WO2022024988A1 - Curing catalyst to be used for curing polymer and method for producing same, moisture-curable composition, and method for producing cured article - Google Patents

Abstract

The purpose of the present invention is to provide a curing catalyst that is highly safe and achieves a practical curing speed.　The present invention provides a curing catalyst [B] to be used for curing a polymer [A] having a reactive hydrolyzable silicon-containing group. This curing catalyst [B] comprises a complex of a titanium compound [B1] and an organic onium salt [B2], said titanium compound [B1] being represented by chemical formula (1).　(1): (R¹-O)_nTi-A_4-n (In the formula: R¹ represents an optionally substituted hydrocarbon group; n is from 1 to 4; and A represents a β-diketone group.)

Description

Curing catalyst used for curing polymer and its production method, moisture-curable composition, method for producing cured product

The present invention relates to a curing catalyst used for curing a polymer, a method for producing the same, a moisture-curable composition, and a method for producing a cured product.

The one-component moisture-curable rubber composition generally has a high curing rate, and it is not necessary to weigh and mix various additives such as a base polymer, a cross-linking agent, and a catalyst before use, so that the one-component type is a two-component type. It is superior in terms of workability.

As these one-component moisture-curable rubber compositions, silicone-based rubbers, modified silicone-based rubbers, urethane-based rubbers, polysulfide-based rubbers, and the like are known.
An organopolysiloxane composition is widely used as a one-component moisture-curable rubber composition of a silicone-based rubber, and is cured at room temperature to form a rubber elastic body. The polymer compound of siloxane having a —Si—O— bond as the main chain, which is cross-linked and polymerized by organosiloxane, has excellent properties such as water repellency, heat resistance, weather resistance, cold resistance, and electrical insulation. Widely used in fields such as civil engineering, electricity, electronics, and automobile industry.

As a one-component moisture-curable rubber composition of modified silicone-based rubber, there is a composition containing a polymer having a crosslinkable reactive hydrolyzable silicon functional group having a polyether as a main chain. The curable composition of this polymer has better storage stability, weather resistance, foaming resistance and discoloration resistance than those of polyurethane-based rubber, and is superior in curability to surroundings as compared with polysulfide-based ones. It is less contaminated and non-toxic.

The reaction mechanism in the process of the silicone-based rubber and the modified silicone-based rubber becoming a cured product is said to be due to the condensation reaction or addition reaction of the reactive hydrolyzable silicon-containing group in the coexistence of water, and the polymerization proceeds. It is believed that a cured polymer with a three-dimensional network structure is formed. Curing catalysts are used in order to accelerate curing in this reaction (Patent Documents 1 to 5).

Japanese Unexamined Patent Publication No. 8-41358 Japanese Unexamined Patent Publication No. 60-161457 Special Publication No. 63-42942 Japanese Unexamined Patent Publication No. 2003-147220 Japanese Patent No. 5446265

As a curing catalyst for the curing composition of the silicone-based rubber having the reactive hydrolyzable silicon-containing group and the modified silicone-based rubber, tin carboxylate compounds, alkyl tin salt compounds and the like have been conventionally used, but endocrine disruption is disrupted. Since there is concern about the effect on the living body as a substance, a combined catalyst of carboxylic acid and amine (Patent Document 1) has been proposed as a moisture-curable composition that does not use such a substance, but it is sufficiently cured at the time of construction. There is a problem that speed cannot be obtained.

In Patent Document 2 and Patent Document 3, it is proposed to use a titanium acid ester compound such as diisopropoxytitanium bis (alkylacetoacetonate) as a catalyst, but it is contained in the additive or filler in the composition. It is easily decomposed by the moisture, and the curing speed varies depending on the humidity at the time of construction, so that there is a problem that a stable cured product cannot be obtained.

Patent Document 4 proposes to use a titanium tetracarboxylic dian compound as a catalyst, but there is a problem that practical satisfaction with respect to the curing rate cannot be obtained.
Patent Document 5 proposes to use a quaternary ammonium salt as a catalyst, but there is a problem that a sufficient curing rate cannot be obtained at the time of construction.

Therefore, it has been desired to develop a curing catalyst having high safety (low toxicity and environmental pollution) and a practical curing rate.

In view of the prior art, an object of the present invention is to provide a curing catalyst having high safety and a practical curing rate.

According to the present invention, it is a curing catalyst [B] used for curing a polymer [A] having a reactive hydrolyzable silicon-containing group.
The curing catalyst [B] contains a complex of a titanium compound [B1] and an organic onium salt [B2].
As the titanium compound [B1], a curing catalyst [B] represented by the chemical formula (1) is provided.
(R1 ^- O) _n Ti-A _4-n (1)
(In the formula, R ¹ is a substituted or unsubstituted hydrocarbon group, n is 1 to 4, and A is a β-diketone group).

As a result of diligent studies, the present inventor has found that when a curing catalyst [B] containing a composite of a titanium compound [B1] and an organic onium salt [B2] is used, the curing rate of the polymer [A] is high. It was found that the invention was significantly increased, and the present invention was completed. Since this catalyst does not contain tin, it is highly safe. In addition, it can be manufactured at low cost.

Hereinafter, the present invention will be described in detail.

The curing catalyst [B] of the present invention is used for curing a polymer [A] having a reactive hydrolyzable silicon-containing group. The polymer [A] is preferably liquid at room temperature.

1. 1. Polymer [A]
The polymer [A] has at least one reactive hydrolyzable silicon-containing group per molecule at the terminal or side chain. The reactive hydrolyzable silicon-containing group may be present at the terminal of the polymer [A] molecule, at the side chain, or at both the terminal and the side chain. The number of reactive hydrolyzable silicon-containing groups may be at least one per molecule of the polymer [A], but the number is 1.5 or more per molecule on average in terms of curing rate and cured physical characteristics. Is preferable. A known method can be adopted as a method for binding the reactive hydrolyzable silicon-containing group to the main chain polymer.

A reactive hydrolyzable silicon-containing group is a group having a silicon atom bonded to a hydrolyzable group (eg, halogen, alkoxy, alkenyloxy, asyloxy, amino, aminooxy, oxime, amide) or a reactive group consisting of a hydroxyl group. It has the property of causing a condensation reaction by using a catalyst or the like as needed in the presence of moisture or a cross-linking agent. Specific examples thereof include a halide silyl group, an alkoxysilyl group, an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group, an aminooxysilyl group, an oximsilyl group, and an amidosilyl group.

Here, the number of reactive hydrolyzable groups bonded to one silicon atom is selected from the range of 1 to 3. Further, the reactive hydrolyzable group bonded to one silicon atom may be one kind or a plurality of kinds. Further, the reactive hydrolyzable group and the non-reactive hydrolyzable group may be bonded to one silicon atom, or the hydrolyzable group and the 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 because it is easy to handle.

Further, among the above-mentioned alkoxysilyl groups, the trialkoxysilyl group is preferable because it has high activity and good curability can be obtained, and the obtained cured product is excellent in restorability, 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 obtained cured product has high elongation and high strength.
When the polymer [A] in which the reactive hydrolyzable silicon-containing group is a dialkoxysilyl group and the polymer [A] in which a trialkoxysilyl group is used in combination, it is preferable to balance the physical properties and curability of the cured product. ..

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

(Organic polymer [A1])
The main chain of the organic polymer [A1] used in the present invention is one having a carbon atom, for example, an alkylene oxide polymer, a polyester polymer, an ether / ester block copolymer, a polymer of an ethylenically unsaturated compound, or a diene. Examples thereof include polymers of system compounds.

As the alkylene oxide polymer, the alkylene oxide polymer
[CH ₂ CH ₂ O] _n
[CH (CH ₃ ) CH ₂ O] _n
[CH (C ₂ H ₅ ) CH ₂ O] _n
[CH ₂ CH ₂ CH ₂ CH ₂ O] _n
Such as those having one kind or two or more kinds of repeating units are exemplified. Here, n is the same or different integer of 2 or more. These alkylene oxide polymers may be used alone or in combination of two or more. Further, a copolymer containing two or more of the above repeating units can also be used.

Examples of the polyester polymer include carboxylic acids such as acetic acid, propionic acid, maleic acid, phthalic acid, citric acid, pyruvate, and lactic acid and their anhydrides, and their intramolecular and / or intermolecular esters and their substitutions. Examples are those having as a repeating unit.

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 the repeating unit.

Examples of the polymer of the ethylenically unsaturated compound and the diene compound include homopolymers such as ethylene, propylene, acrylic acid ester, methacrylic acid ester, vinyl acetate, acrylonitrile, styrene, isobutylene, butadiene, isoprene and chloroprene, or Examples thereof include these two or more kinds of copolymers. More specifically, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-butadiene copolymer, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid. Ester copolymer, polyisoprene, styrene-isoprene copolymer, isobutylene-isoprene copolymer, polychloroprene, styrene-chloroprene copolymer, acrylonitrile-chloroprene copolymer, polyisobutylene, polyacrylic acid ester, polymethacrylic acid Examples include esters. These may be used alone or in combination of two or more.

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 nitrogen-containing characteristic group include a (thio) urethane group-derived linking group such as a (thio) urethane group, an allophanate group, another N-substituted urethane group, and an N-substituted allophanate group, and a (thio) urea group. Biling group derived from (thio) urea group such as biuret group, other N-substituted urea group, N, N'-substituted urea group, N-substituted biuret group, N, N'-substituted biuret group, amide group, Examples include, but are limited to, a binding group derived from an amide group such as an N-substituted amide group, a nitrogen-containing characteristic group represented by a binding group derived from an imino group, a (thio) ester group, a (thio) ether group, and the like. Not done. Among these, a nitrogen-containing characteristic group is preferable because of its high curability, and a (thio) urethane group-derived binding group and a (thio) urea-derived binding group are more preferable because of its ease of synthesis. Further, only one nitrogen-containing characteristic group may be contained in the organic polymer [A1], and one or more nitrogen-containing characteristic groups may be further contained. Here, the notations of "(thio)" and "N-substitution" are the same as above.

When the organic polymer [A1] contains a polar group such as the nitrogen-containing characteristic group, the toughness of the cured product is improved, and the curability and adhesive strength are enhanced. 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 enhanced. 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 polar groups of the nitrogen-containing characteristic groups are strongly attracted to each other, so that the molecules of the curable resin are also strongly bound to each other (domain formation), thereby exhibiting toughness in the cured product. Further, when the crosslinkable silicon group is linked to the main chain via a polar group such as a nitrogen-containing characteristic group, the crosslinkable silicon groups are also close to each other when forming a domain between the nitrogen-containing characteristic groups. As a result, it is considered that the contact probability between the crosslinkable silicon groups is also improved, and further, the condensation reactivity between the crosslinkable silicon groups is improved by catalytic curing by the polar group in the nitrogen-containing characteristic group.

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. .. Commercially available products include, for example, Kaneka MS Polymer series (MS Polymer S203, MS Polymer S303, MS Polymer S903, MS Polymer S911, MS Polymer SAX520, etc.) and Cyril Series (Cyril Polymer SAT200, Cyril) manufactured by Kaneka Corporation. Polymer MA430, Cyril Polymer MAX447, etc.), MA series, SA series, OR series; ES series (ES-GX3440ST, etc.) manufactured by Asahi Glass Co., Ltd., ESGX series, etc. are exemplified.

The number average molecular weight of the organic polymer [A1] used in the present invention is not particularly limited, but an excessively high polymer has a high viscosity and is difficult to use in the case of a curable composition, so 30,000. The following is desirable. Such an organic polymer can be produced by a known method, but a commercially available product such as the above-mentioned Kaneka MS Polymer manufactured by Kaneka Corporation may be used.

(Organopolysiloxane [A2])
The organopolysiloxane [A2] used in the present invention has a main chain composed of a siloxane bond represented by Si—O, and further has an organic group bonded to a silicon atom constituting the siloxane bond. Specific examples of such an organic group include an alkyl group such as methyl, ethyl, propyl and butyl; a cycloalkyl group such as cyclohexyl; an alkenyl group such as vinyl, isopropenyl and substituted vinyl; an allyl group, crotyl, methallyl and the like. Substituent allyl groups; aryl groups such as phenyl, toluyl, 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 groups. Examples thereof include 3,3,3-trifluoropropyl groups.

As an organopolysiloxane [A2],
(-Si (R) ₂ -O-) _m
(In the formula, R is the same or different organic group, and m is an integer of 2 or more.)
Those having a repeating unit represented by are exemplified. As a specific example,
(-Si (CH ₃ ) ₂ -O-) _m
(-Si (C ₂ H ₅ ) ₂ -O-) _m
(-Si (Ph) ₂ -O-) _m
(-Si (-CH = CH ₂ ) ₂ -O-) _m
Such as those having one kind or two or more kinds of repeating units are exemplified. Here, m is the same or different integer of 2 or more. The organopolysiloxane [A2] may be composed of a single main chain, or may be composed of two or more types of main chains.

The organopolysiloxane may be linear or branched, including trifunctional (R'SiO _1.5 ) or tetrafunctional (SiO ₂ ). Further, depending on the physical characteristics and use of the cured product, a bifunctional form ( _R'2 SiO) or a monofunctional form ( _R'3 SiO _0.5 ) may be combined as needed (where R'is an organic group. ). Further, the hydrolyzable silicon-containing group may be bonded to either the end of the molecule or the middle of the molecular chain.
The organopolysiloxane is generally represented by Ra SiO _{4-a / 2 as} an average composition formula (for example, JP-A-2005-194399, JP-A-8-151521, etc.). The above notation followed this.

The viscosity of the organopolysiloxane [A2] used in the present invention is not particularly limited, but an excessively high viscosity may reduce workability or impair the physical properties of the obtained cured product. It is desirable that the viscosity at ° C is in the range of 0.025 to 100 Pa · s. Such organopolysiloxanes can be produced by known methods, but are manufactured by GE Toshiba Silicone Co., Ltd.'s Tosseal series, Shin-Etsu Chemical Co., Ltd.'s sealant series, and Toray Dow Corning Co., Ltd. Commercially available products such as SH series can be used.

2. 2. Curing catalyst [B]
The curing catalyst [B] contains a complex of a titanium compound [B1] and an onium salt [B2]. This complex is a reaction product that can be obtained by reacting a titanium compound [B1] with an onium salt [B2].

<Titanium compound [B1]>
The titanium compound [B1] is represented by the chemical formula (1).
(R1 ^- O) _n Ti-A _4-n (1)
(In the formula, R ¹ is a substituted or unsubstituted hydrocarbon group, n is 1 to 4, and A is a β-diketone group).

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

The substituted or unsubstituted hydrocarbon group represented by ^R1 is a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, and an aliphatic hydrocarbon group is preferable.

Hydrocarbon groups include alkyl groups (eg, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl) and oxyalkylenes. Group etc. can be mentioned.

At least one of R ¹ is preferably an alkyl group having 8 or more carbon atoms or an oxyalkylene group. At least one of R ¹ 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 carbon number 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, and 7, and may be within the range between any two of the numerical values exemplified here. The other hydrocarbon group is preferably an alkyl group, more preferably a branched alkyl group. The number of other hydrocarbon groups is 0, 1, 2, 3 or 4.

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 carbon number is, for example, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, and is between any two of the numerical values exemplified here. It may be within the range of.

The oxyalkylene group is represented by the chemical formula (3). 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 is exemplified here. It may be within the range between any two of the given numerical values.
R ^6- (OR ⁷ ) m- (3)
(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). What is represented, etc.

The carbon number of R ⁶ is preferably 1 to 6, more preferably 1 to 4, the number of carbon atoms of R ⁷ is preferably 2 to 6, more preferably 2 to 3, and m is preferably 1 to 6 and 1 to 2. More preferred.

Examples of the oxyalkylene group include a group obtained by removing the terminal hydroxyl group from the alcohol shown below. Examples of 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 monot-butyl ether, and 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 monot-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 and propylene glycol mono t-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, di Examples thereof include propylene glycol monopentyl ether, dipropylene glycol monoisopropyl ether and dipropylene glycol monot-butyl ether. For example, when the alcohol is butyl carbitol (also known as 2- (2-butoxyethoxy) ethanol), the oxyalkylene group becomes 2- (2-butoxyethoxy) ethyl, and the alcohol is butyl cellosolve (also known as 2-butoxyethanol). ), The oxyalkylene group is 2-butoxyethyl.

The β-diketone group represented by A includes 2,4-pentandione, 2,4-hexanedione, 2,4-pentadecandione, 2,2,6,6-tetramethyl-3,5-heptandione, 1 -Phenyl-1,3-butandione, 1-aryl-1,3-butandione such as 1- (4-methoxyphenyl) -1,3-butandione, 1,3-diphenyl-1,3-propanedione, 1, 1,3-Diaryl-1,3-propanedione such as 3-bis (2-pyridyl) -1,3-propanedione, 1,3-bis (4-methoxyphenyl) -1,3-propanedione, 3 -Diketones such as benzyl-2,4-pentandione, ketoesters such as methylacetate, ethylacetate, butylacetate, t-butylacetate, ethyl-3-oxohexanoate, N, N-dimethyl Ketoamides such as acetoacetamide, N, N-diethylacetacetamide and acetoacetanilide, malonic acid esters such as dimethylmalonate, diethylmalonate and diphenylmalonate, N, N, N', N'- Examples of malonic acid amides such as tetramethylmalonamide, N, N, N', N'-tetraethylmalonamide include 2,4-pentandione, 1-aryl-1,3-butandione and 1,3-diaryl. Diketones such as -1,3-propanedione are particularly preferred.

Among the titanium compounds represented by the chemical formula (1), tetraisopropoxytitanium, triisopropoxyoctoxytitanium, and triisopropoxy2- (2-butoxyethoxy) are used in terms of catalytic activity, compound stability, and handleability. Ethoxytitanium triisopropoxy 2-butoxyethoxytitanium is more preferred.
The above titanium compound [B1] may be used alone or in combination of two or more.

<Organic onium salt [B2]>
The organic onium salt [B2] is a salt containing organic onium. Examples of the organic onium include those in which at least one hydrogen atom of onium is substituted with a hydrocarbon group, and those in which all hydrogen atoms of onium are substituted with a hydrocarbon group are preferable. Hydroxyldo is exemplified as the counter anion of organic onium, but other anions may be used. , Quaternary ammonium salt, quaternary phosphonium salt, quaternary imidazolium salt, quaternary pyrrolidinium salt, quaternary pyridinium salt, quaternary piperidinium salt, quaternary piperidinium salt, as organic onium salt [B2]. Pyridinium salt, tertiary sulfonium salt, tertiary oxonium salt and the like can be mentioned. The organic onium salt [B2] is preferably an organic onium salt other than the quaternary ammonium hydroxide, and more preferably a quaternary phosphonium salt.

The organic onium salt [B2] is more preferably a quaternary phosphonium hydroxide represented by the following formula (2).

(In the formula, R ² , R ³ , R ⁴ , and R ⁵ represent substituted or unsubstituted hydrocarbon groups that are the same or different from each other. X represents a hydroxyl group.)

The substituted or unsubstituted hydrocarbon group represented by R ² , R ³ , R ⁴ , R ⁵ is a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, and an aliphatic hydrocarbon group is preferable. As the aliphatic hydrocarbon group, a linear or branched alkyl group is preferable. The hydrocarbon group preferably has 1 to 16 carbon atoms. Specifically, the carbon number is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, and the numerical values exemplified here. It may be within the range between any two of the above. Examples of the aliphatic hydrocarbon group include a saturated hydrocarbon group such as 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 and an octyl group, and vinyl. Examples thereof include an unsaturated hydrocarbon group such as a group, an allyl group, a prenyl group, a crotyl group and a cyclopentadienyl group, and a methyl group, an ethyl group, a butyl group, an octyl group, a dodecyl group and a hexadecyl group are preferable.

Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a benzyl group and the like.

Examples of the substituent of the hydrocarbon group include a methoxy group, an ethoxy group, a hydroxy group, an acetoxy group and the like. Substituted aliphatic or aromatic hydrocarbon groups include alkoxyalkyl groups such as methoxymethyl group, methoxyethyl group, ethoxymethyl group and ethoxyethyl group, hydroxymethyl group, hydroxyethyl group and 3-hydroxypropyl. Examples thereof include a hydroxyalkyl group such as a group and a 2-acetoxyethyl group.

Specific examples of the phosphonium hydroxyd group represented by the chemical formula (2) include tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrapropylphosphonium hydroxide, tetrabutylphosphonium hydroxide, tetraoctylphosphonium hydroxide, and tributyldodecylphosphonium hydroxydo. Do, tributylhexadecylphosphonium hydroxide, butyltriphenylphosphonium hydroxide, benzyltriphenylphosphonium hydroxydo, tetraphenylphosphonium hydroxydo, etc., in particular tetrabutylphosphonium hydroxide, tetraoctylphosphonium hydroxide, tributyldodecylphosphonium hydroxydo De, tributylhexadecylphosphonium hydroxide is preferred.

<Reaction of titanium compound [B1] and organic onium salt [B2]>
The complex of the titanium compound [B1] and the organic onium salt [B2] is, for example, a transparent liquid, and can be obtained by reacting a mixture of both at, for example, 40 to 100 ° C. Specifically, this temperature is, for example, 40, 50, 60, 70, 80, 90, 100 ° C., and may be in the range between any two of the numerical values exemplified here. The molar ratio of the titanium compound [B1] to the organic onium salt [B2] in the mixture is, for example, 0.1 to 100, 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 numerical values exemplified here.

3. 3. Moisture-curable composition The moisture-curable composition of the present invention contains the above-mentioned curing catalyst [B] and polymer [A], and may contain other additives described later, if necessary. The moisture-curable composition of the present invention may be prepared by mixing the two under dry conditions, and the mixing form thereof is not particularly limited. Usually, it may be mixed in an atmosphere of about 15 to 30 ° C. and 60% RH or less.

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

The filler [C] may be further added to the moisture-curable composition of the present invention. Examples of the filler include calcium carbonate, kaolin, talc, fumed silica, precipitated silica, silicic acid anhydride, hydrous silicic acid, clay, calcined clay, glass, bentonite, organic bentonite, silasburn, glass fiber, asbestos, and the like. Examples thereof include glass filament, crushed 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. The addition of the filler improves the handling of the moisture-curable composition. It also works as a rubber reinforcing agent for cured products. The biggest merit is that the amount of resin used can be reduced by adding it as a bulking agent, so that the cost can be reduced.

Among them, calcium carbonate and titanium oxide are preferable from the viewpoint of maintaining excellent surface non-tack, 50% modulus, workability, weather resistance and the like of the curable composition after curing. When calcium carbonate is used, the ratio thereof is preferably 1 to 200 parts by weight, more preferably 50 to 200 parts by weight, based on 100 parts by weight of the polymer [A]. Within the above range, the characteristics after curing are not impaired.

In the moisture-curable composition of the present invention, other curing catalysts, curing accelerators, colorants, plasticizers, curing retarders, sagging inhibitors, antiaging agents, solvents and the like are usually added to the curable composition. Additives may be added.

Examples of other curing catalysts include organic tin compounds such as dibutyltin dilaurate and dibutyltin bis (acetylacetonate), organic aluminum compounds such as aluminumtris (acetylacetonate) and aluminumtris (ethylacetoacetate), and zirconium tetra (acetyl). Acetonate), organic zirconium compounds such as zirconite tetrabutyrate, metal curing catalysts such as 8-diazabicyclo [5,4,0] undecene-7 (DBU), 2-tertiary butyl-1,1,3,3- Examples thereof include amine compounds such as tetramethylguanidine 1,5,7-triazabicyclo [4.4.0] -5-decene, ethylenediamine, diethylenetriamine, 3,3-diaminopropylamine and triethylenetetramine.

As the curing accelerator, for example, various known amino group-substituted alkoxysilane compounds or condensates thereof can be used. Specifically, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, δ-aminobutyl (methyl) diethoxysilane, N, N-bis (tri). Examples thereof include methoxysilylpropyl) ethylenediamine and partial hydrolysis of these, which also have the effect of improving the adhesion to the substrate.

Specifically, iron oxide, carbon black, phthalocyanine blue, phthalocyanine green, etc. are used as the colorant.

Specific examples of the plasticizer include phthalates such as dibutylphthalate, dioctylphthalate, and butylbenzylphthalate; fatty acid carboxylic acid esters such as dioctyl adipate, dioctyl succinate, diisodecyl succinate, and butyl oleate; penta. Glycol esters such as erythritol esters; phosphate esters such as trioctyl phosphate and tricresyl phosphate; epoxy plasticizers such as epoxidized soybean oil and benzyl epoxy stearate; chlorinated paraffin and the like are used.

Specifically, hydrogenated castor oil, silicic acid anhydride, organic bentonite, colloidal silica, etc. are used as the sagging preventive agent.

Further, as other additives, adhesive-imparting agents such as phenol resin and epoxy resin, ultraviolet absorbers, radical chain inhibitors, peroxide decomposition agents, various antioxidants and the like are used.

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

From 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, and automobiles, adhesives, sealing agents, and sealing materials for waterproofing.

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

<Production Example 1: Tetrabutylphosphonium salt (complex 1)>
6.7874 g (0.02 mol) of tetrabutylphosphonium bromide is dissolved in 20 ml of dehydrated methanol and filled with 20 ml of strongly basic ion exchange resin (Amberlite IRA900 (OH) -HG; Organo's pre-dehydrated methanol replacement). Then, about 35 ml of dehydrated methanol was passed through the column to obtain 66.0555 g of a tetrabutylphosphonium hydroxydomethanol solution having a hydroxy compound conversion ratio of 55.3%.

55.9491 g of this methanol solution was passed through a column filled with 20 ml of a strongly basic ion exchange resin (Amberlite IRA900 (OH) -HG; Organo's pre-dehydrated methanol replacement), and subsequently. 35 ml or more of dehydrated methanol was passed through to obtain 98.3155 g of a tetrabutylphosphonium hydroxydomethanol solution having a hydroxy compound conversion rate of 99.5%.

The obtained methanol solution was concentrated under reduced pressure at 25 ° C. (final decompression degree 85 mmHg) to obtain a 17.6% methanol solution (tetrabutylphosphonium hydroxide: methanol = 1:40).

Tetraisopropoxytitanium: 8.52 g (0.03 mol) and 17.6% tetrabutylphosphonium hydroxydomethanol solution: 15.69 g (0.01 mol) were placed in this order in a 100 mL eggplant flask, replaced with nitrogen, and then placed in a stirrer. And mixed well. The mixture was heated in a water bath at 60 ° C. and concentrated under reduced pressure (final reduced pressure of 14 mmHg) to distill off isopropanol and methanol to obtain 8.39 g of a pale yellow solid tetrabutylphosphonium salt (complex 1). Further, 2.1 g of isopropanol was added, and the mixture was heated and dissolved in a water bath at 60 ° C. to obtain 10.39 g of a pale yellow liquid.

<Production Example 2: Tetraethylphosphonium salt (complex 2)>
4.5434 g (0.02 mol) of tetraethylphosphonium bromide was dissolved in 20 ml of dehydrated methanol and filled with 20 ml of a strongly basic ion exchange resin (Amberlite IRA900 (OH) -HG; Organo's pre-dehydrated methanol replacement). The column was passed through a column, and then about 35 ml of dehydrated methanol was passed through the column to obtain 66.7811 g of a tetraethylphosphonium hydroxydomethanol solution having a hydroxy compound conversion rate of 54.9%.

56.6752 g of this methanol solution was passed through a column filled with 20 ml of a strongly basic ion exchange resin (Amberlite IRA900 (OH) -HG; Organo's pre-dehydrated methanol replacement), and subsequently. 35 ml or more of dehydrated methanol was passed through to obtain 99.0416 g of a tetraethylphosphonium hydroxydomethanol solution having a hydroxy compound conversion rate of 96.7%.

The obtained methanol solution was concentrated under reduced pressure at 25 ° C. (final reduced pressure degree 85 mmHg) to obtain a 11.4% methanol solution (tetraethylphosphonium hydroxide: methanol = 1:40).

Tetraisopropoxytitanium: 8.52 g (0.03 mol), 11.4% tetraethylphosphonium hydroxydomethanol solution: 14.41 g (0.01 mol) was placed in this order in a 100 mL eggplant flask, replaced with nitrogen, and then stirred. It was mixed well. The mixture was heated in a water bath at 60 ° C. and concentrated under reduced pressure (final reduced pressure of 17 mmHg) to distill off isopropanol and methanol to obtain 7.23 g of a yellow liquid tetraethylphosphonium salt (complex 2). Further, 1.82 g of isopropanol was added, and the mixture was heated and dissolved in a water bath at 60 ° C. to obtain 8.94 g of a yellow liquid.

<Production Example 3: Tetraoctylphosphonium salt (complex 3)>
11.2743 g (0.02 mol) of tetraoctylphosphonium bromide is dissolved in 20 ml of dehydrated methanol and filled with 20 ml of strongly basic ion exchange resin (Amberlite IRA900 (OH) -HG; Organo's pre-dehydrated methanol replacement). Then, about 35 ml of dehydrated methanol was passed through the column to obtain 62.133 g of a tetraoctylphosphonium hydroxydomethanol solution having a hydroxy compound conversion rate of 52.6%.

51.9749 g of this methanol solution was passed through a column filled with 20 ml of a strongly basic ion exchange resin (Amberlite IRA900 (OH) -HG; Organo's pre-dehydrated methanol replacement), and subsequently. 35 ml or more of dehydrated methanol was passed through to obtain 87.9017 g of a tetraoctylphosphonium hydroxydethanol solution having a hydroxy compound conversion rate of 94.9%.

The obtained methanol solution was concentrated under reduced pressure at 25 ° C. (final decompression degree 85 mmHg) to obtain a 27.8% methanol solution (tetraoctylphosphonium hydroxide: methanol = 1:40).

Tetraisopropoxytitanium: 8.52 g (0.03 mol) and 27.8% tetraoctylphosphonium hydroxydomethanol solution: 18.03 g (0.01 mol) were placed in this order in a 100 mL eggplant flask, replaced with nitrogen, and then placed in a stirrer. And mixed well. The mixture was heated in a water bath at 60 ° C. and concentrated under reduced pressure (final reduced pressure of 17 mmHg) to distill off isopropanol and methanol to obtain 10.83 g of a yellow liquid tetraoctylphosphonium salt (complex 3). Further, 2.71 g of isopropanol was added, and the mixture was heated and dissolved in a water bath at 60 ° C. to obtain 13.26 g of a yellow liquid.

<Production Example 4: Tributyldodecylphosphonium salt (complex 4)>
Tributyldodecylphosphonium bromide 9.0353 g (0.02 mol) is dissolved in 20 ml of dehydrated methanol and filled with 20 ml of strongly basic ion exchange resin (Amberlite IRA900 (OH) -HG; Organo's pre-dehydrated methanol replacement). Then, about 35 ml of dehydrated methanol was passed through the column to obtain 62.3120 g of a tributyldodecylphosphonium hydroxydomethanol solution having a hydroxy compound conversion rate of 49.5%.

52.1445 g of this methanol solution was passed through a column filled with 20 ml of a strongly basic ion exchange resin (Amberlite IRA900 (OH) -HG; Organo's pre-dehydrated methanol replacement), and subsequently. 35 ml or more of dehydrated methanol was passed through to obtain 94.7871 g of a tributyldodecylphosphonium hydroxydomethanol solution having a hydroxy compound conversion rate of 98.0%.

The obtained methanol solution was concentrated under reduced pressure at 25 ° C. (final decompression degree 85 mmHg) to obtain a 23.2% methanol solution (tributyldodecylphosphonium hydroxide: methanol = 1:40).

Tetraisopropoxytitanium: 8.52 g (0.03 mol) and 23.2% tributyldodecylphosphonium hydroxydomethanol solution: 16.79 g (0.01 mol) were placed in this order in a 100 mL eggplant flask, replaced with nitrogen, and then placed in a stirrer. And mixed well. The mixture was heated in a water bath at 60 ° C. and concentrated under reduced pressure (final reduced pressure of 17 mmHg) to distill off isopropanol and methanol to obtain 9.64 g of a yellow liquid tributyldodecylphosphonium salt (complex 4). Further, 2.43 g of isopropanol was added, and the mixture was heated and dissolved in a water bath at 60 ° C. to obtain 11.78 g of a yellow liquid.

<Production Example 5: Tributylhexadecylphosphonium salt (complex 5)>
10.538 g (0.02 mol) of tributylhexadecylphosphonium bromide was dissolved in 20 ml of dehydrated methanol, and 20 ml of a strongly basic ion exchange resin (Amberlite IRA900 (OH) -HG; Organo's pre-dehydrated methanol was replaced). A solution was passed through the packed column, and then about 35 ml of dehydrated methanol was passed to obtain 677.7780 g of a tributylhexadecylphosphonium hydroxydomethanol solution having a hydroxy compound conversion rate of 52.9%.

57.6370 g of this methanol solution was passed through a column filled with 20 ml of a strongly basic ion exchange resin (Amberlite IRA900 (OH) -HG; Organo's pre-dehydrated methanol replacement), and subsequently. 35 ml or more of dehydrated methanol was passed through to obtain 101.0659 g of a tributylhexadecylphosphonium hydroxydomethanol solution having a hydroxy compound conversion rate of 98.1%.

The obtained methanol solution was concentrated under reduced pressure at 25 ° C. (final decompression degree 85 mmHg) to obtain a 25.7% methanol solution (tributylhexadecylphosphonium hydroxide: methanol = 1:40).

Tetraisopropoxytitanium: 8.52 g (0.03 mol) and 25.7% tributylhexadecylphosphonium hydroxydomethanol solution: 17.32 g (0.01 mol) were placed in this order in a 100 mL eggplant flask, replaced with nitrogen, and then stirred. Was thoroughly mixed in. The mixture was heated in a water bath at 60 ° C. and concentrated under reduced pressure (final reduced pressure of 17 mmHg) to distill off isopropanol and methanol to obtain 9.92 g of a yellow liquid tributylhexadecylphosphonium salt (complex 5). Further, 2.50 g of isopropanol was added, and the mixture was heated and dissolved in a water bath at 60 ° C. to obtain 12.08 g of a yellow liquid.

<Production Example 6: Butyltriphenylphosphonium salt (complex 6)>
7.986 g (0.02 mol) of butyltriphenylphosphonium bromide was dissolved in 20 ml of dehydrated methanol, and 20 ml of a strongly basic ion exchange resin (Amberlite IRA900 (OH) -HG; Organo's pre-dehydrated methanol was substituted) was added. A solution was passed through the packed column, and then about 35 ml of dehydrated methanol was passed to obtain 65.5451 g of a butyltriphenylphosphonium hydroxydomethanol solution having a hydroxy form conversion rate of 50.5%.

55.389 g of this methanol solution was passed through a column filled with 20 ml of a strongly basic ion exchange resin (Amberlite IRA900 (OH) -HG; Organo's pre-dehydrated methanol replacement), and subsequently. 35 ml or more of dehydrated methanol was passed through to obtain 98.8179 g of a butyltriphenylphosphonium hydroxydomethanol solution having a hydroxy compound conversion rate of 97.9%.

The obtained methanol solution was concentrated under reduced pressure at 25 ° C. (final reduced pressure degree 85 mmHg) to obtain a 20.8% methanol solution (butyltriphenylphosphonium hydroxide: methanol = 1:40).

Tetraisopropoxytitanium: 8.52 g (0.03 mol), 20.8% butyltriphenylphosphonium hydroxydomethanol solution: 16.17 g (0.01 mol) was placed in this order in a 100 mL eggplant flask, replaced with nitrogen, and then stirred. Was thoroughly mixed in. The mixture was heated in a water bath at 60 ° C. and concentrated under reduced pressure (final reduced pressure of 18 mmHg) to distill off isopropanol and methanol to obtain 8.40 g of a pale yellow solid butyltriphenylphosphonium salt (complex 6). Further, 2.10 g of isopropanol was added, and the mixture was heated and dissolved in a water bath at 60 ° C. to obtain 10.35 g of a yellow liquid.

<Production Example 7: Tributyldodecylphosphonium salt (complex 7)>
The same operation as in Production Example 4 was carried out to obtain a tributyldodecylphosphonium hydroxydomethanol solution having a hydroxy compound conversion rate of 99.9%. The obtained methanol solution was concentrated under reduced pressure at 25 ° C. (final reduced pressure degree: 85 mmHg) to obtain a 17.0% methanol solution (tributyldodecylphosphonium hydroxide: methanol = 1:60).

Tetraisopropoxytitanium: 8.52 g (0.03 mol) and 17.0% tributyldodecylphosphonium hydroxydomethanol solution: 22.88 g (0.01 mol) were placed in this order in a 100 mL eggplant flask, replaced with nitrogen, and then placed in a stirrer. And mixed well. The mixture was heated in a water bath at 60 ° C. and concentrated under reduced pressure (final reduced pressure of 12 mmHg) to distill off isopropanol and methanol to obtain 8.72 g of a yellow liquid tributyldodecylphosphonium salt (complex 7). Of this, 1.00 g of isopropanol was further added to 4.00 g, and the mixture was heated and dissolved in a water bath at 60 ° C. to obtain 4.70 g of a yellow liquid.

<Production Example 8: Tributyldodecylphosphonium salt (complex 8)>
The same operation as in Production Example 4 was carried out to obtain a tributyldodecylphosphonium hydroxydomethanol solution having a hydroxy compound conversion rate of 99.9%. The obtained methanol solution was concentrated under reduced pressure at 25 ° C. (final reduced pressure degree: 85 mmHg) to obtain a 36.4% methanol solution (tributyldodecylphosphonium hydroxide: methanol = 1:20).

Tetraisopropoxytitanium: 8.52 g (0.03 mol) and 36.4% tributyldodecylphosphonium hydroxydomethanol solution: 10.68 g (0.01 mol) were placed in this order in a 100 mL eggplant flask, replaced with nitrogen, and then placed in a stirrer. And mixed well. The mixture was heated in a water bath at 60 ° C. and concentrated under reduced pressure (final reduced pressure of 17 mmHg) to distill off isopropanol and methanol to obtain 9.99 g of a yellow liquid tributyldodecylphosphonium salt (complex 8). Of this, 1.25 g of isopropanol was further added to 5.00 g, and the mixture was heated and dissolved in a water bath at 60 ° C. to obtain 6.13 g of a yellow liquid.

<Production Example 9: Tributyldodecylphosphonium salt (complex 9)>
The same operation as in Production Example 4 was carried out to obtain a tributyldodecylphosphonium hydroxydomethanol solution having a hydroxy compound conversion rate of 97.5%. The obtained methanol solution was concentrated under reduced pressure at 25 ° C. (final reduced pressure degree: 85 mmHg) to obtain a 16.9% methanol solution (tributyldodecylphosphonium hydroxide: methanol = 1:60).

Tetraisopropoxytitanium: 7.10 g (0.025 mol) and 16.9% tributyldodecylphosphonium hydroxydomethanol solution: 11.47 g (0.005 mol) were placed in this order in a 100 mL eggplant flask, replaced with nitrogen, and then placed in a stirrer. And mixed well. The mixture was heated in a water bath at 60 ° C. and concentrated under reduced pressure (final reduced pressure of 17 mmHg) to distill off isopropanol and methanol to obtain 6.22 g of a pale yellow liquid tributyldodecylphosphonium salt (complex 9).

<Production Example 10: Tributyldodecylphosphonium salt (complex 10)>
The same operation as in Production Example 4 was carried out to obtain a tributyldodecylphosphonium hydroxydomethanol solution having a hydroxy compound conversion rate of 98.8%. The obtained methanol solution was concentrated under reduced pressure at 25 ° C. (final reduced pressure degree: 85 mmHg) to obtain a 16.8% methanol solution (tributyldodecylphosphonium hydroxide: methanol = 1:60).

Tetraisopropoxytitanium: 5.68 g (0.020 mol) and 16.8% tributyldodecylphosphonium hydroxydomethanol solution: 11.57 g (0.005 mol) were placed in this order in a 100 mL eggplant flask, replaced with nitrogen, and then placed in a stirrer. And mixed well. The mixture was heated in a water bath at 60 ° C. and concentrated under reduced pressure (final reduced pressure of 17 mmHg) to distill off isopropanol and methanol to obtain 5.34 g of a yellow liquid tributyldodecylphosphonium salt (complex 10).

<Production Example 11: Tributyldodecylphosphonium salt (complex 11)>
The same operation as in Production Example 4 was carried out to obtain a tributyldodecylphosphonium hydroxydomethanol solution having a hydroxy compound conversion rate of 98.8%. The obtained methanol solution was concentrated under reduced pressure at 25 ° C. (final reduced pressure degree: 85 mmHg) to obtain a 16.8% methanol solution (tributyldodecylphosphonium hydroxide: methanol = 1:60).

Tetraisopropoxytitanium: 5.68 g (0.02 mol) and 16.8% tributyldodecylphosphonium hydroxydomethanol solution: 23.13 g (0.01 mol) were placed in this order in a 100 mL eggplant flask, replaced with nitrogen, and then placed in a stirrer. And mixed well. The mixture was heated in a water bath at 60 ° C. and concentrated under reduced pressure (final reduced pressure of 11 mmHg) to distill off isopropanol and methanol to obtain 7.04 g of a yellow liquid tributyldodecylphosphonium salt (complex 11).

<Production Example 12: Tributyldodecylphosphonium salt (complex 12)>
The same operation as in Production Example 4 was carried out to obtain a tributyldodecylphosphonium hydroxydomethanol solution having a hydroxy compound conversion rate of 97.5%. The obtained methanol solution was concentrated under reduced pressure at 25 ° C. (final reduced pressure degree: 85 mmHg) to obtain a 16.9% methanol solution (tributyldodecylphosphonium hydroxide: methanol = 1:60).

Tetraisopropoxytitanium: 2.84 g (0.01 mol) and 16.9% tributyldodecylphosphonium hydroxydomethanol solution: 22.94 g (0.01 mol) were placed in this order in a 100 mL eggplant flask, replaced with nitrogen, and then placed in a stirrer. And mixed well. The mixture was heated in a water bath at 60 ° C. and concentrated under reduced pressure (final reduced pressure of 16 mmHg) to distill off isopropanol and methanol to obtain 5.23 g of a yellow liquid tributyldodecylphosphonium salt (complex 12).

(Preparation of moisture-curable composition)
Using each component obtained in the above production example and a commercially available component, the components were blended in the blending ratio (parts by mass) shown in Table 1 and kneaded to prepare a moisture-curable composition. The operations of blending, kneading, and curing the materials were performed at 25 ± 1 ° C. and in an atmosphere of 50 to 60% RH.

<Measurement of tack free time>
The tack-free time (the time required from the end of kneading to the time when the sample did not adhere to the fingertips by lightly touching three points on the surface with a fingertip cleaned with ethyl alcohol) was measured for the obtained moisture-curable composition. .. The results of the tack free time measurement are shown in Table 1.

As shown in Examples and Comparative Examples, a remarkable improvement in activity is observed when the titanium compound [B1] and the phosphonium hydroxide [B2], which is an organic onium salt, are used in combination as compared with the case of each alone.

The details of the materials shown in Table 1 are as follows.

(Polymer [A])
MS Polymer SAX520: Organic Polymer Containing a Cyril Group (manufactured by Kaneka Corporation)
MS Polymer S303: Cyril group-containing organic polymer (manufactured by Kaneka Corporation)
STP-E15: Cyril group-containing organic polymer (manufactured by WACKER Chemical Corporation)

(Curing catalyst [B])
Complexes 1 to 12: those produced in Production Examples 1 to 12.

(Other catalysts)
Tetraisopropoxytitanium: manufactured by Tokyo Chemical Industry Co., Ltd. Tetrabutylphosphonium hydroxide: 17.6% tetrabutylphosphonium hydroxydomethanol solution, manufactured in Production Example 1.

(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)

(Other additives)
DINP: Plasticizer (J-PLUS Co., Ltd.)
PPG1000: Plasticizer (manufactured by Kishida Chemical Co., Ltd.)
Disparon 6500: Anti-sauce agent (manufactured by Kusumoto Chemical 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 Shinetsu Silicone Industry Co., Ltd.)
KBM-903: Adhesive-imparting agent (manufactured by Shin-Etsu Silicone Industry Co., Ltd.)

Claims (7)

1. A curing catalyst [B] used for curing a polymer [A] having a reactive hydrolyzable silicon-containing group.
   The curing catalyst [B] contains a complex of a titanium compound [B1] and an organic onium salt [B2].
   The titanium compound [B1] is a curing catalyst [B] represented by the chemical formula (1).
   (R1 ^- O) _n Ti-A _4-n (1)
   (In the formula, R ¹ is a substituted or unsubstituted hydrocarbon group, n is 1 to 4, and A is a β-diketone group).
2. The curing catalyst [B] according to claim 1.
   The organic onium salt [B2] includes a quaternary phosphonium salt, a quaternary imidazolium salt, a quaternary pyrrolidinium salt, a quaternary pyridinium salt, a quaternary piperidinium salt, a quaternary pyrazolium salt, and a tertiary sulfonium. A curing catalyst [B], which is at least one selected from the group consisting of salts.
3. The curing catalyst [B] according to claim 1 or 2, wherein the curing catalyst [B] is used.
   The organic onium salt [B2] is a curing catalyst [B] represented by the chemical formula (2).
   

   

   
   
   (In the formula, R ² , R ³ , R ⁴ , and R ⁵ represent substituted or unsubstituted hydrocarbon groups that are the same or different from each other. X represents a hydroxyl group.)
4. A moisture-curable composition comprising the curing catalyst [B] according to any one of claims 1 to 3 and the polymer [A].
5. A method for producing a cured product, comprising a step of bringing the moisture-curable composition according to claim 4 into contact with moisture.
6. A method for producing a curing catalyst [B] used for curing a polymer [A] having a reactive hydrolyzable silicon-containing group.
   The titanium compound [B1] and the organic onium salt [B2] in a mixture containing the titanium compound [B1] and the organic onium salt [B2] are reacted to form the titanium compound [B1] and the organic onium salt [B2]. Equipped with a process to generate a complex
   The titanium compound [B1] is a method for producing a curing catalyst [B] represented by the chemical formula (1).
   
   (R1 ^- O) _n Ti-A _4-n (1)
   (In the formula, R ¹ , substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, n is 1 to 4, and A is a β-diketone group).
7. The method according to claim 6.
   The method, wherein the molar ratio of the titanium compound [B1] to the organic onium salt [B2] in the mixture is 0.1 to 100.