instead of an organotin compound, the curing properties are good, and the cured product has excellent resistance to yellowing and heat resistance.

[0042] The reactive silicon-containing polyoxyethylene derivatives of the present invention, which have such properties, are suitable for use as base agents (base polymers) in coating agents, adhesives, sealants, etc. Detailed Implementation

[0043] The present invention will now be described in detail.

[0044] The reactive silicon-containing polyoxyalkylene derivatives of the present invention are formed by capping the single or double ends of a polyoxyalkylene chain with groups represented by the following structural formula (1).

[0045] [Chemistry 3]

[0046]

[0047] In equation (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; R 3 Each can independently represent an aliphatic saturated hydrocarbon group with 1 to 10 carbon atoms or an aryl group with 6 to 10 carbon atoms.

[0048] As R 1 R 2 and R 3 It refers to aliphatic saturated hydrocarbon groups with 1 to 10 carbon atoms, which can be straight-chain, cyclic, or branched. Specific examples include straight-chain or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

[0049] As R 1 R 2 and R 3 Specific examples of aryl groups with 6 to 10 carbon atoms include phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, etc.

[0050] In addition, some or all of the hydrogen atoms in these groups can be replaced by halogen atoms such as F, Cl, Br, or cyano groups. Specific examples include 3-chloropropyl, 3,3,3-trifluoropropyl, and 2-cyanoethyl.

[0051] Among these, as R 1 R 2 and R 3 Methyl, ethyl, and phenyl are preferred, with methyl being more preferred in terms of curability, productivity, and cost.

[0052] In equation (1), n ​​is an integer from 2 to 12. From the viewpoint of reactivity, 2 to 8 is preferred, 2 to 3 is more preferred, and 2 is even more preferred.

[0053] The reactive silicon-based polyoxyethylene derivatives of the present invention are not particularly limited as long as they are compounds having groups represented by the above formula (1) at one or both ends of the polyoxyethylene skeleton. From the viewpoint of curability and the mechanical properties of the obtained cured product, it is preferable that the polyoxyethylene skeleton has groups represented by the above formula (1) at both ends.

[0054] Therefore, as the polyoxyethylene derivative containing reactive silicon groups of the present invention, the compound represented by the following structural formula (2) is preferred.

[0055] [Chemistry 4]

[0056]

[0057] (where R) 1 R 2 R 3 (and n represent the same meaning as above.)

[0058] In equation (2), Z represents the polyoxyethylene structure represented by equation (3) below.

[0059] [Chemistry 5]

[0060]

[0061] (In the formula, the line with a wavy line indicates the joint end.)

[0062] In equation (3), R 5 This represents a divalent hydrocarbon group with 1 to 14 carbon atoms, where p is an integer greater than or equal to 1. Furthermore, there exist multiple R groups. 5(When p is 2 or higher), each R 5 They can be the same or different.

[0063] As R 5 The divalent hydrocarbon group is preferably a straight-chain or branched alkylene group with 1 to 14 carbon atoms, and examples include methylene, ethylene, propylene, trimethylene, tetramethylene, isobutylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, etc.

[0064] Among these, as R 5 Especially preferred are straight-chain or branched alkylene groups with 2 to 4 carbon atoms, such as methylene, ethylene, trimethylene, propylene, tetramethylene, and isobutylene.

[0065] That is, as the repeating unit (-OR) in the above equation (3), 5 Specific examples of -) can be listed as oxoalkylene groups such as -OCH2-, -OCH2CH2-, -OCH2CH2CH2-, -OCH(CH3)CH2-, -OCH2CH2CH2CH2-, -OCH(CH2CH3)CH2-, and -OC(CH3)2CH2-.

[0066] In formula (3), p is a number of 1 or more. From the viewpoint of the mechanical properties of the obtained cured product and the workability of the composition, p is preferably 5 to 700, more preferably 10 to 500, and even more preferably 20 to 300.

[0067] Furthermore, the main chain backbone of the oxyalkylene-containing organosilicon compound of the present invention can be composed of one repeating unit or two or more repeating units. In particular, when used in materials such as coating agents, adhesives, and sealants, from the viewpoint of durability, it is preferable to include oxypropylene (-OCH(CH3)CH2-) units.

[0068] The number-average molecular weight of the oxyalkylene-containing organosilicon compound of the present invention is not particularly limited. The viscosity and other properties of the curable composition containing the compound are within an appropriate range to improve workability and to impart sufficient curability. The preferred number-average molecular weight is 200 to 50,000, and more preferably 1,000 to 20,000.

[0069] It should be noted that the number-average molecular weight in this invention is the equivalent value of polystyrene in gel permeation chromatography (GPC) analysis (the same applies below).

[0070] Furthermore, there is no particular limitation on the viscosity of the reactive silicon-based polyoxyethylene derivative of the present invention. The viscosity of the curable composition containing this compound is kept within an appropriate range to improve workability and to impart sufficient curability; preferably, it is between 10 and 100,000 mPa. s, more preferably 50 to 50000 mPa s, further optimized to 100–10000 mPa s.

[0071] The viscosity is the value measured at 25°C using a type B rotational viscometer.

[0072] The reactive silicon-containing polyoxyethylene derivatives of the present invention can be obtained by hydrosilylation reaction of polyoxyethylene (hereinafter also referred to as "alkenyl-containing polyoxyethylene derivatives") with alkenyl groups having 2 to 12 carbon atoms at one or both ends of the molecular chain and a disiloxane compound represented by formula (4) in the presence of a platinum group metal catalyst, in the atmosphere or in an inactive gas such as nitrogen.

[0073] [Chemistry 6]

[0074]

[0075] (where R) 1 R 2 and R 3 This indicates the same meaning as above.

[0076] As specific examples of disiloxane compounds represented by formula (4) above, compounds represented by the following structural formulas can be listed, but are not limited to these. Among these, disiloxane compounds represented by formula (6) are preferred.

[0077] [Chemistry 7]

[0078]

[0079] The disiloxane compound represented by the above formula (4) is obtained, for example, by equilibration reaction of an organooxysilane represented by the following formula (7) and a disiloxane compound represented by the following formula (8) in the presence of acid and water.

[0080] [Chemistry 8]

[0081]

[0082] (where R) 1 R 2 and R 3 This indicates the same meaning as above.

[0083] There is no particular limitation on the type of polyoxyethylene derivative containing alkenyl groups, as long as it is a compound having alkenyl groups with 2 to 12 carbon atoms at one or both ends of the polyoxyethylene skeleton. From the viewpoint of curability and the mechanical properties of the resulting cured product, it is preferred to use a compound represented by the following formula (5) that has alkenyl groups with 2 to 12 carbon atoms at both ends of the polyoxyethylene skeleton.

[0084] [Chemistry 9]

[0085]

[0086] (where R) 5 (and p represent the same meaning as above.)

[0087] In equation (5), R 6 It is an alkenyl group with 2 to 12 carbon atoms.

[0088] The alkenyl group having 2 to 12 carbon atoms is preferably a straight-chain or branched-chain alkenyl group having 2 to 8 carbon atoms. Specific examples 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, and 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, etc.

[0089] Among these, vinyl or allyl is preferred, and vinyl is more preferred.

[0090] Specific examples of polyoxyethylene derivatives containing alkenyl groups include, but are not limited to, compounds represented by the following structural formulas.

[0091] [Chemistry 10]

[0092]

[0093] (In the formula, p represents the same meaning as above.)

[0094] There is no particular limitation on the number average molecular weight of the polyoxyethylene derivative containing alkenyl groups. The viscosity and other properties of the curable composition containing the compound are in an appropriate range to improve workability and to impart sufficient curability. The preferred number average molecular weight is 200 to 50,000, and more preferably 1,000 to 20,000.

[0095] The reaction ratio of the alkenyl-containing polyoxyethylene derivative with the disiloxane compound represented by the above formula (4) is preferably 0.8 to 2.5 of the hydrosilyl group in the disiloxane compound represented by the above formula (4), and more preferably 0.9 to 2.0 of the hydrosilyl group, relative to 1 alkenyl group in the above alkenyl-containing polyoxyethylene derivative.

[0096] There are no particular limitations on the platinum group metal catalysts used in the above-mentioned hydrosilylation reaction. Specific examples include chloroplatinic acid, alcoholic solutions of chloroplatinic acid, toluene or xylene solutions of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complexes, tetra(triphenylphosphine)platinum, dichlorobis(triphenylphosphine)platinum, dichlorobis(acetonitrile)platinum, dichlorobis(benzonitrile)platinum, dichlorocyclooctadieneplatinum, platinum-carbon, platinum-alumina, platinum-silica, and other supported catalysts.

[0097] Among these, from the perspective of selectivity during hydrosilylation, a platinum complex with zero valence is preferred, and a toluene or xylene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex is more preferred.

[0098] There is no particular limitation on the amount of platinum group metal catalyst used. From the perspective of reactivity and productivity, the preferred amount is 0.1 to 1000 ppm, more preferably 0.3 to 100 ppm, relative to the total mass of the alkenyl-containing organopolysiloxane and the disiloxane compound represented by the above formula (4) in terms of the mass conversion of platinum group metal.

[0099] The above-mentioned hydrosilylation reaction can also be carried out in solvent-free conditions, or in organic solvents such as toluene, isopropanol, and methanol, as needed, within a range that does not hinder the reaction.

[0100] There is no particular limitation on the reaction temperature in the above-mentioned hydrosilylation reaction, but 0 to 200°C is preferred, 40 to 110°C is more preferred, and 60 to 100°C is even more preferred. In addition, 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.

[0101] There is no particular limitation on the reaction time; it is usually around 1 to 60 hours, preferably 1 to 24 hours.

[0102] The curable composition of the present invention (hereinafter referred to as the composition) contains at least the above-mentioned (A) a polyoxyethylene derivative containing a reactive silicon group and (B) a curing catalyst.

[0103] The compositions of the present invention comprise the above-described reactive silicon-based polyoxyethylene derivatives of the present invention, thus providing cured products with excellent curability, resistance to yellowing, and heat resistance.

[0104] The curing catalyst (B) is a component that promotes the hydrolytic condensation reaction of the hydrolyzable groups contained in the reactive silicon-containing polyoxyethylene derivative (A) due to moisture in the air, and promotes the curing of the composition. It is added to ensure effective curing.

[0105] As a curing catalyst, there are no particular limitations as long as it is a curing catalyst used in the curing of general moisture condensation curing compositions. Specific examples include alkyltin compounds such as dibutyltin oxide and dioctyltin oxide; alkyltin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctanoate, dioctyltin dioctanoate, and dioctyltin ditert-tert-carbonate; titanate esters and titanium chelate compounds such as tetraisopropoxytitanium, tetra-n-butoxytitanium, tetra(2-ethylhexyloxy)titanium, dipropoxybis(acetylacetone)titanium, diisopropoxybis(ethyl acetoacetate)titanium, and isopropoxyoctanedioltitanium, as well as their partial hydrolysates; zinc naphthenate, zinc stearate, zinc 2-ethyloctanoate, iron 2-ethylhexanoate, cobalt 2-ethylhexanoate, manganese 2-ethylhexanoate, and cobalt naphthenate. Organometallic compounds such as aluminum hydroxide, aluminum alkoxides, aluminum acylates, salts of aluminum acylates, aluminum siloxane compounds, and aluminum chelates; 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, etc. [3-(trimethoxysilyl)propyl]amine, N,N'-bis[3-(trimethoxysilyl)propyl]ethane-1,2-diamine, N,N'-bis[3-(triethoxysilyl)propyl]ethane-1,2-diamine, N-phenyl-3-aminopropyltrimethoxysilane and other aminoalkyl-substituted alkoxysilanes; amine compounds and their salts such as hexylamine and dodecylamine phosphate; quaternary ammonium salts such as benzyltriethylammonium acetate; lower fatty acid salts of alkali metals such as potassium acetate, sodium acetate, and lithium oxalate; dialkylhydroxyamines such as dimethylhydroxyamine and diethylhydroxyamine; 2-[3-(trimethoxysilyl)propyl]-1,1,3,3-tetramethylguanidine, 2-[3-(methyldimethoxysilyl)propyl]-1,1,3,3-tetramethylguanidine, 2-[3-(tri ... Silanes and siloxanes containing guanidine groups, such as 2-[3-(triethoxysilyl)propyl]-1,1,3,3-tetramethylguanidine, 2-[3-(methyldiethoxysilyl)propyl]-1,1,3,3-tetramethylguanidine, and 2-[3-(tri(trimethylsiloxy)silyl)propyl]-1,1,3,3-tetramethylguanidine; and silanes and siloxanes containing phosphazene bases, such as N,N,N',N',N'',N''-hexamethyl-N'''-[3-(trimethoxysilyl)propyl]-phosphoric acid triamide, can be used alone or in combination of two or more.

[0106] Among these, based on superior reactivity, dioctyltin dilaurate, dioctyltin ditert-carbonate, tetraisopropoxy titanium, tetra-n-butoxy titanium, diisopropoxybis(ethyl acetoacetate) titanium, 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, and further, based on the curability of the composition... From the viewpoint of [the composition], dioctyltin dilaurate, dioctyltin ditert-carbonate, 3-aminopropyltrimethoxysilane, and 2-[3-(trimethoxysilyl)propyl]-1,1,3,3-tetramethylguanidine are preferred. If the absence of organotin compounds is considered to result in lower toxicity, 3-aminopropyltrimethoxysilane and 2-[3-(trimethoxysilyl)propyl]-1,1,3,3-tetramethylguanidine are further preferred. From the viewpoint of the curability of the composition, 2-[3-(trimethoxysilyl)propyl]-1,1,3,3-tetramethylguanidine is particularly preferred.

[0107] There is no particular limitation on the amount of curing catalyst added. If it is considered to adjust the curing speed to an appropriate range to improve workability, it is preferred to be 0.01 to 15 parts by mass relative to 100 parts by mass of (A) organopolysiloxane containing reactive silicon groups, and more preferably 0.1 to 5 parts by mass.

[0108] Furthermore, the compositions of the present invention are preferably solvent-free forms that are substantially free of organic solvents (which in most cases are harmful to the human body and are flammable). However, from the perspective of their use and workability, they can also be used with the addition of solvents. Here, "substantially" means that the solvent contained in the composition is 1% by mass or less, particularly 0.1% by mass or less.

[0109] As a solvent, there are no particular limitations as long as component (A) is dissolved. 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-acetic acid; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and ether solvents such as diethyl ether, dibutyl ether, cyclopentylmethyl ether, tetrahydrofuran, and 1,4-dioxane. These can be used individually or in combination.

[0110] Furthermore, in the composition of the present invention, various additives such as adhesive modifiers, inorganic and organic ultraviolet absorbers, preservation stability modifiers, plasticizers, fillers, pigments, and fragrances can be added according to the intended use.

[0111] By applying the composition of the present invention described above to the surface of a solid substrate and allowing it to cure, a coating layer is formed, thereby obtaining a coated solid substrate. Alternatively, by applying the adhesive composition of the present invention to the surface of a solid substrate and then stacking other solid substrates on it, the composition is cured to form an adhesive layer, thereby obtaining an adhesive laminate.

[0112] There are no particular limitations on the coating method of the composition. As specific examples, well-known methods such as spraying, spin coating, dip coating, roller coating, brush coating, bar coating, and flow coating can be appropriately selected and used.

[0113] There are no particular limitations on the material and shape of the solid substrate. Specific examples include: epoxy resin, phenolic resin, polyimide resin, polycarbonate and polycarbonate blends, acrylic resins such as poly(methyl methacrylate), polyethylene terephthalate, polybutylene terephthalate, unsaturated polyester resins, 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, polyethylene resin, and other organic resin substrates; metal substrates such as iron plates, copper plates, and steel plates; coating surfaces; glass; ceramics; concrete; stone slabs; fabrics; wood, stone, tiles; inorganic fillers such as (hollow) silica, titanium dioxide, zirconium oxide, and alumina; and glass fiber products such as glass cloth, glass tape, glass mat, and glass paper, mainly made of glass fiber.

[0114] The composition of the present invention undergoes (A) a hydrolysis-condensation reaction of a polyoxyethylene derivative containing a reactive silicon group by contacting it with moisture in an atmosphere. The moisture content of the atmosphere can be any humidity level from 10% to 100% RH; generally, the higher the humidity, the faster the hydrolysis proceeds. Moisture can be added to the atmosphere as needed.

[0115] The curing temperature and time can be appropriately varied depending on factors such as the substrate, moisture concentration, catalyst concentration, and type of hydrolyzable groups used. From an operational perspective, the curing temperature is generally preferred to be around 10°C to 40°C. To promote the curing reaction, it can be heated to a temperature not exceeding the heat resistance of the substrate. The curing time, from an operational perspective, is generally from 1 minute to approximately 1 week.

[0116] Example

[0117] The following examples of synthesis, embodiments and comparative examples are listed to illustrate the present invention in more detail, but the present invention is not limited to these embodiments.

[0118] It should be noted that, in the following description, viscosity is the value measured at 25°C using a type B rotational viscometer, and molecular weight and degree of polymerization (repetition number of alkylene units) are the number-average molecular weight and number-average degree of polymerization of polystyrene obtained by GPC (gel permeation chromatography).

[0119] [1] Synthesis of disiloxane compounds

[0120] [Synthesis example 1] Synthesis of disiloxane compound a

[0121] [Chemistry 11]

[0122]

[0123] In a 300 mL detachable flask equipped with a stirrer, reflux condenser, and thermometer, 200 g of trimethoxy(methoxymethyl)silane and 40.4 g of 1,1,3,3-tetramethyldisiloxane were added. 1.2 g of concentrated sulfuric acid (98% by mass) was added dropwise while stirring at 7°C. After the addition was complete, the mixture was stirred at 25°C for 5 hours. Then, 6 g of Kyowo Chemical Industry Co., Ltd. (registered trademark) 500SH was added, and the mixture was stirred for 1 hour. After filtration, the reaction solution was collected and distilled (distillation temperature 90°C, vacuum 17 kPa) to obtain disiloxane compound a.

[0124] 1 H-NMR (CDCl3): δ4.46~4.61ppm (s, 1H, -SiH), 3.41~3.34ppm (s, 9H, -Si(OCH3)2, -OCH3), 3.15~3.13ppm (s, 2H, -CH2-), 0.00~0.02ppm (s, 6H, -SiCH3)

[0125] [Synthesis example 2] Synthesis of disiloxane compound b

[0126] [Chemistry 12]

[0127]

[0128] In a 300 mL detachable flask equipped with a stirrer, reflux condenser, and thermometer, 268 g of triethoxy(ethoxymethyl)silane and 40.4 g of 1,1,3,3-tetramethyldisiloxane were placed. 1.2 g of concentrated sulfuric acid (98% by mass) was added dropwise while stirring at 7°C. After the addition was complete, the mixture was stirred at 25°C for 5 hours. Then, 6 g of 500SH chloroform (registered trademark) (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and the mixture was stirred for 1 hour. After filtration, the reaction solution was collected and distilled (distillation temperature 90°C, vacuum 17 kPa) to obtain disiloxane compound b.

[0129] 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)

[0130] [Synthesis example 3] Synthesis of disiloxane compound C

[0131] [Chemistry 13]

[0132]

[0133] In a 300 mL detachable flask equipped with a stirrer, reflux condenser, and 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 Kyowa Chemical Industry Co., Ltd. (registered trademark) 500SH was added, and the mixture was stirred for 1 hour. After filtration, the reaction solution was collected and distilled (distillation temperature 90°C, vacuum 17 kPa) to obtain disiloxane compound c.

[0134] 1 H-NMR (CDCl3): δ7.58~7.32ppm (m, 10H, -SiC6H5), 4.46~4.61ppm (s, 1H, -SiH), 3.41~3.34ppm (s, 9H, -Si(OCH3)2, -OCH3), 3.15~3.13ppm (s, 2H, -CH2-)

[0135] [2] Synthesis of polyoxyethylene derivatives containing reactive silicon groups

[0136] [Example 1-1] Synthesis of polyoxyethylene derivative A-1 containing reactive silicon groups

[0137] In a 200 mL detachable flask equipped with a stirrer, reflux condenser, and thermometer, 100 g of polypropylene glycol with a number average molecular weight of 5100 containing two terminal allyl groups (0.07 mol based on the functional group of the terminal allyl groups) and a toluene solution (50 ppm by mass based on platinum) of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex were added, and the mixture was heated to 60 °C. 27 g of disiloxane compound a (0.11 mol of hydroxysilyl functional group) obtained in Synthesis Example 1 was then added, and the mixture was stirred at 60 °C for 2 hours. 1¹H-NMR analysis confirmed the complete disappearance of the allyl peak from the raw material, and the detection of the peak from the target compound marked the end of the reaction. 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 a polyoxyethylene derivative A-1 containing reactive silicon groups.

[0138] The obtained polyoxyethylene derivative A-1 containing reactive silicon groups is a pale yellow transparent liquid with a number average molecular weight of 6000 and a viscosity of 500 mPa. s.

[0139] [Examples 1-2] Synthesis of polyoxyethylene derivative A-2 containing reactive silicon groups

[0140] In a 200 mL detachable flask equipped with a stirrer, reflux condenser, and thermometer, 100 g of polypropylene glycol with a number average molecular weight of 7800 containing two terminal allyl groups (0.039 mol based on the functional group of the terminal allyl groups) and a toluene solution (50 ppm by mass based on platinum) of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex were added, and the mixture was heated to 60 °C. 15 g of disiloxane compound a (0.06 mol of hydroxysilyl functional group) obtained in Synthesis Example 1 was then added, and the mixture was stirred at 60 °C for 2 hours. 1 ¹H-NMR analysis confirmed the complete disappearance of the allyl peak from the raw material, and the detection of the peak from the target compound marked the end of the reaction. After the reaction was complete, the solvent was distilled off at 100°C and a vacuum of 1.3 kPa for 3 hours to obtain a polyoxyethylene derivative A-2 containing reactive silicon groups.

[0141] The obtained polyoxyethylene derivative A-2 containing reactive silicon groups is a pale yellow transparent liquid with a number average molecular weight of 8600 and a viscosity of 2800 mPa. s.

[0142] [Examples 1-3] Synthesis of polyoxyethylene derivative A-3 containing reactive silicon groups

[0143] In a 200 mL detachable flask equipped with a stirrer, reflux condenser, and thermometer, 1280 g of polypropylene glycol with a number average molecular weight of 12000 containing two terminal allyl groups (0.2 mol based on the functional group of the terminal allyl groups) and a toluene solution (50 ppm by mass based on platinum) of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex were added, and the mixture was heated to 60 °C. 75 g of disiloxane compound a (0.3 mol of hydroxysilyl functional group) obtained in Synthesis Example 1 was then added, and the mixture was stirred at 60 °C for 2 hours. 1¹H-NMR analysis confirmed the complete disappearance of the allyl peak from the raw material, and the detection of the peak from the target compound marked the end of the reaction. After the reaction was complete, the solvent was distilled off at 100°C and a vacuum of 1.3 kPa for 3 hours to obtain a polyoxyethylene derivative A-3 containing reactive silicon groups.

[0144] The obtained polyoxyethylene derivative A-3 containing reactive silicon groups is a pale yellow transparent liquid with a number average molecular weight of 13,000 and a viscosity of 8,000 mPa. s.

[0145] [Examples 1-4] Synthesis of polyoxyethylene derivative A-4 containing reactive silicon groups

[0146] In a 200 mL detachable flask equipped with a stirrer, reflux condenser, and thermometer, 1280 g of polypropylene glycol with a number average molecular weight of 12000 containing two terminal allyl groups (0.2 mol based on the functional group of the terminal allyl groups) and a toluene solution (50 ppm by mass based on platinum) of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex were added, and the mixture was heated to 60 °C. Then, 90 g of disiloxane compound b obtained in Synthesis Example 2 (0.3 mol of silane functional group) was added, and the mixture was stirred at 60 °C for 2 hours. 1 ¹H-NMR analysis confirmed the complete disappearance of the allyl peak from the raw material, and the detection of the peak from the target compound marked the end of the reaction. 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 a polyoxyethylene derivative A-4 containing reactive silicon groups.

[0147] The obtained polyoxyethylene derivative A-4 containing reactive silicon groups is a pale yellow transparent liquid with a number average molecular weight of 13,000 and a viscosity of 7,900 mPa. s.

[0148] [Examples 1-5] Synthesis of polyoxyethylene derivative A-5 containing reactive silicon groups

[0149] In a 200 mL detachable flask equipped with a stirrer, reflux condenser, and thermometer, 1280 g of polypropylene glycol with a number average molecular weight of 12000 containing two terminal allyl groups (0.2 mol based on the functional group of the terminal allyl groups) and a toluene solution (50 ppm by mass based on platinum) of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex 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 silane functional group) was then added, and the mixture was stirred at 60 °C for 2 hours. 1¹H-NMR analysis confirmed the complete disappearance of the allyl peak from the raw material, and the detection of the peak from the target compound marked the end of the reaction. 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 a polyoxyethylene derivative A-5 containing reactive silicon groups.

[0150] The obtained polyoxyethylene derivative A-5 containing reactive silicon groups is a pale yellow transparent liquid with a number average molecular weight of 13200 and a viscosity of 8200 mPa. s.

[0151] [Comparative Example 1-1] Synthesis of A'-6, a polyoxyethylene derivative containing reactive silicon groups

[0152] In a 200 mL detachable flask equipped with a stirrer, reflux condenser, and thermometer, 100 g of polypropylene glycol with a number average molecular weight of 7800 containing diallyl-terminated groups (0.039 mol based on the functional group of the terminal allyl groups) and a toluene solution (50 ppm by mass based on platinum) of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex were added, and the mixture was heated to 60 °C. Then, 6 g of methyldimethoxysilane (0.06 mol of hydroxysilyl functional group) was added, and the mixture was stirred at 60 °C for 2 hours. 1 ¹H-NMR analysis confirmed the complete disappearance of the allyl peak from the raw material, and the detection of the peak from the target compound marked the end of the reaction. After the reaction was complete, the solvent was distilled off at 100°C and a vacuum of 1.3 kPa for 3 hours to obtain a polyoxyethylene derivative A'-6 containing reactive silicon groups.

[0153] The obtained polyoxyethylene derivative A'-6 containing reactive silicon groups is a pale yellow transparent liquid with a number average molecular weight of 8400 and a viscosity of 2700 mPa. s.

[0154] [Comparative Examples 1-2] Synthesis of A'-7, a polyoxyethylene derivative containing reactive silicon groups

[0155] In a 200 mL detachable flask equipped with a stirrer, reflux condenser, and thermometer, 100 g of polypropylene glycol with a number average molecular weight of 7800 containing two terminal allyl groups (0.039 mol of terminal allyl functional group) and 6.6 g of mercaptomethyltrimethoxysilane (0.039 mol of mercapto functional group) were added, and the mixture was heated to 90 °C. Then, 0.1 g of 2,2'-azobis-2-methylbutyronitrile was added, and the mixture was stirred at 90 °C for 3 hours. 1 H-NMR analysis confirmed the complete disappearance of allyl and mercapto peaks from the raw material, and the detection of peaks from the target compound marked the end of the reaction.

[0156] The obtained polyoxyethylene derivative A'-7 containing reactive silicon groups is a pale yellow transparent liquid with a number average molecular weight of 8100 and a viscosity of 3300 mPa. s.

[0157] [Comparative Examples 1-3] Synthesis of A'-8, a polyoxyethylene derivative containing reactive silicon groups

[0158] 100 g of polypropylene glycol with a number average molecular weight of 7600 and containing two terminal hydroxyl groups (0.040 mol based on the functional group of the terminal hydroxyl groups) and 7.1 g of isocyanate-based methyltrimethoxysilane (0.040 mol of isocyanate functional group) were added to a 200 mL detachable flask equipped with a stirrer, reflux condenser, and thermometer. The mixture was heated to 80 °C. 0.1 g of dioctyltin dilaurate was then added, and the mixture was stirred at 80 °C for 3 hours. IR spectroscopy confirmed the complete disappearance of the absorption peak from the isocyanate groups of the starting material, and the detection of the absorption peak from the urethane bond marked the end of the reaction.

[0159] The obtained polyoxyethylene derivative A'-8 containing reactive silicon groups is a pale yellow transparent liquid with a number average molecular weight of 8000 and a viscosity of 3700 mPa. s.

[0160] [Comparative Examples 1-4] Synthesis of A'-9, a polyoxyethylene derivative containing reactive silicon groups

[0161] 100 g of polypropylene glycol (0.040 mol based on the functional group of the terminal hydroxyl groups) with a number average molecular weight of 7600 and 6.1 g of tetramethoxysilane (0.040 mol) were added to a 200 mL detachable flask equipped with a stirrer, reflux condenser, and thermometer. The mixture was stirred at 80 °C for 3 hours. The reaction was considered complete when the absorption peak of the hydroxyl groups from the starting material completely disappeared, as confirmed by IR spectroscopy.

[0162] The obtained polyoxyethylene derivative A'-9 containing reactive silicon groups is a colorless and transparent liquid with a number average molecular weight of 22,000 and a viscosity of 6,800 mPa. s.

[0163] [3] Preparation of the composition and the cured film

[0164] [Example 2-1]

[0165] A composition was prepared by uniformly mixing 100 parts by weight of the reactive silicon-based polyoxyethylene derivative A-1 obtained in Examples 1-1 above and 0.5 parts by weight of the curing catalyst B-1 (2-[3-(trimethoxysilyl)propyl]-1,1,3,3-tetramethylguanidine) using a stirrer under moisture-blocking conditions.

[0166] The obtained composition was coated onto a glass plate using a rod coater No. 14 at 25°C and 50% RH in air, and then dried at 25°C and 50% RH in air. The cured film was produced after curing for 1 day.

[0167] [Examples 2-2 to 2-5 and Comparative Examples 2-1 to 2-4]

[0168] In Example 2-1, the reactive silicon-based polyoxyethylene derivative A-1 was replaced with the reactive silicon-based polyoxyethylene derivatives A-2 to A-5 obtained in Examples 1-2 to 1-5, and the reactive silicon-based polyoxyethylene derivatives A'-6 to A'-9 obtained in Comparative Examples 1-1 to 1-4. Otherwise, the same procedure as in Example 2-1 was followed to prepare the composition and the cured film.

[0169] [Examples 2-6]

[0170] In Example 2-1, curing catalyst B-1 was replaced with 5 parts by mass of curing catalyst B-2 (3-aminopropyltrimethoxysilane). Otherwise, the same procedure as in Example 2-1 was followed to prepare the composition and the cured film.

[0171] [Examples 2-7]

[0172] In Example 2-1, curing catalyst B-1 was replaced with curing catalyst B-3 (dioctyltin ditert-tert-carbonate) in 5 parts by mass. Otherwise, the same procedure as in Example 2-1 was followed to prepare the composition and the cured film.

[0173] [Examples 2-8]

[0174] In Example 2-1, curing catalyst B-1 was replaced with curing catalyst B-4 (diisopropoxybis(ethyl acetoacetate)titanium) in 2 parts by mass. Otherwise, the same procedure as in Example 2-1 was followed to prepare the composition and the cured film.

[0175] [Comparative Examples 2-5]

[0176] In Comparative Example 2-1, curing catalyst B-1 was replaced with curing catalyst B-2 (3-aminopropyltrimethoxysilane) in 5 parts by mass. Otherwise, the same procedure as in Comparative Example 2-1 was followed to prepare the composition and the cured film.

[0177] [Comparative Examples 2-6]

[0178] In Comparative Example 2-1, curing catalyst B-1 was replaced with curing catalyst B-3 (dioctyltin ditert-tert-carbonate) in 5 parts by mass. Otherwise, the same procedure as in Comparative Example 2-1 was followed to prepare the composition and the cured film.

[0179] [Comparative Examples 2-7]

[0180] In Comparative Example 2-2, curing catalyst B-1 was replaced with curing catalyst B-2 (3-aminopropyltrimethoxysilane) in 5 parts by mass. Otherwise, the same procedure as in Comparative Example 2-2 was followed to prepare the composition and the cured film.

[0181] [Comparative Examples 2-8]

[0182] In Comparative Example 2-2, curing catalyst B-1 was replaced with curing catalyst B-3 (dioctyltin ditert-tert-carbonate) in 5 parts by mass. Otherwise, the same procedure as in Comparative Example 2-2 was followed to prepare the composition and the cured film.

[0183] The cured films prepared in Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-8 were evaluated for the following physical properties. The results are shown in Tables 1 and 2.

[0184] [Touch drying time]

[0185] Test pieces obtained by coating the composition onto a glass plate using the above coating method were placed in air at 25°C and 50% RH for moisture curing, thereby showing the time until the coating film no longer adheres to the finger even when pressed on the coated surface. The smaller the value, the better the curing performance.

[0186] [Resistance to yellowing]

[0187] For the test pieces that formed a cured film on the glass plate using the above coating method, they were subjected to ultraviolet irradiation for 2 weeks under a sterilizing lamp at 25°C and 50% RH (cumulative irradiation dose 26000 mJ / cm²). 3 The degree of yellowing of the cured film at this point is evaluated using a colorimeter based on JIS K 7373, using ΔYI (yellowing degree = the range of change in yellowness YI). The smaller the value, the better the resistance to yellowing.

[0188] When ΔYI is less than 0.5, the resistance to yellowing is considered excellent and is rated "○". When ΔYI is 0.5 or higher, it is rated "×".

[0189] [Heat resistance]

[0190] For the test pieces that formed a cured film on the glass plate using the above coating method, they were placed in a desiccator at 150°C for 2 weeks. Then, those that did not leave a finger mark when the coating surface was pressed with a finger were rated as "○". Those that left a finger mark when the coating surface was pressed with a finger were rated as "×".

[0191] [Table 1]

[0192]

[0193] [Table 2]

[0194]

[0195] 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-based polyoxyethylene derivatives A-1 to A-5 obtained in Examples 1-1 to 1-5 have excellent curability, yellowing resistance and heat resistance.

[0196] On the other hand, as shown in Table 2, it can be seen that Comparative Examples 2-1, 2-5 and 2-6, which use a polyoxyethylene derivative A'-6 containing a reactive silicon group that does not have a group represented by the above structural formula (1), and Comparative Example 2-4, which uses a polyoxyethylene derivative A'-9 containing a reactive silicon group, have poor curability. Comparative Examples 2-2, 2-7 and 2-8, which use a polyoxyethylene derivative A'-7 containing a reactive silicon group that has a thioether-methylene-silicon bond, have low heat resistance. Comparative Example 2-3, which uses a polyoxyethylene derivative A'-8 containing a reactive silicon group that has a urethane bond, has poor resistance to yellowing.

Claims

1. Polyoxyethylene derivatives containing reactive silicon groups, wherein, The single or double ends of the polyoxyalkylene chain are capped with groups represented by the following structural formula (1). [Chemistry 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 group independently represents an aliphatic saturated hydrocarbon group with 1 to 10 carbon atoms or an aryl group with 6 to 10 carbon atoms, where n is an integer from 2 to 12, and the line with a wavy line represents the bonding end.

2. The polyoxyethylene derivative containing reactive silicon groups according to claim 1, wherein, The number average molecular weight is 200–50,000.

3. The method for manufacturing the polyoxyethylene derivative containing reactive silicon groups according to claim 1, wherein, An alkenyl-containing polyoxyalkylene derivative, in which one or both ends of a polyoxyalkylene chain are capped with an alkenyl group having 2 to 12 carbon atoms, reacts with a disiloxane compound represented by the following formula (4). [Chemistry 2] In the formula, R 1 R 2 and R 3 It means the same as above.

4. The method for manufacturing a polyoxyethylene derivative containing reactive silicon groups according to claim 3, characterized in that, The number-average molecular weight of the polyoxyethylene derivative containing reactive silicon groups is 200–50,000.

5. A curable composition comprising (A) the reactive silicon-based polyoxyethylene derivative of 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, which is a cured product formed by curing the curing composition according to claim 5 or 6.

8. A coating composition comprising (A) the reactive silicon-based polyoxyethylene derivative of claim 1 and (B) a curing catalyst.

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

10. An article having a coating layer formed by curing the coating agent composition of claim 8 or 9.

11. An adhesive composition comprising (A) the reactive silicon-based polyoxyethylene derivative of 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 formed by curing the adhesive composition of claim 11 or 12.

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