JP5918908B2 - Curing catalyst for organic polymer or organopolysiloxane, moisture curable composition, cured product and method for producing the same - Google Patents

Description

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

  The one-component moisture-curing 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. Compared to, it is superior in terms of workability.

Known as these one-component moisture-curing rubber compositions are silicone rubbers, modified silicone rubbers, urethane rubbers, polysulfide rubbers, and the like.
An organopolysiloxane composition is widely used as a one-component moisture-curing rubber composition of silicone rubber, and is cured at room temperature to produce a rubber elastic body. A high molecular compound of a siloxane having a -Si-O- bond as a main chain in which an organosiloxane is cross-linked and polymerized is excellent in properties such as water repellency, heat resistance, weather resistance, cold resistance, and electrical insulation. Widely used in fields such as civil engineering, electrical, electronics, and automobile industries.
As a one-pack type moisture curable rubber composition of a modified silicone rubber, there is a composition containing a polymer having a crosslinkable reactive silicon functional group having a polyether as a main chain. The curable composition of this polymer has better storage stability, weather resistance, foam resistance and discoloration than polyurethane rubber, and excellent curability compared to polysulfide. Is less toxic and non-toxic.

The reaction mechanism in the process in which the silicone rubber and the modified silicone rubber become a cured product is considered to be a condensation reaction or addition reaction of a reactive silicon-containing group in the presence of water. It is believed that a polymer cured body of structure is formed. A curing catalyst is used to allow the curing to proceed rapidly in this reaction.
Conventionally, tin carboxylate compounds, alkyltin salt compounds, lead carboxylate compounds, and the like are known as curing catalysts for cured compositions of silicone rubbers and modified silicone rubbers having reactive silicon-containing groups.
However, since the lead compound has a large environmental impact, and the tin compound is concerned as an endocrine disrupting substance, there is a concern about the influence on the living body.

As a moisture curable composition that does not use such substances that may cause environmental pollution, it is possible to use a carboxylic acid and amine combined catalyst in Patent Document 1 and a bismuth compound with less safety problems in Patent Document 1. Although all have been proposed, there is a problem that a sufficient curing rate cannot be obtained during construction.
In Patent Document 3 and Patent Document 4, it is proposed to use a titanate compound such as diisopropoxytitanium bis (alkylacetoacetonate) as a catalyst, but it is included in additives and fillers in the composition. There is a problem that a stable cured product cannot be obtained because the curing rate varies depending on the humidity at the time of construction.
In Patent Document 5, it is proposed to use an aluminum compound such as acetylacetone aluminum as a catalyst, but there is a problem that a practical curing rate cannot be obtained during construction.
In Patent Documents 6 to 9, it is proposed to use a zirconium compound or a hafnium compound as a catalyst. However, since both zirconium and hafnium are rare metals, there is a problem that the manufacturing cost is increased.
Therefore, it has been desired to develop a curing catalyst for an organic polymer that has high safety (low toxicity and low environmental pollution), has a practical curing rate, works stably, and has merit in manufacturing cost.

JP-A-8-41358 Japanese Patent Laid-Open No. 5-39428 JP-A-60-161457 Japanese Examined Patent Publication No. 63-42942 JP-A 63-6041 JP 2004-231648 A JP 2004-231649 A JP 2004-238617 A JP 2004-238616 A

  In view of the prior art, an object of the present invention is to provide a curing catalyst for an organic polymer or organopolysiloxane that has high safety, has a practical curing rate, works stably, and can be produced at low cost. And Furthermore, it aims at providing the moisture hardening type composition containing this catalyst.

  According to the present invention, the catalyst [B] used for curing the organic polymer [A1] or organopolysiloxane [A2] having a reactive silicon-containing group, wherein the catalyst [B] is at least one Ti— An organic polymer or organopolysiloxane curing catalyst [B] containing a titanium-aluminum compound TA having an O—Al bond portion is provided.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the titanium-aluminum compound TA having a Ti—O—Al bond portion is an organic polymer [A1] or organopolysiloxane having a reactive silicon-containing group. It has been found that it has excellent characteristics as a curing catalyst for siloxane [A2], and the present invention has been completed. The titanium-aluminum compound TA is inexpensive and can be easily manufactured.

  In addition, the moisture curable composition of the present invention containing the titanium-aluminum compound TA as a curing catalyst cures faster than the conventional moisture curable composition. In addition, the curing catalyst composed of the titanium-aluminum compound TA of the present invention is deactivated by moisture contained in a trace amount in various additives, compared with the curing catalyst composed of a tin compound, a titanium compound, and an aluminum compound that are currently widely used. And can be used stably.

  Further, the moisture curable composition of the present invention (in particular, the moisture curable composition containing the organic polymer [A1]) is a composition containing a curing catalyst composed of a tin compound, a titanium compound, and an aluminum compound that are currently widely used. Compared to the above, the whiteness of the cured product is high and the yellowness is low, so that it is useful as an alternative to the organic tin compound. In particular, in applications such as a sealing material, various color variations are required. Generally, a white cured product is used as a base and various pigments are added to prepare a desired color. For this reason, it is easier to use the whiter one with as little pigment as possible. From this point of view, the moisture-curable composition of the present invention is suitable because no coloring occurs due to the presence of the catalyst.

Furthermore, since a tin compound is not used as a curing catalyst, it is a safe curable composition that does not have to worry about the effects on the living body and the environment due to endocrine disrupting substances.
Such a moisture curable composition is useful as a sealing agent, a coating agent, and an elastic adhesive.

  Hereinafter, the present invention will be described in detail.

  The organic polymer or organopolysiloxane curing catalyst [B] of the present invention is an organic polymer [A1] or organopolysiloxane [A2] having a reactive silicon-containing group (collectively, “polymer [A]”). It is also used for curing. The polymer [A] is preferably liquid at room temperature.

  The polymer [A] has at least one reactive silicon-containing group per molecule at the molecular end or side chain. The reactive silicon-containing group may be present at the terminal of the polymer [A] molecule, may be present at the side chain, and may be present at both the terminal and side chain. There may be at least one reactive silicon-containing group per molecule of the polymer [A], but from the viewpoint of curing speed and cured physical properties, it is preferable that the average number of reactive silicon-containing groups is 1.5 or more per molecule. As a method for bonding the reactive silicon-containing group to the main chain polymer, a known method can be adopted.

  A reactive silicon-containing group is a group having a silicon atom bonded to a hydrolyzable group (eg, halogen, alkoxy, alkenyloxy, acyloxy, 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 necessary in the presence of moisture or a crosslinking agent. Specific examples include a halogenated silyl group, an alkoxysilyl group, an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group, an aminooxysilyl group, an oximesilyl group, and an amidosilyl group.

  Here, the number of reactive groups bonded to one silicon atom is selected from a range of 1 to 3. Further, the reactive group bonded to one silicon atom may be one kind or plural kinds. Furthermore, the reactive group and the non-reactive group may be bonded to one silicon atom, and the hydrolyzable group and the hydroxyl group may be bonded to one silicon atom. As the reactive silicon-containing group, an alkoxysilyl group (including a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group) is particularly preferable in terms of easy handling.

  Of the above alkoxysilyl groups, trialkoxysilyl groups are preferred because they have high activity and good curability, and the resulting cured product is excellent in resilience, durability, and creep resistance. On the other hand, a dialkoxysilyl group and a monoalkoxysilyl group are preferable because they are excellent in storage stability and the obtained cured product has high elongation and high strength. Further, a cured product obtained by curing the polymer [A] having a trialkoxysilyl group tends to be brittle, and there is a tendency that sufficient elongation and flexibility cannot be obtained.

The following method can be employed as a method for compensating for the problems of the polymer [A] having such trialkoxysilyl group.
First, there is a method of using an additive having an effect of improving elongation and flexibility after curing. These additives include dimethoxymethylvinylsilane, diethoxymethylvinylsilane, diethoxydodecylmethylsilane, diethoxymethyloctadecylsilane, dimethoxydodecylmethylsilane, dimethoxymethyloctadecylsilane, propylmethyldimethoxysilane, cyclohexylmethyldimethoxysilane, phenylmethyldimethoxy Examples include silane, diphenyldimethoxysilane, dicyclopentyldimethoxysilane, and the like.
Secondly, by using together the polymer [A] whose reactive silicon-containing group is a dialkoxysilyl group and the polymer [A] which is a trialkoxysilyl group, a balance between physical properties of the cured product and curability is achieved. Is the method.

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

As 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
Those having one type or two or more types of repeating units such as are exemplified. Here, n is the same or different and is an integer of 2 or more. These alkylene oxide polymers may be used alone or in combination of two or more. Moreover, the copolymer containing 2 or more types of said 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, pyruvic acid, and lactic acid, and anhydrides thereof, and intramolecular and / or intermolecular esters and substituted products thereof. What has as a repeating unit is illustrated.

  Examples of the ether / ester block copolymer include those having as a repeating unit both the repeating unit used in the above-described alkylene oxide polymer and the repeating unit used in the above-mentioned polyester polymer.

  In addition, as a polymer of an ethylenically unsaturated compound and a diene compound, a homopolymer such as ethylene, propylene, acrylic ester, methacrylic ester, vinyl acetate, acrylonitrile, styrene, isobutylene, butadiene, isoprene, chloroprene, or These 2 or more types of copolymers are mentioned. 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 (thio) urethane groups, allophanate groups, other N-substituted urethane groups, N-substituted allophanate groups such as (thio) urethane group-derived linking groups, (thio) urea groups, A binding group derived from a (thio) urea group such as a biuret group, other N-substituted urea groups, N, N′-substituted urea groups, N-substituted biuret groups, N, N′-substituted biuret groups, amide groups, Examples include, but are not limited to, amide group-derived linking groups such as N-substituted amide groups, nitrogen-containing characteristic groups typified by imino group-derived linking groups, (thio) ester groups, (thio) ether groups, and the like. It is not done. Among these, a nitrogen-containing characteristic group is preferable because of high curability, and a bonding group derived from (thio) urethane group and a bonding group derived from (thio) urea are more preferable from the viewpoint of ease of synthesis. Further, only one nitrogen-containing characteristic group may be included in the organic polymer [A1], and a plurality of one or two or more nitrogen-containing characteristic groups may be included. Here, the notation of “(thio)” and “N-substituted” is the same as described 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 the adhesive strength are increased. In particular, when the crosslinkable silicon group is connected to the main chain via a polar group such as a nitrogen-containing characteristic group, the curability is further increased. The reason for this is that the polar groups of the nitrogen-containing characteristic group strongly attract each other due to an interaction such as a hydrogen bond. It is considered that the toughness is expressed in the cured product by strongly attracting the polar groups of the nitrogen-containing characteristic group to each other so that the molecules of the curable resin are also strongly bound (form a domain). 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 brought close to each other when forming the domains of the nitrogen-containing characteristic groups. Thus, it is considered that the contact probability between the crosslinkable silicon groups is improved, and further, the condensation reactivity between the crosslinkable silicon groups is improved by the catalyst curing by the polar group in the nitrogen-containing characteristic group.

  Such an organic polymer [A1] (modified silicone polymer) can be produced, for example, 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 Kaneka MS Polymer Series (MS Polymer S-203, MS Polymer S-303, MS Polymer S-903, MS Polymer S-911, etc.) and Silyl Series (Silyl Polymer) manufactured by Kaneka Corporation. SAT-200, silyl polymer MA430, silyl polymer MAX447, etc.), MA series, SA series, OR series; ES series (ES-GX3440ST, etc.), ESGX series, etc. manufactured by Asahi Glass Co., Ltd.

  The number average molecular weight of the organic polymer [A1] used in the present invention is not particularly limited. However, an excessively high molecular weight polymer has a high viscosity and is difficult to use in a curable composition. The following is desirable. Such an organic polymer can be produced by a known method, but commercially available products such as Kaneka MS polymer manufactured by Kaneka Co., Ltd. may be used.

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

As organopolysiloxane [A2],
(—Si (R) ₂ —O—) _m
(In the formula, R is the same or different and is an organic group, and m represents an integer of 2 or more.)
What has a repeating unit represented by these is illustrated. 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
Those having one type or two or more types of repeating units such as 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.

The organopolysiloxane may be linear or branched including trifunctional (R′SiO _1.5 ) or tetrafunctional (SiO ₂ ). Also, the physical properties and applications of the cured product, bifunctional type as required (R may be combined _'2 SiO) and 1 functional type (R' a ₃ SiO _0.5) (wherein, R 'is an organic group).
Incidentally, the organopolysiloxane represented generally as the average composition formula in _{R a SiO 4-a / 2} ( e.g., JP 2005-194399 Patent and Japanese Patent Application 6-290588 Publication). The above notation followed this.

  The viscosity of the organopolysiloxane [A2] used in the present invention is not particularly limited. However, if the viscosity is excessively high, the workability may be deteriorated or the physical properties of the resulting cured product may be impaired. It is desirable that the viscosity at 0 ° C. is in the range of 0.025 to 100 Pa · s. Such an organopolysiloxane can be produced by a known method, such as a tosseal series manufactured by GE Toshiba Silicone Co., Ltd., a sealant series manufactured by Shin-Etsu Chemical Co., Ltd., a product manufactured by Toray Dow Corning Co., Ltd. Commercial products such as SH series can be used.

(Curing catalyst [B])
The curing catalyst [B] contains a titanium-aluminum compound TA having at least one Ti—O—Al bond.

  The number of titanium atoms in the titanium-aluminum compound TA is preferably 1 to 10, more preferably 1 to 5, and further preferably 1 to 3. The number of aluminum atoms in the titanium-aluminum compound TA is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3. The number of titanium atoms and the number of aluminum atoms are 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and may be in a range between any two of the numerical values exemplified here. .

  The titanium-aluminum compound TA preferably includes a titanium-aluminum structural unit configured by bonding a titanium atom and an aluminum atom, titanium atoms, or aluminum atoms bonded via an oxygen atom. This titanium-aluminum structural unit is preferably composed of only Ti—O—Al bonds, or only Ti—O—Al bonds and Ti—O—Ti bonds.

The titanium-aluminum compound TA is preferably composed of at least one of a Ti—O—R ¹ bond and an Al—O—R ² bond and the titanium-aluminum structural unit. R ¹ and R ² are each independently a linear, branched or cyclic alkyl group, aryl group or aralkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms may be linear or branched, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl. Hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, etc., preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, etc. A hydrocarbon group, more preferably methyl, ethyl, propyl or isopropyl. Examples of the aryl group include phenyl, 1-naphthyl, 2-naphthyl, indenyl, biphenylyl, anthryl, phenanthryl, benzyl and the like, preferably an aryl group having 6 to 10 carbon atoms, and more preferably phenyl or benzyl. . Examples of the aralkyl group include benzyl and phenethyl, with benzyl being preferred. The carbon number of R ¹ and R ² is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and is within a range between any two of the numerical values exemplified here. May be.

  The titanium-aluminum compound TA is preferably represented by the following general formula (I) or (II).

(X is _{^{independently, -OR 1, -O-Al-}} Y 2, or is one of _{-O-Ti-X 3,} or two X the following general formula (III) or (IV Y is each independently -OR ² , -O-Al-Y ₂ , -O-Ti-X ₃ , or two Ys are represented by the following general formula ( III) or (IV) is substituted.)

X may be any of —OR ¹ , —O—Al—Y ₂ , and —O—Ti—X ₃ , and Y is —OR ² , —O—Al—Y ₂ , —O—Ti—. it may be any of X _3. When X is —O—Al—Y ₂ , an aluminum atom is bonded to the X position via an oxygen atom, and two Y atoms are bonded to the aluminum atom. Further, when X is —O—Ti—X ₃ , a titanium atom is bonded to the position of X through an oxygen atom, and three X are bonded to the titanium atom. When Y is —O—Al—Y ₂ , an aluminum atom is bonded to the Y position via an oxygen atom, and two Y atoms are bonded to the aluminum atom. When Y is —O—Ti—X ₃ , a titanium atom is bonded to the Y position via an oxygen atom, and three X are bonded to the titanium atom.

Further, two X or Y in the general formula (I) or (II) may be replaced with the general formula (III) or (IV). This introduces an annular portion composed of oxygen atoms and metal atoms (Ti or Al). The number of metal atoms contained in the annular portion is not limited to 2. For example, in the general formula (I), when Y is —O—Ti—X ₃ , X derived from Y and the general formula When X bonded to the titanium atom in (I) is substituted with the general formula (III), the cyclic portion includes three metal atoms. The number of metal atoms is, for example, 2 to 5, for example 2, 3, 4, or 5.

  Thus, X and Y are interpreted recursively. However, since the number of titanium atoms and the number of aluminum atoms contained in the general formula (I) or (II) are limited to 1 to 10 respectively, the recursion of X and Y is not repeated infinitely.

The titanium-aluminum compound TA represented by the general formula (I) or (II) has, for example, the structures of the following chemical formulas (VII-1) to (VII-10) and (VIII-1) to (VIII-29) Have In addition, Pr in the following formulas can be substituted with the above R ¹ or R ² .

<Method for producing titanium-aluminum compound TA>
Next, a method for producing the titanium-aluminum compound TA will be described.
The titanium-aluminum compound TA can be obtained by a reaction that forms a Ti—O—Al bond between a titanium atom contained in the titanium alkoxide and an aluminum atom contained in the aluminum alkoxide.
Preferably, the titanium alkoxide is represented by the following general formula (V), and the aluminum alkoxide is represented by the following general formula (VI). R ¹ and R ² in the general formulas (V) to (VI) are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group, or Aralkyl group.
Ti (OR ¹ ) ₄ (V)
Al (OR ² ) ₃ (VI)

  Examples of the titanium alkoxide represented by the formula (V) include tetramethoxy titanium, tetraethoxy titanium, tetrapropoxy titanium, tetraisopropoxy titanium, tetrabutoxy titanium, tetra sec-butoxy titanium, tetra tert-butoxy titanium, and tetrapentyl. Examples include roxytitanium, tetrahexyloxytitanium, tetraheptyloxytitanium, tetraoctyloxytitanium, tetranonyloxytitanium, tetradecyloxytitanium and the like, and tetraisopropoxytitanium is particularly preferable.

  Examples of the aluminum compound represented by the formula (VI) include trimethoxyaluminum, triethoxyaluminum, tripropoxyaluminum, triisopropoxyaluminum, tributoxyaluminum, trisec-butoxyaluminum, tritert-butoxyaluminum, and tripentyl. Examples include roxyaluminum, trihexyloxyaluminum, triheptyloxyaluminum, trioctyloxyaluminum, trinonyloxyaluminum, tridecyloxyaluminum and the like, and triisopropoxyaluminum is particularly preferable.

  The method for causing the above reaction is not particularly limited. In one example, a titanium carboxylate is obtained by performing a substitution reaction in which at least one alkoxy group of the titanium alkoxide is substituted with a carboxyl group, and the titanium carboxylate is converted into an aluminum alkoxide. (Reaction 1). Note that an aluminum carboxylate may be obtained by performing a substitution reaction in which at least one alkoxy group of the aluminum alkoxide is substituted with a carboxyl group, and this aluminum carboxylate may be reacted with a titanium alkoxide.

The titanium carboxylate formed by the substitution reaction is represented by, for example, general formula (IX).
(R ¹ O) _n -Ti- (OCOR ³ ) _4-n (IX)
In the formula, each R ³ is independently a straight-chain, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group, or an aralkyl group, like R ¹ . n is an integer of 0 to 3, and from the viewpoint of handling the compound, n is preferably 2 to 3.

  Examples of the titanium carboxylate represented by the formula (IX) include methoxy titanium triacetate, dimethoxy titanium diacetate, trimethoxy titanium acetate, titanium tetraacetate, ethoxy titanium triacetate, diethoxy titanium diacetate, triethoxy titanium acetate, and propoxy. Titanium triacetate, dipropoxy titanium diacetate, tripropoxy titanium acetate, isopropoxy titanium triacetate, diisopropoxy titanium diacetate, triisopropoxy titanium acetate, benzyloxy titanium triacetate, dibenzyloxy titanium diacetate, tribenzyloxy titanium acetate, etc. In particular, isopropoxy titanium triacetate, diisopropoxy titanium diacetate, triisopropyl Po alkoxy titanium acetate is preferred.

  Another method includes a method in which titanium alkoxide and aluminum alkoxide are contacted in the presence of water (reaction 2). In this method, a titanium alkoxide or aluminum alkoxide is first activated by reaction of titanium alkoxide or aluminum alkoxide with water, and the activated titanium alkoxide or aluminum alkoxide reacts with another aluminum alkoxide or titanium alkoxide. Ti-O-Al bonds are formed.

  In the above reaction 1 and reaction 2, titanium-aluminum compounds having various Ti—O—Al bonding parts by changing the reaction ratio (molar ratio) of each component (compounds of formula V, VI, IX and water) Can be manufactured.

As the titanium-aluminum compound TA, for example, a compound obtained by reacting 0.1 to 4 moles of an aluminum alkoxide represented by the formula (VI) with respect to 1 mole of a titanium carboxylate represented by the formula (IX). Are mentioned,
In particular, in formula (IX), R ¹ is either methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl (each R ¹ is identical to the other R ^1). Or R ³ is methyl, and the titanium carboxylate (n = 0 to 3) is 1 mol.
In the formula (VI), R ² is propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, phenyl or benzyl. Any compound (each R ² may be the same as or different from other R ² ), which is obtained by reacting 0.3 to 1 mole of aluminum alkoxide, is preferable.

In addition, as the titanium-aluminum compound TA, for example, 0.1 to 4 mol of the aluminum alkoxide represented by the formula (VI) is present in the presence of water with respect to 1 mol of the titanium alkoxide represented by the formula (V). The compound obtained by making it react (1-3 equivalent with respect to aluminum alkoxide) is mentioned, In particular, in formula (V), R < ¹ > is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-. In relation to one mole of titanium alkoxide which is any of butyl (each R ¹ may be the same or different from the other R ¹ ), in formula (VI), R ² is propyl, isopropyl, Butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethyl 0.3 to 1 mole of aluminum alkoxide, which is either hexyl, phenyl or benzyl (each R ² may be the same or different from the other R ² ) in the presence of water (to the aluminum alkoxide). A compound obtained by reacting 1 to 3 equivalents) is preferable.

For example, in the above reaction 1, at least one Ti alkoxide represented by the general formula (VI) is reacted with 1 mole (n = 2) of the titanium carboxylate represented by the formula (IX). A reaction product having an -O-Al bond can be produced.
Usually, in the above reaction 1, under an inert gas atmosphere, a titanium carboxylate represented by the formula (IX) and an aluminum alkoxide represented by the formula (VI) are added, and the resulting ester (R ³ COOR ² ) is produced. By distilling off under reduced pressure, a reaction product having at least one Ti—O—Al bond can be obtained. The reaction temperature is generally about 80 to 150 ° C., and the reaction time is about 2 to 6 hours.

For example, in the above reaction 2, 1 mol of an aluminum alkoxide represented by the general formula (VI) is reacted with 1 mol of a titanium alkoxide represented by the formula (V) in the presence of water, so that at least one Ti A reaction product having an —O—Al bond can be produced.
Usually, in the above reaction 2, in an inert gas atmosphere, a titanium alkoxide represented by the formula (V), an aluminum alkoxide represented by the formula (VI), and 1 to 2 mol of water are added to form an alcohol. Is distilled off under reduced pressure to obtain a reaction product having at least one Ti—O—Al bond. The reaction temperature is generally about 80 to 150 ° C., and the reaction time is about 2 to 6 hours.

  Moreover, the alkoxy group can be easily exchanged by further adding an alcohol to the reaction product obtained in the above reaction 1 or 2 for reaction.

  In addition, the chemical structure of the reaction product having at least one Ti—O—Al bond to be generated varies depending on the type, number of equivalents, etc. of titanium alkoxide, titanium carboxylate, and aluminum alkoxide, and also exists as a mixture. there is a possibility.

<Method for producing titanium-aluminum compound TA having Ti-O-Al bond and Ti-O-Ti bond>
Next, a method for producing a titanium-aluminum compound TA having a Ti—O—Al bond and a Ti—O—Ti bond will be described. In the general formula (I) or (II), when at least one of X is —O—Ti—X ₃ or the general formula (III), the Ti—O—Al bond portion and the Ti—O—Ti bond portion are It has titanium-aluminum compound TA. Such a titanium-aluminum compound TA is preferable from the viewpoint of stability, and specific examples thereof are compounds of the above chemical formulas (VIII-1) to (VIII-29).

  Such a titanium-aluminum compound TA forms a Ti—O—Al bond between a titanium atom contained in the titanium alkoxide and an aluminum atom contained in the aluminum alkoxide, and a Ti—O bond between two titanium atoms. It can be generated by forming a Ti bond.

  The reaction for forming a Ti—O—Ti bond and the reaction for forming a Ti—O—Al bond may be performed at the same time. First, a Ti—O—Ti bond is formed, and then Ti—O— Al bonding may be performed.

In an example of the production method, at least one of the alkoxy groups of the titanium alkoxide is substituted with a carboxyl group and a reaction for forming a Ti—O—Ti bond is performed to obtain a titanium carboxylate. The titanium carboxylate is combined with an aluminum alkoxide. The method of making it react is mentioned (reaction 3).
The titanium carboxylate is represented by, for example, general formula (X). The number of carboxylate groups in general formula (X) is 1-10, for example.

In the formula, each X ¹ is independently —OR ¹ , —OCOR ³ , —O—Ti—X ¹ ₃ , or two X ¹ are substituted by the general formula (XI), At least ^one of X ¹ is —OCOR ³ and the number of titanium atoms is 2 to 10.

  Examples of the titanium carboxylate represented by the formula (X) include, for example, 1,1,3,3-tetramethoxy-1,4-dititanoxane-1,3-acetate, 1,1,3,3-tetra Ethoxy-1,4-dititanooxane-1,3-acetate, 1,1,3,3-tetrapropoxy-1,4-dititanooxane-1,3-acetate, 1,1,3,3-tetraisopropoxy-1 , 4-Dititanooxane-1,3-acetate, 1,1,3,3-tetrabutoxy-1,4-dititanooxane-1,3-acetate, 1,1,3,3-tetrapentanoxy-1,4 -Dititanooxane-1,3-acetate, 1,1,3,3-tetrahexanoxy-1,4-dititanooxane-1,3-acetate, 1,1,3,3-tetraheptanooxy-1,4 -Dititanooxane-1,3-acetate, 1,1,3,3-tetraoctanooxy-1,4-dititaoxane-1,3-acetate, 1,1,3,3-tetra2-ethylhexanoxy- 1,4-dititanooxane-1,3-acetate, 1,1,3,3-tetra Nonanoxy-1,4-dititanooxane-1,3-acetate, 1,1,3,3-tetramedecanoxy-1,4-dititanooxane-1,3-acetate, etc., especially 1,1,3 1,3-tetraisopropoxy-1,4-dititaoxane-1,3-acetate, 1,1,3,3-tetrabutoxy-1,4-dititaoxane-1,3-acetate are preferred.

  As another method, a titanium alkoxide represented by the following general formula (XII) is formed by bonding two titanium atoms derived from titanium alkoxide via an oxygen atom to form a Ti—O—Ti bond. And the titanium alkoxide and aluminum alkoxide are contacted in the presence of water (reaction 4). The principle that a Ti—O—Al bond is formed by this method is the same as in Reaction 2.

In the formula, each X ² is independently —OR ¹ , —O—Ti—X ² ₃ , or two X ² are substituted by the general formula (XIII), and the number of titanium atoms is 2-10.

  Examples of the titanium alkoxide represented by the formula (XII) include 1,1,1,3,3,3-hexamethoxy-1,4-dititaoxane, 1,1,1,3,3,3-hexaethoxy. -1,4-dititaoxane, 1,1,1,3,3,3-hexapropoxy-1,4-dititaoxane, 1,1,1,3,3,3-hexaisopropoxy-1,4-dititaoxane, 1,1,1,3,3,3-hexabutoxy-1,4-dititanoxane, 1,1,1,3,3,3-hexapentanoxy-1,4-dititaoxane, 1,1,1, 3,3,3-hexahexanoxy-1,4-dititanoxane, 1,1,1,3,3,3-hexaheptanooxy-1,4-dititaoxane, 1,1,1,3,3, 3-hexaoctanooxy-1,4-dititanoxane, 1,1,1,3,3,3-hexa-2-ethylhexanoxy-1,4-dititaoxane, 1,1,1,3,3,3 -Hexanonanoxy-1,4-dititaoxane, 1,1,1,3,3,3-hexadecaneoxy-1,4-dititaoxane, etc., especially 1,1,1,3,3,3-hexa Isopropoxy-1,4-di Titanooxane and 1,1,1,3,3,3-hexabutoxy-1,4-dititaoxane are preferred.

  In the above reactions 3 and 4, the reaction ratio (molar ratio) of each component (compounds of formulas VI, X, and XII and water) is changed to have various Ti—O—Al bonds, and Ti A titanium-aluminum compound TA having an —O—Ti bond can be produced.

For example, in formula (X), R ¹ is any ^one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl (each R ¹ is the same as the other R ¹⁾ And R ³ is methyl, which is 1 mol of titanium carboxylate (2 to 7 titanium atoms),
In the formula (VI), R ² is propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, phenyl or benzyl. A compound obtained by reacting 1 to 16 moles of aluminum alkoxide which is either (each R ² may be the same as or different from other R ² ) may be preferable.

For example, in the formula (XII), R ¹ is any of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl (each R ¹ is the same as the other R ^1). In the formula (VI), R ² is propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, and 1 mol of titanium alkoxide (n = 0 to 5). Any of amyl, isoamyl, tert-amyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, phenyl or benzyl (each R ² may be the same as or different from the other R ² ) A compound obtained by reacting 1 to 16 moles of aluminum alkoxide is preferred.

For example, in reaction 3 above, aluminum represented by the formula (VI) with respect to 1 mole of titanium carboxylate represented by the formula (X) (number of titanium atoms = 2, number of carboxylates of each titanium atom is 1). A reaction product having at least one Ti—O—Ti bond represented by formula (I) or (II) and having a Ti—O—Al bond is obtained by reacting 1 to 2 mol of alkoxide. Can be manufactured.
Usually, the reaction is carried out under reduced pressure by adding a titanium carboxylate represented by the formula (X) and an aluminum alkoxide represented by the formula (VI) under an inert gas atmosphere to reduce the resulting ester (R ³ COOR ² ) under reduced pressure. By leaving, a reaction product having at least one Ti—O—Ti bond and a Ti—O—Al bond can be obtained. The reaction temperature is generally about 80 to 150 ° C., and the reaction time is about 2 to 6 hours.

For example, in reaction 4 above, 1 mol of aluminum alkoxide represented by formula (VI) is reacted with 1 mol of titanium alkoxide represented by formula (XII) (n = 0), and (I) Alternatively, a reaction product having at least one Ti—O—Ti bond represented by (II) and having a Ti—O—Al bond can be produced.
Usually, the reaction is an ester alcohol produced by adding a titanium alkoxide represented by the formula (XII), an aluminum alkoxide represented by the formula (VI), and 1 to 2 mol of water under an inert gas atmosphere. Is distilled off under reduced pressure to obtain a reaction product having at least one Ti—O—Ti bond and a Ti—O—Al bond. The reaction temperature is generally about 80 to 150 ° C., and the reaction time is about 2 to 6 hours.

  It should be noted that the reaction product has at least one Ti—O—Al bond portion to be generated and has a Ti—O—Al bond portion according to the type, number of equivalents, etc. of titanium alkoxide, titanium carboxylate, and aluminum alkoxide. The chemical structure of the object may change and may exist as a mixture.

Said titanium-aluminum compound TA may be used independently and may use 2 or more types together.
The catalyst [B] used for curing the organic polymer [A1] or the organopolysiloxane [A2] of the present invention can contain components other than the above titanium-aluminum compound TA. And the like.

  The titanium-aluminum compound TA having at least one Ti—O—Ti bond and Ti—O—Al bond has low toxicity and low environmental pollution, and serves as a curing catalyst for the organic polymer [A1] or organopolysiloxane [A2]. When used, it has fast curability, is difficult to be decomposed by moisture contained in additives and fillers in the composition, and does not vary in curing speed due to humidity during construction, and is stable quickly. Give a cured product. Therefore, it is useful as a curing catalyst in a moisture curable composition comprising the organic polymer [A1] or organopolysiloxane [A2] as a main component, particularly a one-component moisture curable composition.

(Moisture curable composition)
The moisture curable composition of the present invention contains the above-mentioned curing catalyst [B] and the organic polymer [A1] or organopolysiloxane [A2], and may contain other additives as described later as necessary. . The moisture-curable composition of the present invention may be prepared by mixing both under dry conditions, and the mixing form is not particularly limited. Usually, it may be mixed in an atmosphere of a temperature 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 with respect to 100 parts by weight of the organic polymer [A1] or organopolysiloxane [A2]. 0.5 to 10 parts by weight, particularly 4 to 8 parts by weight is preferred. When the content of the curing catalyst [B] is less than 0.1 parts by weight, the curing performance is insufficient. When the content exceeds 20 parts by weight, the properties of the cured product after curing, physical properties such as weather resistance, stability during storage, etc. May get worse.

  The moisture curable composition of the present invention may further contain a filler [C]. 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 barn, glass fiber, asbestos, Examples thereof include glass filaments, pulverized quartz, diatomaceous earth, aluminum silicate, aluminum hydroxide, zinc oxide, magnesium oxide, and titanium dioxide. A filler may be used independently and may use 2 or more types together. By adding a filler, handling of the moisture curable composition is improved. It also acts as a rubber reinforcement for the cured product. The greatest 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 these, 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 using calcium carbonate, the proportion is preferably 1 to 200 parts by weight with respect to 100 parts by weight of the organic polymer [A1] or organopolysiloxane [A2]. Within the above range, the properties after curing are not impaired.

  Additives usually added to the curable composition such as a curing accelerator, a colorant, a plasticizer, a curing retarder, an anti-sagging agent, an anti-aging agent, and a solvent are added to the moisture curable composition of the present invention. May be.

  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 (Methoxysilylpropyl) ethylenediamine and partial hydrolysis thereof, and the like. These also have the effect of improving the adhesion to the substrate.

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

  Specific examples of the plasticizer include phthalic acid esters such as dibutyl phthalate, dioctyl phthalate, and butyl benzyl phthalate; 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 epoxy benzyl stearate; chlorinated paraffin and the like are used.

  As the sagging inhibitor, specifically, hydrogenated castor oil, silicic anhydride, organic bentonite, colloidal silica, or the like is used.

  Further, as other additives, adhesion imparting agents such as phenol resins and epoxy resins, ultraviolet absorbers, radical chain inhibitors, peroxide decomposing agents, various anti-aging agents and the like are used.

  Since the curable composition of the present invention is sufficiently stable at room temperature, it is excellent in storability, and when it comes into contact with moisture, the curing reaction proceeds spontaneously by the blended curing catalyst [B]. Also, the snap time (time until semi-gelling and fluidity is lost) and tack-free time (time until surface tack is eliminated) are short, and the workability is excellent.

  From the above characteristics, the curable composition of the present invention can be used as a one-pack type sealing material. Specifically, it is suitably used for applications such as sealing materials for vehicles such as buildings, ships and automobiles, adhesives, sealants, waterproofing sealing materials and the like.

  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 1A
Titanium (IV) isopropoxide (28.42 g, 0.1 mol) is weighed into a 200 ml eggplant flask equipped with a nitrogen inlet tube, and 6.00 g (0.1 mol) of acetic acid is dropped into the dropping funnel. The reaction by-product isopropyl alcohol was distilled off at 90 to 100 ° C. while thoroughly mixing with a magnetic stirrer. Thereafter, 6.74 g (0.033 mol) of aluminum isopropoxide was added and reacted at 140 to 150 ° C. to distill off isopropyl alcohol as a reaction byproduct. Further, it was concentrated under reduced pressure at 100 ° C. to obtain a light yellow transparent liquid titanium-aluminum compound A.
The compound was analyzed by FT-IR, the disappearance of the absorption of -CO-O-Ti- carbonyl group of medium to 1600~1650cm ^-1, confirmed the absorption of the Ti-O-Al to seven hundred and thirty to seven hundred forty cm ^-1 .

Production Examples 2A to 10A
Titanium-aluminum compounds B to J were obtained in the same manner as in Production Example 1A except that the amounts of acetic acid and aluminum isopropoxide were changed as shown in Table 1. The unit of numerical values in Table 1 is mol. The properties of the titanium-aluminum compound BJ and the results of FT-IR analysis are also shown in Table 1. The indication “○” in the row of the Ti—O—Al bond means that absorption of Ti—O—Al was confirmed at 730 to 740 cm ^−1, and the row of the Ti—O—Ti bond portion The indication “◯” means that absorption of Ti—O—Ti was confirmed at 775 to 785 cm ⁻¹ . Further, in all of the titanium-aluminum compounds BJ, disappearance of absorption of the carbonyl group in -CO-O-Ti- was confirmed.

Production Example 11A
Weigh 34.03 g (0.1 mol) of titanium (IV) n-butoxide into a 100 ml eggplant flask equipped with a nitrogen inlet tube, 20 g (0.3 mol) of isopropyl alcohol, 1.8 g (0.1 mol) of water, 6.74 g of aluminum isopropoxide. (0.033 mol) was added, and the mixture was reacted at 140 to 150 ° C. while thoroughly mixing with a magnetic stirrer to distill off isopropyl alcohol as a by-product. Further, it was concentrated under reduced pressure at 100 ° C. to obtain a light yellow transparent liquid titanium-aluminum compound K.
This compound was analyzed by FT-IR, and absorption of Ti—O—Al was confirmed at 730 to 740 cm ⁻¹ .

Production Example 12A
To a pale yellow transparent liquid titanium-aluminum compound A synthesized by the method of Production Example 1A, 32.44 g (0.3 mol) of benzyl alcohol was added and reacted at 100 to 120 ° C. to distill off isopropyl alcohol as a reaction by-product. Further, the mixture was concentrated under reduced pressure at 100 ° C. to obtain a light yellow transparent liquid titanium-aluminum compound L. This compound was analyzed by FT-IR, and absorption of Ti—O—Al was confirmed at 730 to 740 cm ⁻¹ .

Production Example 13A
39.06 g (0.3 mol) of 2-ethylhexanol was added to the light yellow transparent liquid titanium-aluminum compound A synthesized by the method of Production Example 1A and reacted at 100 to 120 ° C. to distill off isopropyl alcohol as a by-product. . Further, the mixture was concentrated under reduced pressure at 100 ° C. to obtain a light yellow transparent liquid titanium-aluminum compound M.
This compound was analyzed by FT-IR, and absorption of Ti—O—Al was confirmed at 730 to 740 cm ⁻¹ .

Production Example 1B
Titanium (IV) isopropoxide 28.42 g (0.1 mol) was weighed into a 100 ml eggplant flask equipped with a nitrogen inlet tube, and a solution in which 6.00 g (0.1 mol) of acetic acid and 0.90 g (0.05 mol) of water were mixed was added dropwise. Drop with a funnel. The reaction by-product isopropyl alcohol was distilled off at 90 to 100 ° C. while thoroughly mixing with a magnetic stirrer. Thereafter, 10.21 g (0.05 mol) of aluminum isopropoxide was added and reacted at 140 to 150 ° C. to distill off isopropyl alcohol as a reaction byproduct. Further, it was concentrated under reduced pressure at 100 ° C. to obtain a light yellow transparent liquid titanium-aluminum compound a.
The compound was analyzed by FT-IR, absorption of Ti-O-Ti in 775~785cm ^-1, disappearance of the absorption of -CO-O-Ti- carbonyl group of medium to 1600~1650cm ^-1, 730~740 Absorption of Ti-O-Al was confirmed at cm- ¹ .

Production Examples 2B-15B
Titanium-aluminum compounds bo were obtained by the same method as in Production Example 1B except that the amounts of acetic acid and aluminum isopropoxide were changed as shown in Table 2. The unit of numerical values in Table 2 is mol. In Production Examples 5B, 13B, and 14B, 200 ml eggplant flasks were used.
Table 2 shows the properties of the titanium-aluminum compound bo and the results of FT-IR analysis. The meaning of “◯” in the column of Ti—O—Al bonds and the column of Ti—O—Ti bonds is the same as in Table 1. Further, in all of the titanium-aluminum compound bo, the disappearance of absorption of the carbonyl group in -CO-O-Ti- was confirmed.

Production Example 16B
To a 100 ml eggplant flask equipped with a nitrogen inlet tube, 34.03 g (0.1 mol) of titanium (IV) n-butoxide was weighed and a solution in which 20 g (0.3 mol) of isopropyl alcohol and 0.90 g (0.05 mol) of water were mixed was dropped. Drop with a funnel. It mixed at 80 degreeC with the magnetic stirrer. Thereafter, 10.21 g (0.05 mol) of aluminum isopropoxide is added, and a solution in which 20 g of isopropyl alcohol and 1.80 g (0.1 mol) of water are mixed is dropped using a dropping funnel. Reaction was performed at 140 to 150 ° C. to distill off isopropyl alcohol and n-butyl alcohol as reaction by-products. Further, the mixture was concentrated under reduced pressure at 100 ° C. to obtain a light yellow transparent liquid titanium-aluminum compound p.
The compound was analyzed by FT-IR, absorption of Ti-O-Ti in 775~785cm ^-1, confirmed the absorption of the Ti-O-Al to seven hundred and thirty to seven hundred and forty cm ^-1.

Production Example 17B
48.66 g (0.45 mol) of benzyl alcohol was added to the light yellow transparent liquid titanium-aluminum compound a synthesized by the method of Production Example 1B and reacted at 100 to 120 ° C. to distill off isopropyl alcohol as a by-product. Further, the mixture was concentrated under reduced pressure at 100 ° C. to obtain a light yellow transparent liquid titanium-aluminum compound q.
The compound was analyzed by FT-IR, absorption of Ti-O-Ti in 775~785cm ^-1, disappearance of the absorption of -CO-O-Ti- carbonyl group of medium to 1600~1650cm ^-1, 730~740 Absorption of Ti-O-Al was confirmed at cm- ¹ .

Production Example 18B
2-ethylhexanol (58.60 g, 0.45 mol) was added to the light yellow transparent liquid titanium-aluminum compound a synthesized by the method of Production Example 1B and reacted at 100 to 120 ° C. to distill off isopropyl alcohol as a by-product. . Further, it was concentrated under reduced pressure at 100 ° C. to obtain a light yellow transparent liquid titanium-aluminum compound r.
The compound was analyzed by FT-IR, absorption of Ti-O-Ti in 775~785cm ^-1, disappearance of the absorption of -CO-O-Ti- carbonyl group of medium to 1600~1650cm ^-1, 730~740 Absorption of Ti-O-Al was confirmed at cm- ¹ .

(Test 1: Examples 1-31 and Comparative Examples 1-9)
To 100 parts by weight of a silyl group-containing organic polymer (MS polymer S303 manufactured by Kaneka Corporation), various additives are blended in the blending ratios shown in Tables 3 to 5 and kneaded to prepare a moisture-curable composition. did. Further, the catalyst was diluted with a plasticizer and stored in an incubator at 50 ° C., and a moisture-curing composition was prepared by sampling every certain time. The operations up to blending, kneading and curing of the materials were performed in an atmosphere of 25 ± 1 ° C. and 50-60% RH.
The obtained moisture-curable composition was measured for skinning time (time until semi-gelling and loss of fluidity) and tack-free time (time until surface tack disappears).

  For the skinning time, the silyl group-containing organic polymer and additives other than the catalyst were kneaded well, the catalyst was added thereto, and the mixture was further kneaded for 3 minutes. After the kneading, 35 g was weighed and placed in a circular container having a diameter of 6.5 cm and a depth of 1 cm. Counting of the time was started from the end of the kneading, and the time required until rubber elasticity appeared without dripping (holding for 1 minute) even when the container was tilted 90 degrees was measured.

  The tack-free time was measured by measuring the time required from the end of kneading until the sample no longer adheres to the fingertip with a fingertip cleaned with ethyl alcohol.

  Further, the HW value was measured with a color difference meter (TC-PIII type manufactured by Tokyo Denshoku Co., Ltd.). The HW value means whiteness, and the upper limit is 100 and the closer to 100, the closer to white.

The compounding quantity of the material in a table | surface is a mass part. Details of the materials shown in Tables 3 to 11 are as follows.
Calcium carbonate: Filler Titanium dioxide: Made by Titanium Industry Co., Ltd. Hydrogenated castor oil: Made by Ito Oil Co., Ltd. Nocrack NS-6: Anti-aging agent (made by Ouchi Shinsei Chemical Co., Ltd.)
Sumoyle P-350: Liquid paraffin (Muramatsu Oil Co., Ltd.)
A-171: Vinyl alkoxysilane compound (Nihon Unicar Co., Ltd.)
A-1100: Amino group-substituted alkoxysilane compound (manufactured by Nippon Unicar Co., Ltd.)
Acetylacetone aluminum: manufactured by Tokyo Kasei Co., Ltd., first grade reagent Neostan U-200: dibutyltin diacetate (manufactured by Nitto Kasei Co., Ltd.)
Neostan U-100: Dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd.)
Sunny Cat T-100: Diisopropoxy titanium bis (ethyl acetoacetonate) (manufactured by Nitto Kasei Co., Ltd.)
Titanium (IV) isopropoxide: Kishida Chemical Co., Ltd. Reagent Aluminum isopropoxide: Kida Chemical Co., Ltd. Reagent mixture a: 1: 1 (mol ratio) mixture of titanium (IV) isopropoxide and aluminum isopropoxide b: 2: 1 (mol ratio) mixture mixture of titanium (IV) isopropoxide and aluminum isopropoxide c: 3: 1 (mol ratio) mixture of titanium (IV) isopropoxide and aluminum isopropoxide

  From the comparison between Examples and Comparative Examples in Tables 3 to 5, it was confirmed that the curing catalyst of the present invention was excellent in stability over time, and the skinning time and tack-free time were short over a long period of time. Moreover, it turned out that it is remarkably excellent in a HW value rather than the case where the conventional titanium type curing catalyst is used.

(Test 2: Examples 32-62 and Comparative Examples 10-18 (curability test))
With respect to 100 parts by weight of organopolysiloxane having hydrolyzable silicon-containing groups (GE Toshiba Silicone Co., Ltd. Tosseal 371), various additives are blended in the blending ratios shown in Tables 6 to 8, and kneaded. A moisture curable composition was prepared. Further, the catalyst was diluted with a plasticizer and stored in an incubator at 50 ° C., and a moisture-curing composition was prepared by sampling every certain time. The operations up to blending, kneading and curing of the materials were performed in an atmosphere of 25 ± 1 ° C. and 50-60% RH.

  With respect to the obtained moisture-curable composition, the skinning time and tack-free time were measured in the same manner as in Test 1 except that the organic polymer was changed to organopolysiloxane.

  From the comparison of Examples and Comparative Examples in Tables 6 to 8, it was confirmed that the curing catalyst of the present invention was excellent in stability over time, and the skinning time and tack-free time were short over a long period of time.

(Test 3: Examples 63 to 93 and Comparative Examples 19 to 27 (curability test))
An organic polymer having a hydrolyzable silyl group (ES-GX3440ST: manufactured by Asahi Glass Co., Ltd., an organic polymer having a trimethoxysilyl group and a main chain of polyoxyalkylene) and various additives are listed in Tables 9 to 11 was blended and kneaded to prepare a moisture curable composition. Further, the catalyst was diluted with a plasticizer and stored in an incubator at 50 ° C., and a moisture-curing composition was prepared by sampling every certain time. The operations up to blending, kneading and curing of the materials were performed in an atmosphere of 25 ± 1 ° C. and 50-60% RH.

  About the obtained moisture-curable composition, the skinning time and tack-free time were measured in the same manner as in Test 1.

  From the comparison between Examples and Comparative Examples in Tables 9 to 11, it was confirmed that the curing catalyst of the present invention was excellent in stability over time, and the skinning time and tack-free time were short over a long period of time.

Claims (13)

A catalyst [B] used for curing an organic polymer [A1] or organopolysiloxane [A2] having a reactive silicon-containing group,
The catalyst [B] is a curing catalyst for organic polymer or organopolysiloxane [B] containing a titanium-aluminum compound TA having at least one Ti—O—Al bond. The catalyst [B] according to claim 1, wherein the titanium-aluminum compound TA has 1 to 10 titanium atoms and 1 to 10 aluminum atoms. 3. The catalyst according to claim 2, wherein the titanium-aluminum compound TA includes a titanium-aluminum structural unit constituted by a titanium atom and an aluminum atom, titanium atoms, or aluminum atoms bonded together through an oxygen atom. [B]. The catalyst [B] according to claim 3, wherein the titanium-aluminum structural unit is composed of only a Ti-O-Al bond or only a Ti-O-Al bond and a Ti-O-Ti bond. 5. The titanium-aluminum compound TA according to claim 3, wherein the titanium-aluminum compound TA includes at least one of a Ti—O—R ¹ bond and an Al—O—R ² bond, and the titanium-aluminum structural unit. Catalyst [B] (R ¹ and R ² are each independently a linear, branched or cyclic alkyl group, aryl group or aralkyl group having 1 to 10 carbon atoms). The catalyst [B] according to claim 5, wherein the titanium-aluminum compound TA is represented by the following general formula (I) or (II).


(X is _{^{independently, -OR 1, -O-Al-}} Y 2, or is one of _{-O-Ti-X 3,} or two X the following general formula (III) or (IV Y is each independently -OR ² , -O-Al-Y ₂ , -O-Ti-X ₃ , or two Ys are represented by the following general formula ( III) or (IV) is substituted.)

It is a manufacturing method of the catalyst [B] of Claim 1,
The titanium - aluminum compounds TA is a product obtained with titanium atoms contained in the titanium alkoxide, the reaction to form a Ti-O-Al bond between the aluminum atoms contained in the aluminum alkoxide method. The method of claim 7, wherein the product further comprises a Ti—O—Ti bond formed by bonding the two titanium atoms through oxygen atoms. The method of claim 8, wherein the Ti—O—Ti bond is formed prior to formation of the Ti—O—Al bond. The method according to any one of claims 7 to 9, wherein the titanium alkoxide is represented by the following general formula (V), and the aluminum alkoxide is represented by the following general formula (VI).
Ti (OR ¹ ) ₄ (V)
(In the formula, each R ¹ is independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group, or an aralkyl group.)
Al (OR ² ) ₃ (VI)
(In the formula, each R ² may be the same or different and is a linear, branched or cyclic alkyl group, aryl group or aralkyl group having 1 to 10 carbon atoms.) A moisture curable composition comprising the catalyst [B] according to any one of claims 1 to 6 and the organic polymer [A1] or organopolysiloxane [A2]. A moisture-curable composition comprising a step of mixing the catalyst [B] produced by the method according to claim 7 and the organic polymer [A1] or organopolysiloxane [A2]. Production method. A method for producing a cured product , comprising contacting the moisture-curable composition according to claim 11 or the moisture-curable composition produced by the method according to claim 12 with moisture.