Method for producing a composite of a titanium compound and ammonium hydroxide, method for producing a composition, method for producing an ester compound, and method for producing ammonium hydroxide

Abstract

Provided is a method for producing a very safe substance which can be used as a catalyst which exhibits excellent activity.　The present invention provides a method for producing a composite of a titanium compound [B1] and an ammonium hydroxide [B2], the titanium compound [B1] being represented by chemical formula (1), the ammonium hydroxide [B2] being represented by chemical formula (2), and the method being provided with a first step and a second step, wherein the ammonium hydroxide [B2] is generated by reacting an ammonium halide [B21] represented by chemical formula (3) with an alkali metal hydroxide in the first step, and the titanium compound [B1] and the ammonium hydroxide [B2] are reacted with one another in the second step.

Description

Technical Field

[0001] The present invention relates to a method for producing a composite of a titanium compound and ammonium hydroxide, a method for producing a composition, a method for producing an ester compound, and a method for producing ammonium hydroxide.

Background Art

[0002] One-component moisture-curing rubber compositions generally have a fast curing rate and do not require weighing and mixing of various additives such as a base polymer, a crosslinking agent, and a catalyst before use, and thus are superior in workability compared to two-component ones.

[0003] As these one-component moisture-curing rubber compositions, those such as silicone rubber, modified silicone rubber, urethane rubber, polysulfide rubber, etc. are known. As a one-component moisture-curing rubber composition of silicone rubber, organopolysiloxane compositions are widely used and cure at room temperature to form a rubber elastomer. A high molecular compound of siloxane having a -Si-O- bond formed by crosslinking polymerization of organosiloxane as a main chain is excellent in properties such as water repellency, heat resistance, weather resistance, cold resistance, and electrical insulation, and thus is widely used in fields such as construction, civil engineering, electric, electronic industries, and automobile industries.

[0004] As a one-component moisture-curing rubber composition of modified silicone rubber, there is a composition containing a polymer having a crosslinkable reactive hydrolyzable silicon functional group with a polyether as a main chain. The cured composition of this polymer has good storage stability, weather resistance, foam resistance, and discoloration resistance compared to those of polyurethane rubber, is superior in curability compared to those of polysulfide rubber, has less pollution to the surroundings, and is non-toxic.

[0005] It is said that the reaction mechanism in the process of the silicone rubber and the modified silicone rubber becoming a cured product is based on the condensation reaction or addition reaction of the reactive hydrolyzable silicon-containing group in the presence of water, and it is considered that polymerization proceeds to form a polymer cured body having a three-dimensional network structure. In order to accelerate the curing in this reaction, a curing catalyst is used (Patent Documents 1 to 5).

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0007] As a curing catalyst for a curing composition of a silicone rubber and a modified silicone rubber having this reactive hydrolyzable silicon-containing group, tin carboxylate compounds, alkyltin salt compounds, etc. have been conventionally used. However, since there are concerns about the effects on living organisms as endocrine disruptors, a combined catalyst of carboxylic acid and amine (Patent Document 1) has been proposed as a moisture-curing type composition that does not use such substances. However, there is a problem that a sufficient curing rate cannot be obtained during construction.

[0008] In Patent Documents 2 and 3, it has been proposed to use a titanate compound such as diisopropoxytitanium bis(alkylacetoacetonate) as a catalyst. However, it is easily decomposed by moisture contained in additives or fillers in the composition, and the curing rate varies depending on the humidity during construction, so there are problems such as inability to obtain a stable cured product.

[0009] In Patent Document 4, it has been proposed to use a titanium tetracarboxylic acid compound as a catalyst, but there is a problem that a practical level of satisfaction cannot be obtained with respect to the curing rate. In Patent Document 5, it has been proposed to use a quaternary ammonium salt as a catalyst, but there is a problem that a sufficient curing rate cannot be obtained during construction.

[0010] Therefore, the development of a curing catalyst with high safety (low toxicity and low environmental pollution) and a practical curing rate has been desired.

[0011] In view of the above prior art, an object of the present invention is to provide a method for producing a substance that can be used as a catalyst with high safety and excellent activity.

Means for Solving the Problems

[0012] According to the present invention, there is provided a method for producing a complex of a titanium compound [B1] and ammonium hydroxide [B2], wherein the titanium compound [B1] is represented by Chemical Formula (1), the ammonium hydroxide [B2] is represented by Chemical Formula (2), the method includes a first step and a second step, in the first step, ammonium halide [B21] represented by Chemical Formula (3) is reacted with an alkali metal hydroxide to produce the ammonium hydroxide [B2], and in the second step, the ammonium hydroxide [B2] is reacted with the titanium compound [B1].

[0013] By the above method, a complex of a titanium compound and ammonium hydroxide can be obtained. This complex has excellent catalytic activity when used as a catalyst for various reactions. Since this complex does not contain tin, it has high safety. In addition, it can be manufactured at low cost.

Mode for Carrying Out the Invention

[0014] 1. Complex The complex of the present invention is a complex of a titanium compound [B1] and ammonium hydroxide [B2]. This complex is a reaction product that can be obtained by reacting a titanium compound [B1] and ammonium hydroxide [B2].

[0015] First, the titanium compound [B1] and ammonium hydroxide [B2] will be described below, and then the method for producing the complex will be described.

[0016] <Titanium compound [B1]> The titanium compound [B1] is represented by the chemical formula (1). (R 1 -O) n Ti-A 4-n (1) (In the formula, R 1 represents a substituted or unsubstituted hydrocarbon group, n is 1 to 4, and A represents a β-diketone group)

[0017] n is, for example, 1, 1.5, 2, 2.5, 3, 3.5, 4, and may be within the range between any two of the numerical values exemplified here.

[0018] R 1 The substituted or unsubstituted hydrocarbon group represented by is a substituted or unsubstituted, aliphatic or aromatic hydrocarbon group, and an aliphatic hydrocarbon group is preferred.

[0019] Examples of the hydrocarbon group include an alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl) and an oxyalkylene group.

[0020] R 1 At least one of them is preferably an alkyl group having 8 or more carbon atoms or an oxyalkylene group. R 1 At least one of them is preferably a hydrocarbon group (other hydrocarbon group) that is neither an alkyl group having 8 or more carbon atoms nor an oxyalkylene group. The number of carbon atoms of the other hydrocarbon group is, for example, 1 to 7, preferably 1 to 5. Specifically, the number of carbon atoms is, for example, 1, 2, 3, 4, 5, 6, 7, and may be within the range between any two of the exemplified values. The other hydrocarbon group is preferably an alkyl group, more preferably a branched alkyl group. The number of the other hydrocarbon groups is 0, 1, 2, 3, or 4.

[0021] The number of carbon atoms of the alkyl group having 8 or more carbon atoms is, for example, 8 to 20, preferably 8 to 15. Specifically, the number of carbon atoms is, for example, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, and may be within the range between any two of the exemplified values.

[0022] The oxyalkylene group is represented by the chemical formula (4). The number of atoms in the main chain of the oxyalkylene group is, for example, 4 to 20, more preferably 6 to 14. Specifically, the number of atoms is, for example, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, and may be within the range between any two of the exemplified values. R 6 -(O-R 7 )m- (4) (In the formula, R 6 is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, R 7 is a substituted or unsubstituted hydrocarbon group having 2 to 10 carbon atoms, and m is an integer of 1 to 10)

[0023] R 6 preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. For R 7 preferably has 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms, m preferably has 1 to 6, more preferably 1 to 2.

[0024] Examples of the oxyalkylene group include groups obtained by removing the terminal hydroxyl group from the following alcohols. Such alcohols include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monopentyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monopentyl ether, propylene glycol monoisopropyl ether, propylene glycol mono-t-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopentyl ether, dipropylene glycol monoisopropyl ether, and dipropylene glycol mono-t-butyl ether. For example, when the alcohol is butyl carbitol (alias: 2-(2-butoxyethoxy)ethanol), the oxyalkylene group is 2-(2-butoxyethoxy)ethyl, and when the alcohol is butyl cellosolve (alias: 2-butoxyethanol), the oxyalkylene group is 2-butoxyethyl.

[0025] Examples of the β-diketone group represented by A include 1-aryl-1,3-butanediones such as 2,4-pentanedione, 2,4-hexanedione, 2,4-pentadecanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1-phenyl-1,3-butanedione, 1-(4-methoxyphenyl)-1,3-butanedione; 1,3-diaryl-1,3-propanediones such as 1,3-diphenyl-1,3-propanedione, 1,3-bis(2-pyridyl)-1,3-propanedione, 1,3-bis(4-methoxyphenyl)-1,3-propanedione; diketones such as 3-benzyl-2,4-pentanedione; ketoesters such as methyl acetoacetate, ethyl acetoacetate, butyl acetoacetate, t-butyl acetoacetate, ethyl 3-oxohexanoate; ketamides such as N,N-dimethylacetoacetamide, N,N-diethylacetoacetamide, acetoacetanilide; malonic esters such as dimethyl malonate, diethyl malonate, diphenyl malonate; malonic amides such as N,N,N',N'-tetramethylmalonamide, N,N,N',N'-tetraethylmalonamide. Diketones such as 2,4-pentanedione, 1-aryl-1,3-butanedione, 1,3-diaryl-1,3-propanedione are particularly preferred.

[0026] Specific examples of the titanium compound [B1] include tetramethoxytitanium, trimethoxyethoxysilane titanium, trimethoxyisopropoxytitanium, trimethoxybutoxytitanium, dimethoxydiethoxytitanium, dimethoxydipropoxytitanium, dimethoxydibutoxytitanium, methoxytriethoxytitanium, methoxytriisopropoxytitanium, methoxytributoxytitanium, tetraethoxytitanium, triethoxyisopropoxytitanium, triethoxybutoxytitanium, diethoxydipropoxytitanium, diethoxydibutoxytitanium, ethoxytriisopropoxytitanium, ethoxytributoxytitanium, tetraisopropoxytitanium, triisopropoxybutoxytitanium, diisopropoxydibutoxytitanium, tetrabutoxytitanium, diisopropoxytitanium bis(acetylacetonate), isopropoxytributyl carbitol titanium, diisopropoxybisbutyl carbitol titanium, triisopropoxybisbutyl carbitol titanium, tetrakisbutyl carbitol titanium, etc. From the viewpoints of catalytic activity, compound stability, and handleability, tetraisopropoxytitanium, triisopropoxy 2-(2-butoxyethoxy)ethoxytitanium, and triisopropoxy 2-butoxyethoxytitanium are more preferable. The above titanium compound [B1] may be used alone or in combination of two or more.

[0027] <ammonium hydroxide [B2]> Ammonium hydroxide [B2] is represented by the following formula.

Chemical formula

[0028] R 2 , R 3 , R 4 , R 5The substituted or unsubstituted hydrocarbon group represented by is a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, and an aliphatic hydrocarbon group is preferred. As the aliphatic hydrocarbon group, a linear or branched alkyl group is preferred. The number of carbon atoms of the hydrocarbon group is 1 to 8, preferably 1 to 6, and more preferably 1 to 4. Specifically, this number of carbon atoms is, for example, 1, 2, 3, 4, 5, 6, 7, 8, and may also be within the range between any two of the numerical values exemplified here. Examples of the aliphatic hydrocarbon group include saturated hydrocarbon groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, and unsaturated hydrocarbon groups such as vinyl group, allyl group, prenyl group, crotyl group, cyclopentadienyl group. Methyl group, ethyl group, butyl group are preferred.

[0029] Examples of the aromatic hydrocarbon group include phenyl group, tolyl group, benzyl group, etc.

[0030] Examples of the substituent of the hydrocarbon group include methoxy group, ethoxy group, hydroxy group, acetoxy group, etc. Examples of the substituted aliphatic or aromatic hydrocarbon group include alkoxyalkyl groups such as methoxymethyl group, methoxyethyl group, ethoxymethyl group, ethoxyethyl group, hydroxyalkyl groups such as hydroxymethyl group, hydroxyethyl group, 3-hydroxypropyl group, and 2-acetoxyethyl group, etc.

[0031] Specific examples of the ammonium hydroxide represented by Chemical Formula (2) include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, benzyltriethylammonium hydroxide, trimethylphenylammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, etc. Tetrabutylammonium hydroxide is particularly preferred.

[0032] 2. Method for producing the composite The method for manufacturing the complex comprises a first step and a second step. Hereinafter, each step will be described.

[0033] <First step: Production of ammonium hydroxide [B2]> In the first step, ammonium halide [B21] represented by chemical formula (3) is reacted with an alkali metal hydroxide to produce ammonium hydroxide [B2].

[0034] The ammonium halide [B21] is represented by the following formula.

Chemical formula

[0035] R 2 , R 3 , R 4 , R 5 The substituted or unsubstituted hydrocarbon group represented by is the same as that in the description of ammonium hydroxide [B2].

[0036] Examples of the halide include iodide, bromide, chloride, fluoride, etc. From the viewpoint of particularly good reactivity, bromide is preferred. Therefore, the ammonium halide [B21] is preferably ammonium bromide.

[0037] Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, etc. Potassium hydroxide is preferred from the viewpoints of good solubility in a solvent such as alcohol and easy removal of by-produced alkali halide.

[0038] The purity of the alkali metal hydroxide is preferably 80% or more, more preferably 90% or more, from the viewpoint of suppressing coloring during the heat acceleration of ammonium hydroxide [B2]. Specifically, for example, it can be 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, and it may also be within the range between any two of the numerical values exemplified here.

[0039] In the first-step reaction, it is preferable to use a solvent from the viewpoint of smoothly progressing the reaction. Examples of the solvent to be used include methanol, ethanol, propanol, isopropanol, butanol, etc. Since ammonium hydroxide can be synthesized at a high concentration, methanol and ethanol are preferable, and methanol is more preferable. The usage amount is arbitrarily selected within the range of 0.5 to 20 times the mass of ammonium halide [B21], and preferably within the range of 0.5 to 5 times the mass.

[0040] The reaction temperature of the first-step reaction is preferably 0 to 90 °C, and particularly preferably in the temperature range of room temperature to 60 °C.

[0041] In the first-step reaction, from the viewpoint of reducing the amount of alkali halide contained in the reaction product, the reaction molar ratio of the alkali metal hydroxide to ammonium halide [B21] is preferably 0.7 to 0.99, more preferably 0.7 to 0.9, still more preferably 0.75 to 0.85, and particularly preferably 0.8 to 0.85. Specifically, this reaction molar ratio is, for example, 0.7, 0.75, 0.76, 0.77, 0.78, 0.79, 0.8, 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0.9, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98, 0.99, and it may also be within the range between any two of the numerical values exemplified here.

[0042] As the amount of alkali halide contained in the reaction product increases, removal becomes difficult, which may cause problems such as a decrease in catalytic activity as a catalyst or appearance problems such as the solution of ammonium hydroxide becoming cloudy.

[0043] Incidentally, the first step may be recognized as a step included in the method for producing ammonium hydroxide [B2]. The ammonium hydroxide [B2] obtained in the first step may be used in the second step described later, or may be used for other purposes. For example, the ammonium hydroxide [B2] obtained in the first step and the titanium compound [B1] may be mixed to obtain a catalyst composed of a mixture of both.

[0044] <Second Step: Reaction of Ammonium Hydroxide [B2] and Titanium Compound [B1]> In the second step, ammonium hydroxide [B2] and the titanium compound [B1] are reacted. As a result, a complex of a transparent liquid, for example, is produced as a reaction product.

[0045] The second step can be carried out by reacting a mixture of ammonium hydroxide [B2] and the titanium compound [B1] at, for example, 20 to 100°C. In this step, it is preferable to drop and react ammonium hydroxide [B2] with respect to the titanium compound [B1] at the above temperature.

[0046] Specifically, the temperature is, for example, 20, 30, 40, 50, 60, 70, 80, 90, 100°C, and may be within the range between any two of the values exemplified here. The molar ratio of the titanium compound [B1] to ammonium hydroxide [B2] in the mixture is, for example, 0.1 to 100, and is 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 50, 100, and may be within the range between any two of the values exemplified here.

[0047] 3. Method of Using the Catalyst The composite obtained by the above manufacturing method, or the mixture of ammonium hydroxide [B2] and titanium compound [B1] obtained in the first step, can be used as a catalyst.

[0048] Examples of the method of using the catalyst include a method for producing a moisture-curing composition, a method for producing a urethane resin composition, and a method for producing an ester compound.

[0049] 3-1. Method for producing a moisture-curing composition The method for producing a moisture-curing composition includes a step of mixing a curing catalyst and a polymer [A] having a reactive hydrolyzable silicon-containing group. As the curing catalyst, the above-described composite or mixture can be used.

[0050] Hereinafter, each component will be described.

[0051] 3-1-1. Polymer [A] Polymer [A] has at least one reactive hydrolyzable silicon-containing group per molecule at the molecular terminal or side chain. The reactive hydrolyzable silicon-containing group may be present at the terminal of the polymer [A] molecule, may be present in the side chain, or may be present in both the terminal and the side chain. The reactive hydrolyzable silicon-containing group only needs to be at least one per molecule of polymer [A], but from the viewpoints of curing rate and cured physical properties, it is preferably 1.5 or more on average per molecule. As a method for bonding the reactive hydrolyzable silicon-containing group to the main chain polymer, a known method can be adopted. Polymer [A] is preferably liquid at room temperature.

[0052] The reactive hydrolyzable silicon-containing group is a group having a silicon atom bonded to a reactive group composed of a hydrolyzable group (e.g., halogen, alkoxy, alkenyloxy, acyloxy, amino, aminooxy, oxime, amide) or a hydroxyl group, and has the property of causing a condensation reaction by using a catalyst etc. as necessary in the presence of moisture or a crosslinking agent. Specifically, examples include a halosilyl group, an alkoxysilyl group, an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group, an aminooxysilyl group, an oximesilyl group, an amidosilyl group, etc.

[0053] Here, the number of reactive hydrolyzable groups bonded to one silicon atom is selected from the range of 1 to 3. Also, the reactive hydrolyzable groups bonded to one silicon atom may be of one type or a plurality of types. Further, a reactive hydrolyzable group and a non-reactive hydrolyzable group may be bonded to one silicon atom, or a hydrolyzable group and a hydroxyl group may be bonded to one silicon atom. As the reactive hydrolyzable silicon-containing group, an alkoxysilyl group (including a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group) is particularly preferable in terms of ease of handling.

[0054] Among the above alkoxysilyl groups, the trialkoxysilyl group is preferable because it has high activity and good curability, and the resulting cured product is excellent in resilience, durability, and creep resistance. On the other hand, the dialkoxysilyl group and the monoalkoxysilyl group are preferable because they have excellent storage stability and the resulting cured product has high elongation and high strength. When a polymer [A] having a reactive hydrolyzable silicon-containing group that is a dialkoxysilyl group and a polymer [A] having a trialkoxysilyl group are used in combination, it is preferable because a balance can be achieved between the physical properties and curability of the cured product.

[0055] Examples of the polymer [A] include an organic polymer [A1] and an organopolysiloxane [A2].

[0056] <Organic polymer [A1]> As the main chain of the organic polymer [A1] used in the present invention, those having carbon atoms, for example, alkylene oxide polymers, polyester polymers, ether-ester block copolymers, polymers of ethylenically unsaturated compounds, polymers of diene compounds, etc. can be mentioned.

[0057] Examples of the alkylene oxide polymer include [CH2CH2O] n [CH(CH3)CH2O] n [CH(C2H5)CH2O] n [CH2CH2CH2CH2O] n Those having one or more of the repeating units such as these are exemplified. Here, n is an integer of 2 or more, which may be the same or different. These alkylene oxide polymers may be used alone or in combination of two or more. Also, copolymers containing two or more of the above repeating units can be used.

[0058] Examples of the polyester polymer include those having carboxylic acids such as acetic acid, propionic acid, maleic acid, phthalic acid, citric acid, pyruvic acid, lactic acid and their anhydrides, and their intra- and / or intermolecular esters and their substituents, etc. as repeating units.

[0059] Examples of the ether-ester block copolymer include those having both the repeating unit used for the above-mentioned alkylene oxide polymer and the repeating unit used for the above-mentioned polyester polymer as repeating units.

[0060] In addition, examples of the polymer of the ethylenically unsaturated compound and the diene compound include homopolymers of ethylene, propylene, acrylic ester, methacrylic ester, vinyl acetate, acrylonitrile, styrene, isobutylene, butadiene, isoprene, chloroprene, etc., or copolymers of two or more of these. More specifically, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-butadiene copolymer, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic ester copolymer, polyisoprene, styrene-isoprene copolymer, isobutylene-isoprene copolymer, polychloroprene, styrene-chloroprene copolymer, acrylonitrile-chloroprene copolymer, polyisobutylene, polyacrylic ester, polymethacrylic ester, etc. are included. These may be used alone or in combination of two or more.

[0061] As the organic polymer [A1], an organic polymer having a polar group such as a nitrogen-containing characteristic group in the molecule can also be used. Specific examples of the above nitrogen-containing characteristic group include (thio)urethane group, allophanate group, other N-substituted urethane groups, N-substituted allophanate groups and other bonding groups derived from (thio)urethane groups, (thio)urea group, biuret group, other N-substituted urea groups, N,N'-substituted urea groups, N-substituted biuret groups, N,N'-substituted biuret groups and other bonding groups derived from (thio)urea groups, amide group, bonding groups derived from amide groups such as N-substituted amide groups, and nitrogen-containing characteristic groups represented by bonding groups derived from imino groups, and (thio)ester groups, (thio)ether groups, etc., but are not limited thereto. Among these, nitrogen-containing characteristic groups are preferred because of their high curability, and bonding groups derived from (thio)urethane groups and (thio)urea groups are more preferred because of the ease of synthesis. Further, the nitrogen-containing characteristic group may be contained only one in the above organic polymer [A1], or may contain a plurality of one or more nitrogen-containing characteristic groups. Here, the notations of "(thio)" and "N-substituted" are the same as above.

[0062] When a polar group such as the above nitrogen-containing characteristic group is contained in the organic polymer [A1], the toughness of the cured product is improved, and the curability and adhesive strength are increased. In particular, when the crosslinkable silicon group is linked to the main chain via a polar group such as a nitrogen-containing characteristic group, the curability is further increased. The reason is that the polar groups of the nitrogen-containing characteristic groups are strongly attracted to each other by an interaction such as a hydrogen bond. It is considered that the toughness is expressed in the cured product by the strong binding (domain formation) of the molecules of the curable resin due to the strong attraction between the polar groups of the nitrogen-containing characteristic group. Further, when the crosslinkable silicon group is linked to the main chain via a polar group such as a nitrogen-containing characteristic group, when the nitrogen-containing characteristic groups form a domain, the crosslinkable silicon groups also approach each other accordingly, so that the contact probability of the crosslinkable silicon groups is improved. Furthermore, it is considered that the condensation reactivity of the crosslinkable silicon groups is improved by the catalytic curing by the polar groups in the nitrogen-containing characteristic group.

[0063] Such an organic polymer [A1] (modified silicone-based polymer) can be produced by a known method such as the method described in Japanese Patent Publication No. 61-18569, or is commercially available. Examples of commercially available products include the Kaneka MS polymer series (MS polymer S203, MS polymer S303, MS polymer S903, MS polymer S911, MS polymer SAX520, etc.), the silyl series (silyl polymer SAT200, silyl polymer MA430, silyl polymer MAX447, etc.), the MA series, the SA series, the OR series manufactured by Kaneka Corporation; the ES series (ES-GX3440ST, etc.), the ESGX series, etc. manufactured by Asahi Glass Co., Ltd.

[0064] The number average molecular weight of the organic polymer [A1] used in the present invention is not particularly limited, but if it is excessively high molecular weight, it has a high viscosity and becomes difficult to use when made into a curable composition, so it is preferably 30,000 or less. Such an organic polymer can be produced by a known method, but commercially available products such as the Kaneka MS polymer manufactured by the above-mentioned Kaneka Corporation may also be used.

[0065] <Organopolysiloxane [A2]> The organopolysiloxane [A2] used in the present invention is composed of siloxane bonds represented by Si-O in the main chain, and an organic group is bonded to the silicon atom constituting the siloxane bond. Specific examples of such organic groups include alkyl groups such as methyl, ethyl, propyl, and butyl; cycloalkyl groups such as cyclohexyl; alkenyl groups such as vinyl, isopropenyl, and substituted vinyl; substituted allyl groups such as allyl, crotyl, and methallyl; aryl groups such as phenyl, toluyl, and xylyl; aralkyl groups such as benzyl and phenylethyl; and groups in which all or part of the hydrogen atoms of these organic groups are substituted with halogen atoms, such as chloromethyl group and 3,3,3-trifluoropropyl group.

[0066] Examples of the organopolysiloxane [A2] include (-Si(R)2-O-) m (In the formula, R is the same or different organic group, and m represents an integer of 2 or more.) Those having repeating units represented by are exemplified. Specific examples include (-Si(CH3)2-O-) m (-Si(C2H5)2-O-) m (-Si(Ph)2-O-) m (-Si(-CH=CH2)2-O-) m Those having one or more of the following repeating units are exemplified. Here, m is the same or different and is an integer of 2 or more. The organopolysiloxane [A2] may be composed of a single main chain or may be composed of two or more main chains.

[0067] The organopolysiloxane may be linear or branched including trifunctional form (R'SiO 1.5 ) or tetrafunctional form (SiO2). Also, depending on the physical properties and uses of the cured product, bifunctional form (R'2SiO) or monofunctional form (R'3SiO 0.5They may be combined (wherein R' is an organic group). Further, the hydrolyzable silicon-containing group may be bonded to either the molecular terminal or the middle of the molecular chain. Note that organopolysiloxanes generally have an average composition formula of R a SiO 4-a / 2 as shown (for example, see Japanese Patent Application Laid-Open Nos. 2005-194399 and 8-151521). The above notation follows this.

[0068] The viscosity of the organopolysiloxane [A2] used in the present invention is not particularly restricted, but if it is overly high-viscosity, there is a risk that the workability will decrease or the physical properties of the resulting cured product will be impaired. Therefore, it is desirable that the viscosity at 25 °C be in the range of 0.025 to 100 Pa·s. Such organopolysiloxanes can be produced by known methods, but commercially available products such as the Tos Seal series manufactured by GE Toshiba Silicones Co., Ltd., the Sealant series manufactured by Shin-Etsu Chemical Co., Ltd., and the SH series manufactured by Toray Dow Corning Co., Ltd. can be used.

[0069] 3-1-2. Details of the moisture-curing type composition The moisture-curing type composition contains a curing catalyst and a polymer [A], and may contain other additives described later as necessary. The moisture-curing type composition of the present invention can be prepared by mixing the two under dry conditions, and the mixing form is not particularly limited. Usually, it may be mixed in an atmosphere at a temperature of about 15 to 30 °C and 60% RH or less.

[0070] In the moisture-curing composition of the present invention, the content of the curing catalyst [B] is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and particularly preferably 3 to 8 parts by weight with respect to 100 parts by weight of the polymer [A]. If the content of the curing catalyst [B] is less than 0.1 part by weight, the curing performance is insufficient, and if it exceeds 20 parts by weight, the physical properties such as the restoration rate and weather resistance of the cured product after curing may deteriorate, and the stability during storage may also deteriorate. Specifically, the content of the curing catalyst [B] is, for example, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 parts by mass with respect to 100 parts by weight of the polymer [A], and it may be within the range between any two of the values exemplified herein.

[0071] A filler may be further blended in the moisture-curing composition of the present invention. Examples of the filler include calcium carbonate, kaolin, talc, fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid, clay, calcined clay, glass, bentonite, organic bentonite, shirasu balloon, glass fiber, asbestos, glass filament, pulverized quartz, diatomaceous earth, aluminum silicate, aluminum hydroxide, zinc oxide, magnesium oxide, titanium dioxide, and the like. The filler may be used alone or in combination of two or more. By adding the filler, the handling of the moisture-curing composition is improved. It also acts as a rubber reinforcing agent for the cured product. The greatest merit is that the amount of the resin used can be reduced by adding it as an extender, so the cost can be reduced.

[0072] Among them, calcium carbonate and titanium dioxide are preferred from the viewpoint of maintaining excellent surface non-tack, 50% modulus, workability, weather resistance, etc. of the cured curable composition after curing. When using calcium carbonate, the ratio is preferably 1 to 200 parts by weight, more preferably 50 to 200 parts by mass with respect to 100 parts by weight of the polymer [A]. Within the above range, the properties after curing are not impaired.

[0073] The moisture-curing composition of the present invention may further contain additives commonly added to curable compositions, such as other curing catalysts, curing accelerators, colorants, plasticizers, curing retardants, anti-sagging agents, anti-aging agents, solvents, etc.

[0074] Examples of other curing catalysts include metal curing catalysts such as organotin compounds like dibutyltin dilaurate and dibutyltin bis(acetylacetonate), organoaluminum compounds such as aluminum tris(acetylacetonate) and aluminum tris(ethylacetoacetate), organozirconium compounds such as zirconium tetra(acetylacetonate) and zirconium tetrabutyrate, etc., and amine compounds such as 1-amino-2-ethylhexane, 3-(trimethoxysilyl)propylamine, N-2-aminoethyl-3-aminopropyltrimethoxysilane, N,N,N',N'-tetramethyl-N''-[3-(trimethoxysilyl)propyl]guanidine, 1,5,7-triazabicyclo-[4,4,0]dec-5-ene, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, etc.

[0075] As the curing accelerator, for example, various known amino group-substituted alkoxysilane compounds or their condensates can be used. Specific examples include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-(trimethoxysilylpropyl)ethylenediamine, δ-aminobutyl(methyl)diethoxysilane, N,N-bis(trimethoxysilylpropyl)ethylenediamine, and their partial hydrolysis products, etc. These also have the effect of improving the adhesion to the substrate.

[0076] Specific examples of the colorant include iron oxide, carbon black, phthalocyanine blue, phthalocyanine green, etc.

[0077] As plasticizers, specifically, phthalic acid esters such as dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate, etc.; fatty acid carboxylic acid esters such as dioctyl adipate, dioctyl succinate, diisodecyl succinate, butyl oleate, etc.; glycol esters such as pentaerythritol esters, etc.; phosphate esters such as trioctyl phosphate, tricresyl phosphate, etc.; epoxy plasticizers such as epoxidized soybean oil, benzyl epoxy stearate, etc.; chlorinated paraffin, etc. are used.

[0078] As anti-sagging agents, specifically, hydrogenated castor oil, silicic anhydride, organic bentonite, colloidal silica, etc. are used.

[0079] Also, as other additives, adhesion promoters such as phenolic resins, epoxy resins, etc., ultraviolet absorbers, radical chain inhibitors, peroxide decomposers, various anti-aging agents, etc. are used.

[0080] The curable composition of the present invention is sufficiently stable at room temperature, so it has excellent storage properties, and when it comes into contact with moisture, the curing reaction proceeds spontaneously by the incorporated curing catalyst [B]. Also, the snap time (the time until semi-gelation and loss of fluidity) and the tack-free time (the time until the surface tack disappears) are short, and it has excellent workability.

[0081] Due to the above characteristics, the curable composition of the present invention can be used as a one-component sealing material. Specifically, it is suitably used for applications such as sealing materials for vehicles such as buildings, ships, automobiles, adhesives, sealants, and waterproof caulking materials.

[0082] 3-2. Method for producing urethane resin composition The method for producing a urethane resin composition includes a step of reacting a polyol component and an isocyanate component in the presence of a catalyst. As the catalyst, the above-described composite or mixture can be used.

[0083] The polyol component is a component composed of a compound having a plurality of hydroxyl groups, and examples of the polyol component include polypropylene glycol and the like.

[0084] The isocyanate component is a component composed of a compound having an isocyanate group, and it is preferably a polyisocyanate compound having two or more isocyanate groups in the molecule.

[0085] 3-3. Method for producing an ester compound The method for producing an ester compound includes a step of reacting an alcohol component with an ester component in the presence of a catalyst. As the catalyst, the above-described composite or mixture can be used.

[0086] The alcohol component is not particularly limited, and examples thereof include ethanol, 1-butanol, 2-butanol, tert-butyl alcohol, amyl alcohol, t-amyl alcohol, 1-hexanol, 2-hexanol, 1-octanol, 2-ethyl-1-hexanol, isodecyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, bisphenol A, hydrogenated bisphenol A, an adduct of bisphenol A with ethylene oxide or propylene oxide, trimethylolethane, trimethylolpropane, glycerin, pentaerythritol and other aliphatic alcohols, alicyclic alcohols such as cyclopentanol, cyclohexanol, adamantanol, aromatic alcohols such as benzyl alcohol, methylbenzyl alcohol, 1-phenylethanol, 2-phenylethanol, Dimethylethanolamine, diethylethanolamine, dipropylethanolamine, 6 -aminohexanol, trans-4-aminocyclohexanol, amino alcohols such as prolinol, and the like can be mentioned.

[0087] The ester component is not particularly limited and can be appropriately selected according to the type of ester compound to be produced. For example, carbonate esters such as dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, diphenyl carbonate, dinaphthyl carbonate, Aromatic carboxylic acid esters such as benzoic acid esters and their derivatives, α,β-unsaturated carboxylic acid esters such as (meth)acrylic acid esters, Polyvalent carboxylic acid esters such as diethyl oxalate, diethyl malonate, diethyl succinate, diethyl glutarate, diethyl adipate, and the like can be mentioned.

Examples

[0088] Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereby.

[0089] 1. First step: Production of ammonium hydroxide [B2]) According to the method shown below, ammonium halide [B21] and an alkali metal hydroxide were reacted to produce ammonium hydroxide [B2]. Table 1 summarizes the blending ratios in each production example.

[0090]

Table 1

[0091] <Production Example 1> A 300 mL four-necked round-bottom flask equipped with a nitrogen inlet tube was charged with potassium hydroxide: 15.93 g (purity 96.3%, 0.27336 mol) and methanol: 120.77 g (3.76948 mol), and stirred. After the exotherm subsided, tetrabutylammonium bromide: 100.00 g (98.7%, 0.30616 mol) was added, and the mixture was stirred at an internal temperature of 60 °C for 30 minutes. After cooling to room temperature, filtration was performed to obtain 186.58 g of a clear liquid of B2a: tetrabutylammonium hydroxide (hereinafter, "TBAH") methanol solution.

[0092] When NMR measurement of TBAH was carried out, the following results were obtained. 1H NMR (400 MHz CDCl3): δ=3.35 - 3.31 (m, 8H), δ=1.70 - 1.64(m, 8H), δ=1.46 (q, 7.4Hz,8H), δ=1.02 (t, 7.4Hz, 12H), δ=0 (TMS) Similar NMR spectra were obtained for the TBAH obtained in the following Production Examples 2 to 12.

[0093] <Production Example 2> A 300 mL four-necked round-bottom flask equipped with a nitrogen inlet tube was charged with tetrabutylammonium bromide: 100.00 g (98.7%, 0.30616 mol) and methanol: 50.00 g (1.56055 mol), and stirred. After dissolution, a solution prepared by previously dissolving potassium hydroxide: 15.93 g (purity 96.3%, 0.27336 mol) in methanol: 70.77 g (2.20880 mol) was added dropwise over 1 hour, and the mixture was stirred at an internal temperature of 60 °C for 30 minutes. After cooling to room temperature, filtration was performed to obtain 186.58 g of a clear liquid of B2b: TBAH methanol solution.

[0094] <Production Example 3> Into a 300 mL four-necked round-bottom flask equipped with a nitrogen inlet tube, tetrabutylammonium bromide: 100.00 g (98.7%, 0.30616 mol) and methanol: 120.77 g (3.76948 mol) were charged and stirred. After dissolution, potassium hydroxide: 15.93 g (purity 96.3%, 0.27336 mol) was added and stirred at an internal temperature of 60 °C for 30 minutes. After cooling to room temperature, filtration was carried out to obtain 186.58 g of B2c: TBAH methanol solution as a clear liquid.

[0095] <Production Example 4> Into a 50 mL four-necked round-bottom flask equipped with a nitrogen inlet tube, potassium hydroxide: 4.78 g (purity 96.3%, 0.08201 mol) and methanol: 21.28 g (0.66425 mol) were charged and stirred. After the exotherm subsided, tetrabutylammonium bromide: 30.00 g (98.7%, 0.09185 mol) was added and stirred at an internal temperature of 60 °C for 30 minutes. After cooling to room temperature, filtration was carried out, and 26.89 g of methanol was added to obtain 64.88 g of B2d: TBAH methanol solution as a clear liquid.

[0096] <Production Example 5> Into a 100 mL four-necked round-bottom flask equipped with a nitrogen inlet tube, potassium hydroxide: 3.72 g (purity 96.3%, 0.06378 mol) and methanol: 28.18 g (0.87954 mol) were charged and stirred. After the exotherm subsided, tetrabutylammonium bromide: 25.00 g (98.7%, 0.07654 mol) was added and stirred at an internal temperature of 60 °C for 30 minutes. After cooling to room temperature, filtration was carried out to obtain 43.81 g of B2e: TBAH methanol solution as a clear liquid.

[0097] <Production Example 6> Into a 100 mL four-necked round-bottom flask equipped with a nitrogen inlet tube, 4.33 g of potassium hydroxide (purity 96.3%, 0.07431 mol) and 32.83 g of methanol (1.02471 mol) were charged and stirred. After the exotherm subsided, 25.00 g of tetrabutylammonium bromide (98.7%, 0.07654 mol) was added, and the mixture was stirred at an internal temperature of 60 °C for 30 minutes. After cooling to room temperature, it was filtered to obtain 48.29 g of a clear liquid of B2f: TBAH methanol solution.

[0098] <Production Example 7> Into a 50 mL four-necked round-bottom flask equipped with a nitrogen inlet tube, 4.78 g of potassium hydroxide (purity 96.3%, 0.08201 mol) and 26.01 g of methanol (0.81173 mol) were charged and stirred. After the exotherm subsided, 30.00 g of tetrabutylammonium bromide (98.7%, 0.09185 mol) was added, and the mixture was stirred at an internal temperature of 60 °C for 30 minutes. After cooling to room temperature, it was filtered to obtain 44.15 g of a clear liquid of B2g: TBAH methanol solution.

[0099] <Production Example 8> Into a 300 mL four-necked round-bottom flask equipped with a nitrogen inlet tube, 3.98 g of potassium hydroxide (purity 96.3%, 0.06834 mol) and 159.59 g of methanol (4.9811 mol) were charged and stirred. After the exotherm subsided, 25.00 g of tetrabutylammonium bromide (98.7%, 0.07654 mol) was added, and the mixture was stirred at an internal temperature of 60 °C for 30 minutes. After cooling to room temperature, it was filtered to obtain 180.63 g of a clear liquid of B2h: TBAH methanol solution.

[0100] <Production Example 9> Into a 300 mL four-necked round-bottom flask equipped with a nitrogen inlet tube, tetrabutylammonium bromide: 10.00 g (98.3%, 0.03049 mol) and isopropanol: 150.29 g (2.5007 mol) were charged and stirred. After dissolution, potassium hydroxide: 1.58 g (purity 96.3%, 0.02818 mol) was added and stirred at room temperature for 24 hours. After completion of the reaction, filtration was carried out to obtain 155.89 g of B2i: TBAH isopropanol solution as a clear liquid.

[0101] <Production Example 10> The operation was carried out in the same manner as in Production Example 1 except that the raw material used was changed from tetrabutylammonium bromide to tetrabutylammonium chloride to obtain a B2j: TBAH methanol solution.

[0102] <Production Example 11> Into a 100 mL four-necked round-bottom flask equipped with a nitrogen inlet tube, potassium hydroxide: 4.46 g (purity 96.3%, 0.07654 mol) and methanol: 33.82 g (1.0555 mol) were charged and stirred. After the exotherm subsided, tetrabutylammonium bromide: 25.00 g (98.7%, 0.07654 mol) was added and stirred at an internal temperature of 60 °C for 30 minutes. After cooling to room temperature, filtration was carried out to obtain 48.31 g of B2k: TBAH methanol solution as a clear liquid.

[0103] <Production Example 12> The operation was carried out in the same manner as in Production Example 1 except that the raw material used was changed from potassium hydroxide with a purity of 96.3% to potassium hydroxide with a purity of 86.6% to obtain a B2l: TBAH methanol solution.

[0104] 2. Second Step: Production of Composite According to the method shown below, ammonium hydroxide [B2] and titanium compound [B1] were reacted to produce a composite. Tables 2 to 3 summarize the blending ratios in each example.

[0105]

Table 2

[0106]

Table 3

[0107] <Example 1> 143.49 g (0.50486 mol) of titanium tetraisopropoxide was charged into a 500 mL four-necked round-bottom flask equipped with a nitrogen inlet tube. While stirring, 130.00 g (33.59%, 0.16829 mol) of the B2a:TBAH methanol solution obtained in Production Example 1 was added dropwise over 30 minutes. After the internal temperature was raised to 80 °C, the mixture was concentrated under reduced pressure (final reduced pressure: 10 mmHg) to distill off isopropanol and methanol, and 148.42 g of a solution of Complex 1 was obtained. Further, 37.13 g (0.61780 mol) of isopropanol was added to obtain 185.55 g of an isopropanol solution of Complex 1.

[0108] When NMR measurement of Complex 1 was carried out, the following results were obtained. 1H NMR (400 MHz CDCl3): δ 3.40 - 3.37 = (m, 8H,), δ = 1.72 - 1.66 (m, 8H), δ = 1.49 - 1.45 (m, 8H), δ = 1.02 (t, 7.2 Hz, 12H), δ = 0 (TMS)

[0109] The chemical shifts of 3.35 - 3.31 of TBAH and 3.40 - 3.37 of Complex 1 are respectively attributed to the α-hydrogen atoms (hydrogen atoms of N-CH2) of the butyl group of TBAH. Therefore, it was confirmed that in Complex 1, the chemical shift of the α-hydrogen atom is shifted by +0.05 ppm compared with TBAH. Similar NMR spectra were obtained for the following Complexes 2 - 13.

[0110] <Examples 2 - 12> Instead of the B2a:TBAH methanol solution obtained in Production Example 1, the same operations as in Example 1 were carried out except that the B2b~B2l:TBAH solutions obtained in Production Examples 2~12 were used, and solutions of Complexes 2~12 were obtained.

[0111] <Example 13> 143.49 g (0.50486 mol) of tetra isopropoxytitanium was charged into a 500 mL four-necked round-bottom flask equipped with a nitrogen inlet tube. While stirring, 130.00 g (33.59%, 0.16829 mol) of the B2a:TBAH methanol solution obtained in Production Example 1 was added dropwise over 30 minutes. After the internal temperature was raised to 80 °C, it was concentrated under reduced pressure (final reduced pressure: 10 mmHg) to distill off isopropanol and methanol, and 148.42 g of a solution of Complex 13 was obtained. Further, 37.13 g (0.22887 mol) of butyl carbitol was added to obtain 185.55 g of a butyl carbitol solution of Complex 13.

[0112] <Example 14> 143.49 g (0.50486 mol) of tetra isopropoxytitanium and 37.13 g (0.22887 mol) of butyl carbitol were charged into a 500 mL four-necked round-bottom flask equipped with a nitrogen inlet tube. After the internal temperature was raised to 80 °C, it was concentrated under reduced pressure (final reduced pressure: 10 mmHg) to distill off 13.76 g (0.22887 mol) of isopropanol, and 166.86 g of a colorless liquid was obtained. 130.00 g (33.59%, 0.16829 mol) of the B2a:TBAH methanol solution obtained in Production Example 1 was added dropwise thereto over 30 minutes. After the internal temperature was raised to 80 °C again, it was concentrated under reduced pressure (final reduced pressure: 10 mmHg) to distill off isopropanol and methanol, and 167.05 g of a solution of Complex 14 was obtained.

[0113] When NMR measurement of Complex 14 was carried out, the following results were obtained. 1H NMR (400 MHz CDCl3): δ = 4.97 - 3.55 (m, 36H), δ = 3.42 - 3.38 (m, 8H), δ = 1.74 - 1.66 (m, 8H), δ = 1.47 (td, 7.4 Hz, 8H), δ = 1.29 - 1.21 (m, 12H), δ = 1.01 (t, 7.4 Hz, 12H), δ = 0 (TMS)

[0114] The chemical shifts of 3.35 - 3.31 for TBAH and 3.42 - 3.38 for complex 14 are respectively attributed to the α - hydrogen atoms (hydrogen atoms of N - CH2) of the butyl groups of TBAH. Therefore, in complex 14, it was confirmed that the chemical shift of the α - hydrogen atoms is shifted by +0.07 ppm compared to TBAH. Similar NMR spectra were obtained for the following complexes 15 - 17.

[0115] <Example 15> Into a 500 mL four - necked round - bottom flask equipped with a nitrogen inlet tube, 143.49 g (0.50486 mol) of tetra - isopropoxytitanium, 37.13 g (0.22887 mol) of butyl carbitol, and 130.00 g (33.59%, 0.16829 mol) of the B2a:TBAH methanol solution obtained in Production Example 1 were charged. After heating to an internal temperature of 80°C and then concentrating under reduced pressure (final reduced pressure of 10 mmHg) to distill off isopropanol and methanol, 167.05 g of a solution of complex 15 was obtained.

[0116] <Examples 16, 17> The same operations as in Example 14 were carried out except that the B2e - B2f:TBAH solutions obtained in Production Examples 5 - 6 were used instead of the B2a:TBAH methanol solution obtained in Production Example 1, and solutions of complexes 16 and 17 were obtained.

[0117] <Example 18> 50 mL four-necked round-bottom flask equipped with a nitrogen inlet tube was charged with 5.68 g (0.01998 mol) of titanium tetraisopropoxide, and while stirring, 7.71 g (33.59%, 0.00998 mol) of the TBAH methanol solution obtained in Production Example 1 was added dropwise over 5 minutes. After heating to an internal temperature of 80 °C, the mixture was concentrated under reduced pressure (final reduced pressure: 10 mmHg) to distill off isopropanol and methanol, obtaining 6.84 g of a solution of Complex 18. Further, 1.71 g (0.02845 mol) of isopropanol was added to obtain 8.55 g of an isopropanol solution of Complex 18.

[0118] When NMR measurement of Complex 18 was carried out, the following results were obtained. 1H NMR (400 MHz CDCl3): δ 3.41 - 3.37 (m, 8H), 1.73 - 1.65 (m, 8H), 1.47 (q, 7.4 Hz, 8H), 1.01 (t, 7.3 Hz, 12H) δ = 0 (TMS)

[0119] The chemical shifts of 3.35 - 3.31 of TBAH and 3.41 - 3.37 of Complex 18 are respectively attributed to the α-hydrogen atoms (hydrogen atoms of N-CH2) of the butyl group of TBAH. Therefore, it was confirmed that in Complex 18, compared with TBAH, the chemical shift of the α-hydrogen atom is shifted by +0.06 ppm.

[0120] 3. Preparation of curable composition Using each component obtained in the above production examples and examples and commercially available components, they were blended at the blending ratios (parts by mass) shown in Table 4 and kneaded to prepare a curable composition. The operations from blending, kneading to curing of the materials were carried out in an atmosphere of 25 ± 1 °C and 50 - 60% RH.

[0121]

Table 4

[0122] Details of the materials in the table are as follows. (Polymer [A]) MS Polymer SAX520: Organopolysiloxane Containing Silyl Group (manufactured by Kaneka Corporation) MS Polymer S303: Organopolysiloxane Containing Silyl Group (manufactured by Kaneka Corporation) GENIOSIL STP-E15: Organopolysiloxane Containing Silyl Group (manufactured by WACKER Chemical Corporation) KE-66: Organopolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0123] (Mixture of polyol component and isocyanate component) Reaction product of polypropylene glycol and XDI: m-Xylylene diisocyanate: 77.7 g, polypropylene glycol molecular weight 3200 diol type: 607.6 g, polypropylene glycol molecular weight 4000 triol type: 70.0 g were placed in a 900 cc mayonnaise bottle and heated in an oven at 80 °C overnight for preparation.

[0124] m-Xylylene diisocyanate: manufactured by Tokyo Chemical Industry Co., Ltd. Polypropylene glycol molecular weight 3200 diol type: manufactured by FUJIFILM Wako Pure Chemical Corporation Polypropylene glycol molecular weight 4000 triol type: manufactured by FUJIFILM Wako Pure Chemical Corporation

[0125] (Catalyst) Tetraisopropoxytitanium: manufactured by Tokyo Chemical Industry Co., Ltd.

[0126] (Filler) Carlex 300: Calcium carbonate (manufactured by Maruo Calcium Co., Ltd.) FR-41: Titanium oxide (manufactured by Furukawa Chemicals Co., Ltd.) REOLOSIL PM-20: Fumed silica (manufactured by Tokuyama Corporation)

[0127] (Other additives) DINP: Plasticizer (manufactured by J-PLAS Co., Ltd.) Polypropylene glycol (1000): Plasticizer (manufactured by Kishida Chemical Co., Ltd.) Disparon 6500: Anti-sagging agent (manufactured by Kusumoto Chemicals, Ltd.) Hydrogenated castor oil: thickening agent (manufactured by Ito Oil Co., Ltd.) Songsorb 3260P: UV absorber (manufactured by SONGWON) Sabostab UV70: light stabilizer (manufactured by SONGWON) Irganox245: antioxidant (manufactured by BASF Japan Ltd.) KBM-1003: dehydrating agent (manufactured by Shin-Etsu Silicone Co., Ltd.) p-Toluenesulfonyl isocyanate: manufactured by Tokyo Chemical Industry Co., Ltd. Nocrack NS-6: anti-aging agent (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) Smoil P-350: liquid paraffin (manufactured by Muramatsu Oil Co., Ltd.) KBM-903: adhesion promoter (manufactured by Shin-Etsu Silicone Co., Ltd.)

[0128] 4. Measurement of tack-free time (TFT) For the cured composition obtained in "3. Preparation of cured composition", the tack-free time (the time required until the sample no longer adhered to the fingertip after kneading, by lightly touching three places on the surface with a fingertip cleaned with ethyl alcohol) was measured.

[0129] The results of the measurement of the tack-free time are shown in Tables 1 to 3. Also, the tack-free time of Formulation Example 8 was 6 hours.

[0130] In Formulation Examples 1, 2, 7, and 8, only the catalyst is different, and the difference in the tack-free time of Formulation Examples 1, 2, 7, and 8 indicates the difference in catalyst performance regarding the curing reaction.

[0131] Comparing the tack-free times of Formulation Examples 1 and 7 in Table 1, the tack-free time of Formulation Example 2 in Tables 2 to 3, and the tack-free time of Formulation Example 8, it can be seen that the tack-free times of Formulation Examples 1 and 2 are shorter than those of Formulation Examples 7 and 8, and the tack-free time of Formulation Example 2 is shorter than that of Formulation Example 1.

[0132] This result indicates that the composite or mixture of the titanium compound [B1] and ammonium hydroxide [B2] has superior catalytic performance for the curing reaction compared to the case where the titanium compound [B1] and ammonium hydroxide [B2] are used alone, and the composite of the titanium compound [B1] and ammonium hydroxide [B2] has superior catalytic performance for the curing reaction compared to the mixture.

[0133] Furthermore, comparing the tack-free times of Formulation Example 1 for Production Example 1 and Production Example 11 in Table 1, it can be seen that Production Example 1 has a shorter tack-free time. This result indicates that when the reaction molar ratio of the alkali metal hydroxide to ammonium halide [B21] is 0.7 to 0.99, the catalytic performance for the curing reaction is excellent.

[0134] 5. Measurement of Transesterification Rate Into a 100 mL eggplant flask equipped with a nitrogen inlet tube, the reaction raw materials and catalyst were charged at the ratios (molar equivalents) shown in Table 5, and heated and concentrated in an oil bath at 170 °C for 1 hour. After the reaction was completed, the reaction solution was measured by gas chromatography. In the obtained measurement results, the peak area of 2-ethylhexyl benzoate was designated as S1, and the peak area of methyl benzoate was designated as S2, and the transesterification rate was calculated based on the following formula. Transesterification rate (%) = 100 × S1 / (S1 + S2)

[0135] The results of the transesterification rate are shown in Tables 1 to 3. Referring to Tables 1 to 3, it can be seen that the composite of the titanium compound [B1] and ammonium hydroxide [B2] has superior catalytic performance for the transesterification reaction compared to the mixture.

[0136] Furthermore, comparing the transesterification rates of Production Example 1 and Production Example 11 in Table 1, it can be seen that Production Example 1 has a higher transesterification rate. This result indicates that when the reaction molar ratio of the alkali metal hydroxide to ammonium halide [B21] is 0.7 to 0.99, the catalytic performance for the transesterification reaction is excellent.

[0137]

Table 5

[0138] Methyl benzoate: manufactured by FUJIFILM Wako Pure Chemical Corporation 2-Ethylhexanol: manufactured by Tokyo Chemical Industry Co., Ltd.

Claims

1. A method for producing a moisture-curable composition, comprising a step of mixing a curing catalyst and a polymer [A] having a reactive hydrolyzable silicon-containing group, wherein the curing catalyst is a complex produced by a first method or a mixture of ammonium hydroxide [B2] produced by a second method and a titanium compound [B1] represented by the chemical formula (1), The first method is, A method for producing a complex of a titanium compound [B1] and ammonium hydroxide [B2], wherein the titanium compound [B1] is represented by the chemical formula (1), wherein the ammonium hydroxide [B2] is represented by the chemical formula (2), The method comprises a first step and a second step, In the first step, an ammonium halide [B21] represented by the chemical formula (3) is reacted with an alkali metal hydroxide to produce the ammonium hydroxide [B2], In the second step, the ammonium hydroxide [B2] and the titanium compound [B1] are reacted, The second method is, A method for producing ammonium hydroxide [B2], A method comprising a step of reacting an ammonium halide [B21] represented by the chemical formula (3) with an alkali metal hydroxide to produce ammonium hydroxide [B2]. (R1−O)4Ti (1) (In the formula, three of the four Rs １ are alkyl groups, and the remaining one represents an alkyl group or an oxyalkylene group. The alkyl group is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, or decyl, and the oxyalkylene group has 4 to 20 carbon atoms in the main chain) 【Chemical 2】 (In the formula, R2, R3, R4, and R5 are the same as or different from each other and represent a saturated hydrocarbon group, and the saturated hydrocarbon group is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, or an octyl group. X represents a hydroxyl group.) 【Chemical Formula 3】 (In the formula, R2, R3, R4, and R5 are the same as or different from each other and represent a saturated hydrocarbon group, and the saturated hydrocarbon group is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, or an octyl group. X represents a halide.)

2. A method for producing a urethane resin composition, comprising a step of reacting a polyol component and an isocyanate component in the presence of a catalyst, wherein the catalyst is a complex produced by a first method or a mixture of ammonium hydroxide [B2] produced by a second method and a titanium compound [B1] represented by the chemical formula (1), The first method is, A method for producing a composite of a titanium compound [B1] and ammonium hydroxide [B2], wherein the titanium compound [B1] is represented by the chemical formula (1), the ammonium hydroxide [B2] is represented by the chemical formula (2), the method comprises a first step and a second step, in the first step, an ammonium halide [B21] represented by the chemical formula (3) is reacted with an alkali metal hydroxide to produce the ammonium hydroxide [B2], in the second step, the ammonium hydroxide [B2] and the titanium compound [B1] are reacted, The second method is a method for producing ammonium hydroxide [B2], which comprises a step of reacting an ammonium halide [B21] represented by the chemical formula (3) with an alkali metal hydroxide to produce ammonium hydroxide [B2]. (R1−O)4Ti (1) (In the formula, three of the four Rs １ are alkyl groups, and the remaining one represents an alkyl group or an oxyalkylene group. The alkyl group is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, or decyl, and the oxyalkylene group has 4 to 20 carbon atoms in the main chain) [Chemical Formula 2] (In the formula, R2, R3, R4, and R5 are the same as or different from each other and represent a saturated hydrocarbon group, and the saturated hydrocarbon group is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, or an octyl group. X represents a hydroxyl group.) [Chemical Formula 3] (In the formula, R2, R3, R4, and R5 are the same as or different from each other and represent a saturated hydrocarbon group, and the saturated hydrocarbon group is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, or an octyl group. X represents a halide.) [

3. ] A method for producing an ester compound, comprising a step of reacting an alcohol component and an ester component in the presence of a catalyst, wherein the catalyst is a composite produced by the first method, The first method is a method for producing a composite of a titanium compound [B1] and ammonium hydroxide [B2], wherein the titanium compound [B1] is represented by the chemical formula (1), the ammonium hydroxide [B2] is represented by the chemical formula (2), the method comprises a first step and a second step, in the first step, an ammonium halide [B21] represented by the chemical formula (3) is reacted with an alkali metal hydroxide to produce the ammonium hydroxide [B2], in the second step, the ammonium hydroxide [B2] and the titanium compound [B1] are reacted. (R1−O)4Ti (1) (In the formula, three of the four Rs １ are alkyl groups, and the remaining one represents an alkyl group or an oxyalkylene group. The alkyl group is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, or decyl, and the oxyalkylene group has 4 to 20 carbon atoms in the main chain.) 【Chemical Formula 2】 (In the formula, R2, R3, R4, and R5 are the same as or different from each other and represent a saturated hydrocarbon group, and the saturated hydrocarbon group is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, or an octyl group. X represents a hydroxyl group.) [Chemical Formula 3] (In the formula, R2, R3, R4, and R5 are the same as or different from each other and represent a saturated hydrocarbon group, and the saturated hydrocarbon group is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, or an octyl group. X represents a halide.) (4) The method according to claim 1 or claim 2, wherein In the second method, the reaction molar ratio of the alkali metal hydroxide to the ammonium halide [B21] is 0.7 to 0.

99. (5) The method according to any one of claims 1 to 4, wherein In the first method, the reaction molar ratio of the alkali metal hydroxide to the ammonium halide [B21] is 0.7 to 0.99.

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