JP6240378B2 - Two-component curable composition and sealing material using the same - Google Patents

Description

  The present invention relates to a two-component curable composition and a sealing material using the same.

  Sealing materials are widely used in buildings and the like for filling joints and gaps between various members and ensuring watertightness and airtightness. Typical sealing materials for buildings include sealing materials made of urethane resin, modified silicone resin, silicone resin, polysulfide resin, and the like. Depending on the curing method, the sealing material is classified into a two-component form that is cured by mixing the main agent and the curing agent, and a one-component form that is cured using moisture and oxygen in the air.

  Of these, one-component sealants, especially one-component sealants made of urethane-based prepolymers containing isocyanate groups at the end, do not have to mix the main agent and curing agent, and cure due to mismeasurement of the main agent and curing agent. Since there is no defect, it is excellent in workability and can be used with confidence (see, for example, Patent Document 1). In addition, one-component sealants made of urethane-based prepolymers containing isocyanate groups at the ends are low modulus after curing, high elongation, good rubber elasticity, and excellent adhesion and durability. Usage is increasing.

Japanese Patent Laid-Open No. 2005-314683

  However, a sealing material obtained by curing a curable composition containing an isocyanate group-containing urethane-based prepolymer, when exposed to the outdoors, adheres dirt components such as mold and dust to the surface of the sealing material, There exists a problem that the external appearance of the joint part and joint peripheral member (adhered body) which comprise a building was impaired.

  Further, when the sealing material is exposed to the outdoors for a long time, there is a problem that cracks or discoloration occur on the surface of the sealing material due to deterioration of the sealing material.

  Therefore, the sealing material obtained by hardening | curing the curable composition which mix | blended the urethane type prepolymer containing an isocyanate group was limited to the use predicated on coating the surface with a coating material.

  In addition, since the one-component sealing material has a slow deep-curing property after construction, there is a problem that a curing period is required before proceeding to the next process, and the construction period becomes long.

  In view of the above problems, the present invention can shorten the work period by accelerating deep-part curability, suppresses adhesion of dirt components even when exposed outdoors for a long period of time, and causes cracks and discoloration to occur on the surface of the sealing material. It aims at providing the curable composition excellent in suppressing, and the sealing material using the composition.

The present invention includes the following (1) to (13).
(1) A polyisocyanate compound (D) was reacted with a mixture of a polysulfide polymer (A) having a hydroxyl group, a polyoxyalkylene polyol (B), and a hydroxyl group-containing (meth) acrylic monomer (C). A main agent containing a prepolymer (E);
A curing agent containing water;
A two-component curable composition comprising:
(2) The two-component curable property according to (1), wherein the curing agent is an aqueous solution having a combustible liquid amount of less than 60% by mass and a flash point exceeding the flash point of a 60% by mass aqueous solution of ethyl alcohol. Composition.
(3) The two-component curable composition according to the above (1) or (2), wherein the curing agent contains water and an alkylene oxide polymer.
(4) The two-component curable composition according to (3) above, wherein the alkylene oxide polymer contains an ethylene oxide polymer.
(5) The two-component curable product according to any one of (1) to (4), wherein the main agent further includes a latent curing agent (F) that reacts with moisture to generate an active hydrogen group. Composition.
(6) The two-component curable composition according to the above (5), wherein the latent curing agent (F) is an oxazolidine compound.
(7) The main agent further includes a carboxylic acid silyl ester compound (G) as a reaction accelerator of the latent curing agent (F),
The carboxylic acid silyl ester compound (G) includes a carboxylic acid silyl ester group represented by the following formulas (1) and (2), and the number M of the carboxylic acid silyl ester group represented by the following formula (1): The two-component curable composition according to the above (5) or (6), wherein the number N of the carboxylic acid silyl ester group represented by the following formula (2) satisfies the relationship of the following formula (3).
R ¹ COO-Si≡ (1)
R ² COO-Si≡ (2)
0.10 ≦ M / (M + N) ≦ 0.80 (3)
(In the formula, R ¹ represents a monovalent hydrocarbon group having 13 to 21 carbon atoms, and R ² represents an alkyl group having 5 to 11 carbon atoms.)
(8) The two-component curable composition according to any one of (1) to (7), wherein the main agent further contains calcium carbonate (H) as a filler.
(9) The two-component curable composition according to any one of (1) to (8), wherein the main agent further contains an anti-aging agent (I).
(10) The two-component curable composition according to any one of (1) to (9), wherein the main agent further contains a photocurable unsaturated compound (J).
(11) The two-component curable composition according to any one of (1) to (10), wherein the main agent further contains a photopolymerization initiator (K).
(12) The two-component curable composition according to any one of (1) to (11), wherein the polyisocyanate compound (D) is aliphatic or alicyclic.
(13) A sealing material using the two-component curable composition according to any one of (1) to (12) above.

  According to the present invention, it is possible to shorten the work period by accelerating deep-part curability, and to suppress the adhesion of dirt components even when exposed to the outdoors for a long time, and to suppress the occurrence of cracks and discoloration on the surface of the sealing material. Can provide a two-component curable composition having excellent resistance and a sealing material using the same.

  The present invention will be described in detail below. The present invention is not limited by the following modes for carrying out the invention (hereinafter referred to as embodiments). In addition, constituent elements in the following embodiments include those that can be easily assumed by those skilled in the art, those that are substantially the same, and those in a so-called equivalent range. Furthermore, the constituent elements disclosed in the following embodiments can be appropriately combined.

  The two-component curable composition according to the present embodiment (hereinafter referred to as “the composition of the present embodiment”) includes a polysulfide polymer (A) having a hydroxyl group, a polyoxyalkylene polyol (B), and a hydroxyl group-containing ( A two-component sealant composition comprising a main component containing a prepolymer (E) obtained by reacting a polyisocyanate compound (D) with a mixture with a (meth) acrylic monomer (C), and a curing agent containing water. It is a curable composition that can be used as a product.

<Main agent>
The main agent contained in the composition of the present embodiment is a mixture of a polysulfide polymer (A) having a hydroxyl group, a polyoxyalkylene polyol (B), and a hydroxyl group-containing (meth) acrylic monomer (C). A prepolymer (E) obtained by reacting a polyisocyanate compound (D) is contained.

[Prepolymer (E)]
The prepolymer (hereinafter also referred to as “polysulfide-containing prepolymer”) (E) contained in the main component of the composition of the present embodiment includes a polysulfide polymer (A) having a hydroxyl group, a polyoxyalkylene polyol (B), and A prepolymer (E) obtained by reacting a polyisocyanate compound (D) with a mixture with a hydroxyl group-containing (meth) acrylic monomer (C). The polysulfide-containing prepolymer (E) is obtained by reacting the mixture (polyol compound) and the polyisocyanate compound (D) so that the isocyanate group (NCO group) is excessive with respect to the hydroxyl group (OH group). Reaction product.

  The polysulfide-containing prepolymer (E) is a one-component moisture-curable composition in which isocyanate groups contained in the molecule react with moisture (water) at room temperature to form urea bonds, crosslink and cure. It can also be used as a product. A polysulfide polymer (A) having a hydroxyl group, a polyoxyalkylene polyol (B), a hydroxyl group-containing (meth) acrylic monomer (C) and a polyisocyanate compound (D) are converted into an isocyanate group / active hydrogen (group). Polysulfide by reacting simultaneously or successively in a molar ratio of 1.2 to 1.0 to 10.0 to 1.0, preferably 1.4 to 1.0 to 2.0 to 1.0. It can manufacture suitably so that an isocyanate group may remain in a content prepolymer (E). If the molar ratio of isocyanate group / active hydrogen (group) is less than 1.2 to 1.0, the resulting polysulfide-containing prepolymer (E) has too few crosslinking points, and the elongation and tensile strength after curing of the sealing material This is because the rubber elastic properties such as are lowered and the adhesiveness is poor. This is because if the isocyanate group / active hydrogen (group) molar ratio exceeds 10.0 to 1.0, the amount of carbon dioxide generated increases when it reacts with moisture such as moisture, which causes foaming.

  The content of isocyanate groups in the polysulfide-containing prepolymer (E) is preferably 0.3% by mass or more and 15.0% by mass or less, and particularly preferably 0.5% by mass or more and 5.0% by mass or less. When the isocyanate group content is less than 0.3% by mass, the rubber elastic properties are lowered for the same reason as described above, and sufficient adhesion cannot be obtained. Even when the content of the isocyanate group exceeds 15.0% by mass, foaming due to carbon dioxide gas occurs for the same reason as described above, which is not preferable.

(Polysulfide polymer having a hydroxyl group (A))
The polysulfide polymer (A) contained in the composition of the present embodiment has a sulfide bond or a polysulfide bond in the main chain as a polymer skeleton, and has a hydroxyl group.

  The polymer is not particularly limited as long as the polymer has a sulfide bond or a polysulfide bond as a polymer skeleton. The polysulfide polymer (A) having a hydroxyl group may have, for example, a diethyl formal skeleton, an ether bond, a urethane bond, or an ester bond in the polymer skeleton. The position of the sulfide bond or polysulfide bond in the polysulfide polymer is not particularly limited.

  Specific examples of the polysulfide polymer (A) having such a hydroxyl group include those represented by the following formula (4).

(However, in the formula, the average value of X is 1 or more and 5 or less, and n is an integer of 2 or more and 50 or less. R ₁ is an alkyl group having 2 to 16 carbon atoms or an ether bond-containing alkyl group. R ₂ is an alkyl group having 1 to 100 carbon atoms or an ether bond-containing alkyl group.

Examples of R ₁ include —CH (CH ₃ ) CH ₂ —, —CH ₂ CH ₂ —O—CH ₂ CH ₂ —, —CH ₂ CH ₂ —, —CH ₂ CH ₂ —O—CH ₂ —O—. _{CH 2 CH 2 -, - CH} (CH 3) CH 2 -O-CH (CH 3) -O-CH (CH 3) CH 2 -, - CH 2 CH 2 -O- (CH 2 CH 2 -O) _p- CH ₂ CH ₂ — (p = 1 to 30) and the like can be mentioned. R ₁ is preferably —CH ₂ CH ₂ —O—CH ₂ —O—CH ₂ CH ₂ — (ethyl formal group) from the viewpoint of low viscosity and good workability and curability.

As R ₂ , —CH (CH ₃ ) CH ₂ —, —CH ₂ CH ₂ —, —CH ₂ CH (CH ₃ ) C (═O) O—CH ₂ (C ₃ H ₆ O) n (C _{3 H 6) -, - CH} 2 CH 2 C (= O) O-CH 2 (C 3 H 6 O) n (C 3 H 6) -, - CH 2 CH (CH 3) C (= O) O _{-CH 2 (C 2 H 4 O} ) n (C 2 H 4) -, - CH 2 CH 2 C (= O) O-CH 2 (C 2 H 4 O) n (C 2 H 4) - and Can be mentioned.

In the polysulfide polymer represented by this specific example, the structural unit represented by — (R ₁ —S _X ) — preferably forms all (100% by mass) of the main chain. Even if it contains, it is preferable to form 5 mass% or more and 95 mass% or less.

  Commercially available products can be used as the polysulfide polymer, and specific examples thereof include THIOPLAST polymer manufactured by AKZO NOBEL, LP282 polymer manufactured by Toray Fine Chemical Co., Ltd. .

  In the present embodiment, the number average molecular weight (Mn) of the polysulfide polymer is usually preferably 500 or more and 100,000 or less, and more preferably 500 or more and 20,000 or less. In the present embodiment, the number average molecular weight (Mn) is measured by gel permeation chromatography (GPC).

  The polysulfide polymer can be produced, for example, by a method of adding a hydroxyl group-containing (meth) acrylate to a polysulfide polymer as described in JP-A-4-363325 and JP-A-2010-116452. it can. Moreover, it can manufacture by the method of making an epoxy react with a polysulfide polymer.

  The polysulfide polymer (A) having a hydroxyl group may be a modified polysulfide polymer having a terminal hydroxyl group by modifying the polysulfide polymer. The modified polysulfide polymer having a hydroxyl group is a polymer having a hydroxyl group and having a sulfide bond or a polysulfide bond in the main chain.

(Polyoxyalkylene polyol (B))
The polyoxyalkylene polyol (B) contained in the composition of the present embodiment has a hydroxyl group at the end and is polyadded with the polyisocyanate compound (D) to form urethane. By using the polyoxyalkylene polyol (B) in the composition of the present embodiment, a curable composition having further improved storage stability can be obtained. Examples of the polyoxyalkylene polyol include polyethylene glycol (PEG), polypropylene ethylene polyol, and polytetramethylene ether glycol (PTG) in addition to the polyoxypropylene polyol.

  The number average molecular weight (Mn) of the polyoxyalkylene polyol (B) is preferably from 200 to 20,000. This is because when the number average molecular weight (Mn) is less than 200, the cured product becomes brittle, and when the number average molecular weight (Mn) exceeds 20,000, the physical properties of the cured product become soft.

(Hydroxyl group-containing (meth) acrylic monomer (C))
As the hydroxyl group-containing (meth) acrylic monomer (C) contained in the composition of the present embodiment, an alcoholic hydroxyl group-containing (meth) acrylic monomer is preferable from the viewpoint of the viscosity of the obtained polymer. Specifically, ethanediol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,14- Hydroxyalkyl (meth) acrylates such as tetradecanediol diacrylate, 1,15-pentadecanediol diacrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate; pentaerythritol tri (meth) Acrylate, Mono (meth) acrylates such as lysine mono (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, polypropylene glycol mono (meth) acrylate and the like ( And (meth) acrylates or hydroxyl group residual poly (meth) acrylates. Any of these may be used alone or in admixture of two or more. In some cases, one or more kinds of (meth) acrylic monomers having 9 or less carbon atoms and one or more kinds of (meth) acrylic monomers having 10 or more carbon atoms are used in combination. May be.

(Polyisocyanate compound (D))
The polyisocyanate compound (D) contained in the composition of the present embodiment is not particularly limited as long as it is used in the production of a urethane prepolymer and has two or more isocyanate groups in the molecule. Examples of the polyisocyanate compound include an aromatic polyisocyanate in which an isocyanate group is bonded to an aromatic hydrocarbon, an aliphatic polyisocyanate in which an isocyanate group is bonded to an aliphatic hydrocarbon, and an isocyanate group having an alicyclic hydrocarbon. And an alicyclic polyisocyanate bonded to the. Examples of the aromatic polyisocyanate include toluene such as TDI (for example, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), or a mixture thereof. Diisocyanate), MDI (e.g., diphenylmethane diisocyanate such as 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), or mixtures thereof), 1 , 4-phenylene diisocyanate, diphenyl diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1, - naphthalene diisocyanate (NDI), diphenyl ether diisocyanate, and triphenylmethane triisocyanate. Examples of the aliphatic polyisocyanate include propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI), and the like. Examples of the alicyclic polyisocyanate include cyclohexane diisocyanate, methylene bis (cyclohexyl isocyanate), transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis (isocyanate methyl) cyclohexane (H ₆ XDI), and dicyclohexylmethane diisocyanate (H ₁₂ MDI). These aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanate carbodiimide-modified polyisocyanates, biuret-modified polyisocyanates, allophanate-modified polyisocyanates, polymethylene polyphenyl polyisocyanates (crude MDI or polymeric MDI), isocyanurates Examples thereof include modified polyisocyanates.

  Such polyisocyanate compounds can be used alone or in combination of two or more. Among these polyisocyanate compounds, TDI and MDI are preferable among aromatic polyisocyanates and HDI among aliphatic polyisocyanates because the viscosity becomes low after curing and the handling of the main agent containing the prepolymer is easy. Of XDI and alicyclic polyisocyanate, IPDI is preferred.

  In addition, aliphatic polyisocyanates and alicyclic polyisocyanates are particularly preferable from the viewpoints of compatibility and weather resistance of the obtained prepolymer.

[Latent curing agent (F)]
The main ingredient of the composition of the present embodiment can further contain a latent curing agent. The latent curing agent (F) does not function as a curing agent in a sealed state, that is, in a moisture blocking state, but is a hydrolyzed latent that functions as a curing agent by opening the sealed state and hydrolyzing in the presence of moisture. Curable hardener, does not function as a hardener at room temperature, but melts, dissolves or activates when a certain amount of heat is applied. Examples thereof include a photocuring initiator for initiating a group reaction. As the photocuring initiator, there are a visible curing initiator and an ultraviolet light (UV) curing initiator. A UV cure initiator is an initiator that initiates and induces cure in response to UV. A visible curing initiator is an initiator that initiates and induces curing in response to visible light. In the latent curing agent, two or more of these may be used in combination.

  In the present embodiment, among these, a hydrolytic latent curing agent that reacts with moisture as a curing component to generate an active hydrogen group is suitably used. Specific examples include amine-based latent curing agents such as ketimines and enamines that are a reaction product of a polyamine and a carbonyl compound; and oxazolidine compounds that are a reaction product of an amino alcohol and a carbonyl compound. From the viewpoint of shortening the curing time at room temperature and storage stability of the composition of the present embodiment, it is preferable to use an oxazolidine compound as a latent curing agent.

  By using an oxazolidine compound as a latent curing agent, the composition of the present embodiment obtained can be moisture-cured at room temperature, has excellent storage stability, excellent curability, and adjusts the curing rate. And the curing time can be greatly shortened. Also, the foam resistance can be improved.

  The oxazolidine compound is a compound having 1 or more, preferably 1 to 6 oxazolidine rings in the molecule, which is a saturated 5-membered heterocyclic ring containing an oxygen atom and a nitrogen atom. The oxazolidine compound reacts with moisture (humidity) to undergo hydrolysis, and the oxazolidine ring generates (regenerates) a secondary amino group and an alcoholic hydroxyl group, thereby serving as a latent curing agent for the polysulfide-containing prepolymer (E). It functions. When the isocyanate group of the polysulfide-containing prepolymer (E) reacts with moisture (humidity), it forms a urea bond and cures. At this time, carbon dioxide is also generated, and bubbles due to carbon dioxide are generated in the cured product. However, when a mixture of a polysulfide-containing prepolymer (E) and an oxazolidine compound is exposed to moisture (humidity), the moisture (humidity) Before the isocyanate group reacts, the oxazolidine ring of the oxazolidine compound is hydrolyzed by moisture (humidity) to regenerate secondary amino groups and alcoholic hydroxyl groups, and these active hydrogens react with the isocyanate groups to generate carbon dioxide. By curing without carrying out, foaming by the carbon dioxide gas of the composition of the present embodiment can be prevented.

  In addition, in the synthesis of the polysulfide-containing prepolymer (E), when an aliphatic polyisocyanate is used as the polyisocyanate compound (D), the curing rate is extremely delayed if the reaction is only with water, but oxazolidine By using the compound in combination, the reaction between the secondary amino group regenerated by the reaction with water and the isocyanate group derived from the aliphatic polyisocyanate has a higher reaction speed than the reaction with water, so that the curing speed can be increased. There is an effect that the amount of the curing accelerating catalyst described later can be reduced.

  Examples of the oxazolidine compound include a urethane bond-containing oxazolidine compound, an ester group-containing oxazolidine compound, an oxazolidine silyl ether, and a carbonate group-containing oxazolidine. These oxazolidine compounds are obtained by reacting the hydroxyl group of the compound having a hydroxyl group and an oxazolidine ring with the isocyanate group of the polyisocyanate compound (D) or the carboxyl group of the organic carboxylic acid compound. Of these oxazolidine compounds, urethane bond-containing oxazolidine compounds are preferred from the viewpoint of easy production and low viscosity.

  Specific examples of the compound having a hydroxyl group and an oxazolidine ring include N-hydroxyalkyloxazolidine obtained by a dehydration condensation reaction between a secondary amino group of an alkanolamine and a carbonyl group of a ketone compound or an aldehyde compound. As a method for synthesizing the compound having a hydroxyl group and an oxazolidine ring, the carbonyl group of the aldehyde compound or the ketone compound is 1.0 times mol or more, preferably 1.0 times the 1.0 mol of the secondary amino group of the alkanolamine. Used in a solvent such as toluene, xylene, etc., and dehydrated while removing by-product water. The method of performing a condensation reaction is mentioned. Excess aldehyde compounds and ketone compounds may be removed by distillation.

  Examples of the alkanolamine include diethanolamine, dipropanolamine, N- (2-hydroxyethyl) -N- (2-hydroxypropyl) amine and the like. Examples of the ketone compound include acetone, diethyl ketone, isopropyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl tert-butyl ketone, diisobutyl ketone, cyclopentanone, and cyclohexanone. Examples of the aldehyde compound include acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, 2-methylbutyraldehyde, n-hexylaldehyde, 2-methylpentylaldehyde, n-octylaldehyde, 3, 5 Aliphatic aldehyde compounds such as 1,5-trimethylhexylaldehyde; aromatic aldehyde compounds such as benzaldehyde, methylbenzaldehyde, trimethylbenzaldehyde, ethylbenzaldehyde, isopropylbenzaldehyde, isobutylbenzaldehyde, methoxybenzaldehyde, dimethoxybenzaldehyde, and trimethoxybenzaldehyde . Any of these may be used alone or in admixture of two or more.

  Of these, diethanolamine is preferred as the alkanolamine because it is easy to produce a compound having a hydroxyl group and an oxazolidine ring, and has excellent antifoaming properties when the resulting two-component room temperature curable sealing material is cured. Of the ketone compounds or aldehyde compounds, aldehyde compounds are preferred, and isobutyraldehyde, 2-methylpentylaldehyde, and benzaldehyde are more preferred.

  Specific examples of the compound having a hydroxyl group and an oxazolidine ring include 2-isopropyl-3- (2-hydroxyethyl) oxazolidine, 2- (1-methylbutyl) -3- (2-hydroxyethyl) oxazolidine, 2-phenyl- 3- (2-hydroxyethyl) oxazolidine and the like can be mentioned.

  As the urethane bond-containing oxazolidine compound, the hydroxyl group of the compound having a hydroxyl group and an oxazolidine ring and the isocyanate group of the organic isocyanate compound have an isocyanate group / hydroxyl molar ratio in the range of 0.9 to 1.2, preferably 0.8. Suitable examples include those obtained by reacting at a temperature of 50 ° C. or higher and 120 ° C. or lower in the presence or absence of an organic solvent.

  Examples of the organic isocyanate compound used for the synthesis of the urethane bond-containing oxazolidine compound include the same as those used for the synthesis of the polysulfide-containing prepolymer (E), and of these, the crystallinity of the urethane bond-containing oxazolidine compound Is preferable, and an aliphatic polyisocyanate is preferable, and hexamethylene diisocyanate (HDI) is particularly preferable in that the workability of the sealing material can be improved.

  The ester group-containing oxazolidine compound can be obtained by reacting the aforementioned compound having a hydroxyl group and an oxazolidine ring with a lower alkyl ester of dicarboxylic acid or polycarboxylic acid.

  The oxazolidine silyl ether includes a compound having a hydroxyl group and an oxazolidine ring as described above, trimethoxysilane, tetramethoxysilane, triethoxysilane, dimethoxydimethylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltri It can be obtained by dealcoholization reaction with alkoxysilane such as methoxysilane and 3-glycidoxypropyltriethoxysilane.

  The carbonate group-containing oxazolidine can be obtained by reacting the above-mentioned compound having a hydroxyl group and an oxazolidine ring with a carbonate such as diallyl carbonate using a polyhydric alcohol such as diethylene glycol or glycerin.

  Any of these may be used alone or in admixture of two or more.

  In addition, the oxazolidine compound has an active hydrogen group-containing functional group such as an amino group or a hydroxyl group, or an isocyanate group that reacts with an isocyanate group of a prepolymer containing an isocyanate group at room temperature (or room temperature) of 5 ° C to 35 ° C. It is preferable not to have. This is to prevent a rise in the viscosity of the urethane-based prepolymer and a decrease in the anti-foaming performance of the oxazolidine compound. However, in the synthesis of the urethane bond-containing oxazolidine compound described above, a small amount of active hydrogen group-containing functional group or isocyanate group may remain in the molecule depending on the molar ratio selected. In this case, the object of the present embodiment is achieved. Can be regarded as not having. The “small amount” means that the amount of the active hydrogen group-containing functional group or isocyanate group remaining in the molecule is preferably 0.05 mmol or less, more preferably 0.02 mmol or less, per 1 g of the oxazolidine compound.

  The amount of the oxazolidine compound used is such that the active hydrogen of the secondary amino group regenerated by hydrolysis of the oxazolidine compound is 0.1 mol or more and 1.0 mol relative to 1.0 mol of the isocyanate group in the polysulfide-containing prepolymer (E). It is preferable to use so that it may become below, and it is more preferable to use it so that it may become 0.3 mol or more and 1.0 mol or less. This is because if the amount of the oxazolidine compound used is less than 0.1 mol, foaming prevention is insufficient, which is not preferable.

  When the oxazolidine compound is used as the latent curing agent (F) from the viewpoint of adjusting the curing rate of the polysulfide-containing prepolymer (E), the latent curing agent (F) is 100 parts by mass of the polysulfide-containing prepolymer (E). 2.0 parts by mass or more and 20.0 parts by mass or less is preferable, more preferably 5.0 parts by mass or more and 15.0 parts by mass or less, and more preferably 7.0 parts by mass or more and 10.0 parts by mass or less. More preferably, it is blended in an amount of at most parts. This is because when the content of the latent curing agent (F) is less than 2.0 parts by mass, the curing rate of the polysulfide-containing prepolymer (E) becomes slow. Moreover, it is because the cure rate of a polysulfide containing prepolymer (E) will be too quick when content of a latent hardener (F) exceeds 20.0 mass parts.

[Carboxylic acid silyl ester compound (G)]
The main component of the composition of the present embodiment can further contain a carboxylic acid silyl ester compound (G) as a reaction accelerator for the latent curing agent (F). In the composition of this embodiment, when the prepolymer (E) containing an isocyanate group and the oxazolidine compound are combined, it is preferable that the carboxylic acid silyl ester compound (G) is included. The carboxylic acid silyl ester compound (G) is used as a reaction accelerator for the oxazolidine compound (hereinafter also referred to as “ring-opening catalyst”) when the prepolymer (E) containing an isocyanate group and the oxazolidine compound are combined. The reaction accelerator (ring-opening catalyst) accelerates the oxazolidine compound to react with water (humidity) and hydrolyze to regenerate the active hydrogen, and the regenerated active hydrogen and the prepolymer (E ) To promote the reaction with the isocyanate group and to accelerate the curing of the composition of the present embodiment.

The carboxylic acid silyl ester compound (G) has a carboxylic acid silyl ester group represented by the following formulas (5) and (6), and has a number M of carboxylic acid silyl ester groups represented by the following formula (5): It is preferable that the number N of the carboxylic acid silyl ester group represented by the following formula (6) satisfies the relationship of the following formula (7).
R ¹ COO-Si≡ (5)
R ² COO-Si≡ (6)
0.10 ≦ M / (M + N) ≦ 0.80 (7)
(In the formula, R ¹ represents a monovalent hydrocarbon group having 13 to 21 carbon atoms, preferably 13 to 17 carbon atoms, and R ² represents an alkyl group having 5 to 11 carbon atoms, preferably 7 to 11 carbon atoms.)

  Even if the carboxylic acid silyl ester compound (G) is used in combination with compounds having carboxylic acid silyl ester groups represented by the above formulas (5) and (6) in different molecules, these carboxylic acid silyl ester compounds It may be a compound itself having an ester group in the same molecule or a compound containing the compound. Among these, the latter is preferable from the viewpoint of productivity of the composition of the present embodiment and the ring-opening catalyst. In the present embodiment, the latter aspect includes an aspect in which the silicon (Si) atoms of the carboxylic acid silyl ester groups represented by the above formulas (5) and (6) are the same atom.

In the above formula (5), examples of the monovalent hydrocarbon group having 13 to 21 carbon atoms represented by R ¹ include unsaturated monovalent aliphatic hydrocarbon groups such as unsaturated groups such as alkenyl groups or alkyl groups; And monovalent alicyclic hydrocarbon groups such as hexyl groups; monovalent aromatic-containing hydrocarbon groups such as phenyl groups, tolyl groups, benzyl groups, and styryl groups; and the like. Specifically, preferable examples of the alkyl group include n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group and the like.

Specific examples of the alkyl group having 5 to 11 carbon atoms of R ^{2 in} the above formula (6) include, for example, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, tert- Pentyl group, neopentyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 2,2-dimethylpentyl group, 3,3-dimethylpentyl group, 2,3-dimethylpentyl group 2,4-dimethylpentyl group, 2-ethylpentyl, 3-ethylpentyl group, 2,2,3-trimethyl butyl group, n- octyl group, n- nonyl, n- undecyl group, and the like. Of these, a 1-ethylpentyl group and an n-undecyl group are preferable.

  On the other hand, as shown by the above formula (7), the ratio of the number M of the carboxylic acid silyl ester group represented by the above formula (5) and the number N of the carboxylic acid silyl ester group represented by the above formula (6). (M / (M + N)) is in the range of 0.10 to 0.80, and preferably in the range of 0.20 to 0.80.

  The carboxylic acid silyl ester compound (G) has a siloxane unit represented by the following formulas (8) and (9) including the carboxylic acid silyl ester groups represented by the above formulas (5) and (6). preferable.

In the above formulas (8) and (9), R ¹ represents a monovalent hydrocarbon group having 13 to 21 carbon atoms, R ² represents an alkyl group having 5 to 11 carbon atoms, and R ³ represents a hydrogen atom. Alternatively, it represents a monovalent hydrocarbon group having 1 to 8 carbon atoms which may have a substituent.

Here, R ¹ in the above formula (8) and R ² in the above formula (9) are respectively R ¹ explained in the above formula (5) and R ² explained in the above formula (6). It is the same. In the above formulas (8) and (9), examples of the monovalent hydrocarbon group having 1 to 8 carbon atoms that may have a substituent of R ³ include an alkyl group, a vinyl group, and an allyl group. A monovalent aliphatic hydrocarbon group such as cyclohexyl group; a monovalent alicyclic hydrocarbon group such as cyclohexyl group; a monovalent aromatic hydrocarbon group such as phenyl group, tolyl group, benzyl group, styryl group; and Group which combined these; etc. are mentioned. Specifically, preferred examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-octyl group. Of these, a methyl group and a phenyl group are preferable.

  Specifically as a siloxane unit represented by the said Formula (8), the siloxane unit represented by each formula of following formula (I) is illustrated suitably.

Specifically as a siloxane unit represented by the said Formula (9), the siloxane unit represented by each formula of following formula (II) is illustrated suitably.

  The siloxane units represented by the above formulas (8) and (9) can be used alone or in combination of two or more.

The carboxylic acid silyl ester compound (G) preferably further has an ether-containing silyl group represented by the following formula (10), and the carboxylic acid silyl ester is represented by the above formulas (5) and (6). A compound having a carboxylic acid silyl ester group and an ether-containing silyl group represented by the following formula (10) in the same molecule is more preferable.
R ⁶ O— (R ⁵ O) _r —R ⁴ —Si≡ (10)
(In the above formula (10), R ⁴ and R ⁵ each independently represents an alkylene group having 2 to 6 carbon atoms which may have a substituent, and R ⁶ represents a hydrogen atom or 1 to 30 carbon atoms. Or an organic group represented by R ¹³ — (CO) — (R ¹³ represents a hydrocarbon group having 1 to 30 carbon atoms), r represents an integer of 1 or more, and r is 2. In the case of the above integers, the plurality of R ⁵ may be the same or different.)

Specific examples of the alkylene group having 2 to 6 carbon atoms that may have a substituent of R ^{4 in} the above formula (10) include, for example, an ethylene group and a trimethylene group (—CH ₂ CH ₂ CH ₂ -), propylene group _{(-CH (CH 3) -CH 2} -), tetramethylene group, 1,1-dimethylethylene group, and the like. Of these, an ethylene group and a trimethylene group are preferable.

R ⁵ in the above formula (10) is the same as R ⁴ in the above formula (10), but when r is 2 or more, the plurality of R ⁵ may be the same or different. Good. In the above formula (10),-(OR ⁵ ) _r -is not particularly limited with respect to the arrangement thereof, and examples thereof include random, block, and arrangement by mixing random and block. Among these, it is preferable that R ⁵ is an ethylene group or a propylene group. That, - (OR ⁵⁾ _r - is - with a repeating unit represented _{by, - - (OCH 2 CH 2} ) (OCH (CH 3) CH 2) - preferably comprises a repeating unit represented by .

In the formula (10), R ⁶ is, for example, a monovalent aliphatic hydrocarbon group such as an alkyl group, a vinyl group or an allyl group; a monovalent alicyclic hydrocarbon group such as a cyclohexyl group. Monovalent aromatic hydrocarbon groups such as phenyl group, tolyl group, benzyl group and styryl group; and combinations thereof; and the like. Specifically, preferred examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-octyl group, and a 2-ethylhexyl group. Of these, an n-butyl group, an n-octyl group, and a 2-ethylhexyl group are preferable.

  In the above formula (10), the integer of 1 or more of r is preferably an integer of 5 or more, more preferably 10 or more and 100 or less.

  The carboxylic acid silyl ester compound (G) preferably has a siloxane unit represented by the following formula (11) including the ether-containing silyl group represented by the above formula (10).

In the above formula (11), R ³ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, and R ⁴ and R ⁵ are each independently a substituent. Represents an alkylene group having 2 to 6 carbon atoms, and R ⁶ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an organic group represented by R ¹³ — (CO) — (R ¹³ represents Represents a hydrocarbon group having 1 to 30 carbon atoms, and r represents an integer of 1 or more. When r is an integer greater than or equal to 2, several R < ⁵ > may be same or different, respectively. Here, ^{R 3} in the formula (11) is the same as R ³ as described in the above formula (8) and (9) in. Further, R ^4, R ⁵ and R ⁶ and r in the formula (11) are respectively the same as R ^4, R ⁵ and R ⁶ and r described in the above formula (10) in.

  Specific examples of the siloxane unit represented by the above formula (11) include siloxane units represented by the following formula (III).

  The siloxane units represented by the above formula (11) can be used alone or in combination of two or more.

  As the carboxylic acid silyl ester compound (G), the siloxane unit represented by the above formulas (8) and (9) and the siloxane unit represented by the above formula (11) are either or both of the inside of the molecule and the molecular end. It is preferable to use polysiloxane contained in

  In the present embodiment, the siloxane units represented by the above formulas (8), (9), and (11) are not particularly limited with respect to the arrangement. For example, the arrangement is random, block, or a mixture of random and block. Can be mentioned.

  The polysiloxane may have a siloxane unit other than the siloxane units represented by the above formulas (8), (9) and (11). Examples of such a siloxane unit include the following formula (12): And siloxane units represented.

In the above formula (12), R ⁸ represents a methyl group, an ethyl group or a phenyl group, and R ⁹ represents a hydrogen atom or a monovalent hydrocarbon group. Examples of the monovalent hydrocarbon group include unsaturated monovalent aliphatic hydrocarbon groups such as unsaturated or alkenyl groups such as alkenyl groups; monovalent alicyclic hydrocarbon groups such as cyclohexyl groups; phenyl And monovalent aromatic-containing hydrocarbon groups such as a group, tolyl group, benzyl group and styryl group. Specifically, preferred examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-octyl group. Of these, a methyl group and a phenyl group are preferable.

  Specifically as a siloxane unit represented by the said Formula (12), the siloxane unit represented by the following formula (13) or (14) is illustrated suitably.

The molecular terminal of the polysiloxane is not particularly limited, and examples of the terminal group include -SiR ¹⁰ ₃ , -Si (OR ¹⁰ ) ₃ , -Si (R ¹⁰ ) ₂ (OH) (wherein R ¹⁰ is A hydrocarbon group having 1 to 12 carbon atoms, specifically, a methyl group, an ethyl group or a phenyl group, and a plurality of R ^{10 s} may be the same or different. In particular, a trimethylsilyl group, a triethylsilyl group and the like are preferably exemplified.

  The polymerization degree of the polysiloxane is preferably 2 or more and 1000 or less, more preferably 10 or more and 100 or less. When the polymerization degree of the polysiloxane is within this range, the handleability is good.

  Among the polysiloxanes, examples of the polysiloxane having a siloxane unit represented by the above formulas (8) and (9) include a polysiloxane represented by the following formula (15).

In the above formula (15), R ¹ represents a monovalent hydrocarbon group having 13 to 21 carbon atoms, R ² represents an alkyl group having 5 to 11 carbon atoms, and R ³ has a hydrogen atom or a substituent. Represents a monovalent hydrocarbon group having 1 to 8 carbon atoms which may be present. R ¹⁰ represents a hydrocarbon group having 1 to 12 carbon atoms, specifically, a methyl group, an ethyl group or a phenyl group, which may be the same or different, and a and b in the above formula (15) are each Independently represents an integer of 1 or more.

Wherein, R ¹ and R ² in the formula (15) are each the same as R ² described in R ¹ and the formula (6) in which described in the above formula (5), the formula ( 15) ^{R 3} in is the same as R ³ as described in the above formula (8) and (9) in.

  A in the formula (15) represents the number of repeating units of the siloxane unit having a carboxylic acid silyl ester group represented by the formula (5), that is, the siloxane unit represented by the formula (8). It is the above integer, preferably 1 or more and 100 or less, more preferably 1 or more and 50 or less.

  B in the formula (15) represents the number of repeating units of the siloxane unit having a carboxylic acid silyl ester group represented by the formula (6), that is, the siloxane unit represented by the formula (9). It is the above integer, preferably 1 or more and 100 or less, more preferably 1 or more and 50 or less.

  In the above formula (15), each of the two siloxane units having a carboxylic acid silyl ester group is not particularly limited with respect to the arrangement thereof, and examples thereof include random, block, and arrangement by mixing random and block.

  Specific examples of the polysiloxane represented by the above formula (15) include polysiloxane represented by the following formula (16).

  In the above formula (16), each of the two siloxane units having a carboxylic acid silyl ester group is not particularly limited in terms of arrangement, and examples thereof include random, block, and arrangement by mixing random and block.

  The production method of the polysiloxane having the siloxane unit represented by the above formulas (8) and (9) is not particularly limited. For example, by a method of reacting a Si-H group-containing polysiloxane described later with a predetermined carboxylic acid. Can be manufactured. In this reaction, a Group VIII transition metal complex such as palladium, rhodium, nickel, or platinum can be used as a catalyst.

On the other hand, among the polysiloxanes, specific examples of polysiloxanes having siloxane units represented by the above formulas (8) and (9) and siloxane units represented by the above formula (11) include the following formulas ( The organosiloxane represented by 17) is preferably exemplified.
(R ¹ COO) _a (R ² COO) _b R ³ _c R ⁷ _d SiO _{(4-a-bc-d) / 2} (17)
0.10 ≦ a / (a + b) ≦ 0.8 (18)
1 ≦ c <2 (19)
0.001 ≦ d <1 (20)
1.95 ≦ a + b + c + d ≦ 2.60 (21)

In the above formula (17), R ¹ represents a monovalent hydrocarbon group having 13 to 21 carbon atoms, R ² represents an alkyl group having 5 to 11 carbon atoms, and R ³ has a hydrogen atom or a substituent. Represents a monovalent hydrocarbon group having 1 to 8 carbon atoms which may be present. In the formula, R ⁷ represents a polyether-containing group represented by —R ⁴ — (OR ⁵ ) _r —OR ⁶ , and R ⁴ and R ⁵ each independently have a substituent. R ⁶ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an organic group represented by R ¹³ — (CO) — (R ¹³ is an alkyl group having 1 to 30 carbon atoms). 30 represents a hydrocarbon group), and r represents an integer of 1 or more. When r is an integer of 2 or more, the plurality of R ⁵ in the polyether-containing group may be the same or different. Further, a, b, c and d in the above formulas (17) to (21) represent numbers satisfying the relations of the above formulas (18) to (21).

Wherein, R ¹ and R ² in the formula (17) are respectively the same as R ² described in R ¹ and the formula (6) in which described in the above formula (5). Further, ^{R 3} in the formula (17) is the same as R ³ as described in the above formula (8) and (9) in. R ⁴ , R ^5, R ⁶ and r in the polyether-containing group (—R ⁴ — (OR ⁵ ) _r —OR ⁶ ) represented by R ⁷ in the above formula (17) are each represented by the above formula ( 10) The same as R ⁴ , R ⁵ and R ⁶ and r described in 10).

  A, b, c and d representing the numbers satisfying the relations of the above formulas (18) to (21) are 0.01 ≦ a ≦ 1.0, 0.05 ≦ b ≦ 1.0, 1.0, respectively. It is preferable that ≦ c ≦ 1.3 and 0.005 ≦ d ≦ 0.05.

  In the above formula (17), the ratio of the polyether-containing group to the total number of carboxylic acid silyl ester groups, that is, d / (a + b) is preferably 0.01 or more and 0.7 or less, and 0.01 or more More preferably, it is 0.5 or less.

  Examples of such an organosiloxane include polysiloxane represented by the following formula (22).

In the above formula (22), R ¹ represents a monovalent hydrocarbon group having 13 to 21 carbon atoms, R ² represents an alkyl group having 5 to 11 carbon atoms, and R ³ has a hydrogen atom or a substituent. Represents a monovalent hydrocarbon group having 1 to 8 carbon atoms which may be present. R ⁴ and R ⁵ each independently represents an optionally substituted alkylene group having 2 to 6 carbon atoms, and R ⁶ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or R ^13- ( CO) — represents an organic group (R ¹³ represents a hydrocarbon group having 1 to 30 carbon atoms), and r represents an integer of 1 or more. When r is an integer of 2 or more, the plurality of R ⁵ in the polyether-containing group may be the same or different. R ¹⁰ represents a hydrocarbon group having 1 to 12 carbon atoms, specifically, a methyl group, an ethyl group or a phenyl group, and may be the same or different. In the above formula (22), a, b and d each independently represent an integer of 1 or more.

Wherein, R ¹ and R ² in the formula (22) are each the same as R ² described in R ¹ and the formula (6) in which described in the above formula (5), the formula ( 22) R ³ in is the same as R ³ as described in the above formula (8) and (9) in, R ^4, R ⁵ and R ⁶ and r in the formula (22), respectively, the This is the same as R ⁴ , R ^5, R ⁶ and r described in formula (10).

  A and b in the above formula (22) are the same as a and b described in the above formula (15), respectively. Moreover, d in the said Formula (22) represents the number of repeating units of the siloxane unit which has an ether containing silyl group represented by the said Formula (10), ie, the siloxane unit represented by the said Formula (11), It is an integer of 1 or more, preferably from 1 to 10, and more preferably from 1 to 5.

  In the above formula (22), each of the two siloxane units having a carboxylic acid silyl ester group and the siloxane unit having an ether-containing silyl group are not particularly limited with respect to the arrangement thereof, for example, random, block, random and block, The arrangement | sequence by mixing is mentioned.

  Specific examples of the organosiloxane represented by the above formula (22) include polysiloxane represented by the following formula (23).

  In the above formula (23), a, b and d each independently represent an integer of 1 or more, s and t each independently represents an integer of 0 or more, and s + t is 1 or more.

Here, a and b in the above formula (23) are respectively the same as a and b described in the above formula (15), and d in the above formula (23) is in the above formula (22). It is the same as d explained in. In the above formula (23), s represents the number of repeating units of —OCH ₂ CH ₂ —, and t represents the number of repeating units of —OCH ₂ CH (CH ₃ ) —. In the above formula (23), s and t have a relationship of r = s + t with r in the above formula (10) or (11). s + t is 1 or more, preferably 5 or more, and more preferably 10 to 100. In the formula (23), —OCH ₂ CH ₂ — and —OCH (CH ₃ ) CH ₂ — are not particularly limited with respect to the arrangement thereof. For example, the arrangement is random, block, or a mixture of random and block. Is mentioned.

  In the above formula (23), each of the two siloxane units having a carboxylic acid silyl ester group and the siloxane unit having an ether-containing silyl group are not particularly limited with respect to the arrangement thereof, for example, random, block, random and block, The arrangement | sequence by mixing is mentioned.

  A more specific example of the organosiloxane represented by the above formula (23) includes a polysiloxane represented by the following formula (24).

  The production method of the polysiloxane having the siloxane unit represented by the above formulas (8) and (9) and the siloxane unit represented by the above formula (11) is not particularly limited. Siloxane and alkenyl ether are reacted to form a siloxane unit represented by the above formula (11), and then a predetermined carboxylic acid is reacted to form siloxane units represented by formulas (8) and (9). It can be produced by a method of forming and producing polysiloxane; a method of reacting Si—H group-containing polysiloxane, alkenyl ether and a predetermined carboxylic acid simultaneously; In these reactions, it is desirable to use a group VIII transition metal catalyst such as platinum, rhodium, palladium, nickel as the catalyst. Specifically, chloroplatinic acid, alcohol-modified chloroplatinic acid, A platinum-vinylsiloxane complex or the like can be preferably used. In addition, the usage-amount of a catalyst is not specifically limited, It is preferable that it is 50 ppm or less with a metal content, and it is more preferable that it is 20 ppm or less.

  Specifically, as the former production method, for example, a Si-H group-containing polysiloxane and an alkenyl ether, which will be described later, are reacted by adding a Group VIII transition metal complex such as platinum as a catalyst, and then reacting. One preferred embodiment is a method of reacting the carboxylic acid.

  In this production method, when the Si—H group-containing polysiloxane and the alkenyl ether are not compatible, a hydrocarbon solvent such as toluene or xylene can be used. As a result, the reaction proceeds promptly. The reaction temperature is preferably 60 ° C. or higher and 120 ° C. or lower, particularly preferably 80 ° C. or higher and 110 ° C. or lower.

  In the reaction with the carboxylic acid, the Group VIII transition metal complex can be used as a catalyst as in the reaction with the Si—H group-containing polysiloxane and the alkenyl ether. The reaction temperature with the carboxylic acid is usually 80 ° C. or higher and 110 ° C. or lower. In particular, it is preferable from the viewpoint of safety and efficiency that the reaction temperature is low in the early stage of the reaction and higher in the late stage of the reaction.

  The Si—H group-containing polysiloxane used for the production of the polysiloxane is not particularly limited, and specific examples thereof include polysiloxane having an alkyl hydrogen siloxane unit represented by the following formula (25).

In the above formula (25), R ¹¹ is a methyl group, an ethyl group, or a phenyl group.

  The polysiloxane having an alkylhydrogensiloxane unit represented by the above formula (25) is not particularly limited, and conventionally known ones can be used. Specific examples include polysiloxanes represented by the following formulas (IV).

  The Si—H group-containing polysiloxanes can be used alone or in combination of two or more.

The said alkenyl ether used for manufacture of the said polysiloxane is not specifically limited, As the specific example, the alkenyl ether represented by following formula (26) is mentioned.
CH ₂ = CH—R ¹² — (OR ⁵ ) _r —OR ⁶ (26)

In the above formula (26), R ⁵ represents an optionally substituted alkylene group having 2 to 6 carbon atoms, R ⁶ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or R ¹³ — (CO )-Represents an organic group (R ¹³ represents a hydrocarbon group having 1 to 30 carbon atoms), R ¹² does not exist (is a single bond) or represents a methylene group, and r is 1 It represents the above integer. When r is an integer of 2 or more, the plurality of R ⁵ in the polyether-containing group may be the same or different.

Here, R ^5, R ⁶ and r in the formula (26) are the same as R ^5, R ⁶ and r described in the above formula (10) in.

  Examples of the alkenyl ether represented by the above formula (26) include polyethylene glycol, polypropylene glycol, and a copolymer of ethylene glycol and propylene glycol represented by the following formulas (V).

In the following formula representing a copolymer of ethylene glycol and propylene glycol, s represents the number of repeating units of —OCH ₂ CH ₂ —, t represents the number of repeating units of —OCH (CH ₃ ) CH ₂ —, s and t are each independently an integer of 0 or more. Further, s + t is 1 or more, preferably 5 or more, and more preferably 10 or more and 100 or less. Note that r in the above formula (26) and the formulas s and t in the following formula (V) have a relationship of r = s + t. Among these, a copolymer of ethylene glycol and propylene glycol having a molecular weight of 500 or more is preferable. The alkenyl ethers can be used alone or in combination of two or more.

  The predetermined carboxylic acid used in the production of the polysiloxane is, for example, tridecyl acid, tetradecanoic acid (myristic acid), pentadecanoic acid, hexadecanoic acid as a carboxylic acid for forming the siloxane unit represented by the above formula (8). (Palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid) and the like can be used, and as the carboxylic acid for forming the siloxane unit represented by the above formula (9), for example, hexanoic acid (caproic acid), Heptanoic acid, octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), dodecylic acid (lauric acid) can be used. Especially, as carboxylic acid for forming the siloxane unit represented by the said Formula (8), a palmitic acid and a stearic acid are preferable, As carboxylic acid for forming the siloxane unit represented by the said Formula (9) Is preferably capric acid or lauric acid. These carboxylic acids can be used alone or in combination of two or more.

  As a reaction accelerator (ring-opening catalyst), in addition to the carboxylic acid silyl ester compound (G), a metal-based catalyst, an amine-based catalyst, an organic carboxylic acid-based catalyst, and a phosphoric acid ester-based catalyst are excellent in the effect of promoting the curing. , P-toluenesulfonyl monoisocyanate, a reaction product of p-toluenesulfonyl monoisocyanate and moisture, and the like.

  As the metal-based catalyst and amine-based catalyst, the same organometallic compounds, tertiary amines, tertiary amines and carboxylic acids as those mentioned as curing accelerators for the polysulfide-containing prepolymer (E) described later as additives. Examples include salts such as acids.

  Examples of organic carboxylic acid catalysts include formic acid, acetic acid, propionic acid, caproic acid, oxalic acid, succinic acid, adipic acid, 2-ethylhexanoic acid (octylic acid), octenoic acid, lauric acid, oleic acid, stearic acid, etc. Examples thereof include α, β-unsaturated carboxylic acids such as aliphatic carboxylic acid, maleic acid and acrylic acid, aromatic carboxylic acids such as phthalic acid, benzoic acid and salicylic acid, and acid anhydrides thereof.

  Examples of phosphoric acid ester-based catalysts include orthophosphoric acid ester compounds and phosphite ester compounds. Examples of orthophosphoric acid ester compounds include ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, and oleyl acid phosphate. Examples of the phosphite compound include triethyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, diphenyl mono (2-ethylhexyl) phosphite, and the like. Arsenic triester compounds such as diphenyl monodecyl phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen Phosphite diester compounds such Sufaito the like.

  The reaction product of p-toluenesulfonyl monoisocyanate and moisture may be obtained by reacting p-toluenesulfonyl monoisocyanate and moisture in advance before blending into the composition of the present embodiment, What was reacted with water added while p-toluenesulfonyl monoisocyanate was blended in the composition of the present embodiment, or reacted with water present in the composition of the present embodiment. Alternatively, it may be produced by reacting with moisture contained in an additive, which will be described later, during storage after blending in the composition of the present embodiment.

  In the composition of this embodiment, the carboxylic acid silyl ester compound (G) can be used alone, but the ring-opening catalyst (reaction promotion) other than the carboxylic acid silyl ester compound (G) and the carboxylic acid silyl ester compound (G). One or more agents may be used in combination. The carboxylic acid silyl ester compound (G) can improve the storage stability of the sealing material, and the ring-opening catalyst other than the carboxylic acid silyl ester compound (G) improves the curing acceleration effect of the composition of the present embodiment. Can be made.

  The blending amount of the ring-opening catalyst of the oxazolidine compound is preferably 0.001 part by mass or more and 10 parts by mass or less, and further 0.1 part by mass or more with respect to 100 parts by mass of the urethane-based prepolymer (E) containing an isocyanate group. 10 parts by mass or less is preferable. If it is less than 0.001 part by mass, the effect of promoting hydrolysis is small, and if it exceeds 10 parts by mass, the storage stability of the sealing material and the water resistance and heat resistance of the cured product are deteriorated.

[Calcium carbonate (H)]
The main ingredient of the composition of the present embodiment can further contain calcium carbonate. In the composition of this embodiment, calcium carbonate (H) is used as a filler for the polysulfide-containing prepolymer (E) contained in the main agent. The calcium carbonate (H) used in the present embodiment is not particularly limited, and examples thereof include heavy calcium carbonate, precipitated calcium carbonate (light calcium carbonate), colloidal calcium carbonate, and organic surface-treated calcium carbonate. Calcium carbonate (H) can be used alone or in combination of two or more.

(Organic surface treated calcium carbonate)
As the organic surface-treated calcium carbonate contained in the composition of the present embodiment, organic surface-treated calcium carbonate surface-treated with a fatty acid, a resin acid such as rosin acid, a fatty acid ester, a higher alcohol addition isocyanate compound, or the like can be used. . The organic surface-treated calcium carbonate can be produced by a known method. By treating the surface of finely powdered calcium carbonate with the purpose of imparting thixotropy to calcium carbonate with a metal salt or ester of resin acid such as fatty acid or rosin acid and preventing secondary aggregation, the surface of fatty acid Organic surface-treated calcium carbonate such as treated calcium carbonate or resin acid surface-treated calcium carbonate can be obtained. As the fatty acid metal salt, sodium, potassium, calcium and aluminum salts of fatty acids having 10 to 25 carbon atoms such as stearic acid are preferable. Commercially available products of calcium carbonate surface-treated with fatty acids include Calfine 200 (manufactured by Maruo Calcium Co., Ltd.), Ryton 26-A (heavy calcium carbonate, manufactured by Bihoku Flour & Chemical Co., Ltd.), Baiyinhua CC, CCR, R06, VIGOT -10, VIGOT-15, STAVIGOT-15A, Viscolite MBP (manufactured by Shiraishi Kogyo Co., Ltd.), NCC # 3010, NCC # 1010 (manufactured by Nitto Flour Chemical Co., Ltd.), and the like. As calcium carbonate surface-treated with modified fatty acids, Ryton A-4 (heavy calcium carbonate, manufactured by Bihoku Flour & Chemical Co., Ltd.), as calcium carbonate surface-treated with fatty acid esters, Sealets 200 (manufactured by Maruo Calcium Co., Ltd.), Snow Light SS (heavy calcium carbonate, manufactured by Maruo Calcium Co., Ltd.) and the like can be mentioned. Of these, those having a surface treatment with a fatty acid, a modified fatty acid, a fatty acid ester, a higher alcohol-added isocyanate compound, or the like are particularly preferable in that the thixotropic imparting effect is high. These may be used alone or in combination of two or more.

  The surface-treated organic surface-treated calcium carbonate can give an effect of imparting thixotropy and can suppress secondary aggregation. Further, the organic surface-treated calcium carbonate contributes to shape retention and workability because the viscosity is increased, and contributes to storage stability because the surface is hydrophobic.

The average particle diameter of the organic surface-treated calcium carbonate is preferably 0.01 μm or more and 0.5 μm or less, and more preferably 0.03 μm or more and 0.15 μm or less. The BET specific surface area of the organic surface-treated calcium carbonate is preferably 5 m ² / g or more and 200 m ² / g or less, and more preferably 10 m ² / g or more and 60 m ² / g. When the average particle diameter of the organic surface-treated calcium carbonate is less than 0.01 μm or the BET specific surface area is more than 200 m ² / g, the viscosity of the cured product obtained by curing the composition of the present embodiment is increased. This is not preferable because the properties deteriorate. Moreover, if the average particle diameter of the organic surface-treated calcium carbonate exceeds 0.5 μm or the BET specific surface area is less than 5 m ² / g, the thixotropic effect is lost, which is not preferable.

  The content of the organic surface-treated calcium carbonate is preferably 20 parts by mass or more and 300 parts by mass or less, more preferably 50 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the polysulfide-containing prepolymer (E). . If the content of the organic surface-treated calcium carbonate is less than 20 parts by mass, the thixotropic imparting effect of the composition of the present embodiment is remarkably reduced, which is not preferable. Moreover, when content of organic surface treatment calcium carbonate exceeds 300 mass parts, since the viscosity of the composition of this embodiment will become high and workability | operativity will deteriorate, it is unpreferable.

  The content of calcium carbonate (H) is preferably 30 parts by mass or more and 400 parts by mass or less, more preferably 30 parts by mass or more and 400 parts by mass with respect to 100 parts by mass of the polysulfide-containing prepolymer (E) described above. Or less. When the content of calcium carbonate (H) is within the above range, the viscosity of the composition of the present embodiment does not become too high, and the workability is excellent.

[Anti-aging agent (I)]
The main ingredient of the composition of the present embodiment can further contain an anti-aging agent. The anti-aging agent (I) prevents oxidation, photodegradation and thermal degradation after curing of the polysulfide-containing prepolymer, and further improves the weather resistance and heat resistance. Examples of the anti-aging agent (I) include N, N'-diphenyl-p-phenylenediamine (DPPD), N, N'-dinaphthyl-p-phenylenediamine (DNPD), 2,2,4-trimethyl-1 , 3-dihydroquinoline (TMDQ), N-phenyl-1-naphthylamine (PAN), tris (tridecyl) phosphite, hindered phenol compounds, hindered amine light stabilizers, hindered phenol antioxidants, etc. Can do.

  Examples of the hindered amine light stabilizer include bis (1,2,2,6,6-pentamethyl-4-piberidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl. ] Butyl malonate, bis (2,2,6,6-tetramethyl-4-piberidyl) sebacate, methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 4-benzoyloxy-2 2,6,6-tetramethylpiberidine and the like. In addition, low molecular weight hindered amines having a molecular weight of less than 1,000, such as LA-52, LA-57, LA-62, LA-67, LA-77, LA-82, and LA-87 of ADK STAB series manufactured by Asahi Denka Kogyo Co., Ltd. High molecular weight hindered amine light stabilizers having a molecular weight of 1,000 or more such as 119FL, 2020FDL, 944FD, 944LD of the CHIMASSORB series manufactured by Ciba Specialty Chemicals, also LA-63P, LA-68LD, Also included are TINUVIN series hindered amine light stabilizers such as TINUVIN 765.

  Examples of the hindered phenol antioxidant include IRGAFOS XP series IRGANOX 1010 (pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) manufactured by Ciba Specialty Chemicals. ) Propionate]), IRGANOX 1035 (thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]), IRGANOX 1076 (octadecyl-3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propionate), IRGANOX 1135 (benzenepropanoic acid 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester), IRGANOX 1520L (4,6 In addition to hindered phenolic antioxidants such as bis (octylthiomethyl) -o-cresol), N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propioamide], 2,4-dimethyl-6- (1-methylpentadecyl) phenol and the like.

  These anti-aging agents (I) may be used alone or in combination of two or more. In particular, it is preferable to use any one or both of a hindered amine light stabilizer and a hindered phenol antioxidant as the anti-aging agent because of excellent weather resistance.

  From the viewpoint of providing weather resistance, the antioxidant (I) is preferably blended in an amount of 0.1 parts by mass or more and 10.0 parts by mass or less, based on 100 parts by mass of the polysulfide-containing prepolymer (E), and 0.5 parts by mass. More preferably, it is blended in an amount of 5.0 parts by mass or more and 5.0 parts by mass or less. This is because the weather resistance of the composition of the present embodiment does not change so much even if the content of the antioxidant (I) exceeds 10.0 parts by mass.

[Photocurable unsaturated compound (J)]
The main component of the composition of the present embodiment can further contain a photocurable unsaturated compound. The photocurable unsaturated compound (J) is cured by irradiation with predetermined light. The photocurable unsaturated compound (J) is preferably a polyfunctional ethylenic photocurable unsaturated compound having at least two ethylenically unsaturated bonds in the molecule. The polyfunctional ethylenically photocurable unsaturated compound effectively receives an active group (radical) generated by the photopolymerization initiator and is efficiently polymerized (cured) by radical polymerization. Examples of such polyfunctional ethylenic photocurable unsaturated compounds include (meth) acrylic acid esters, allyl compounds, vinyl ether compounds, vinyl ester compounds, and cinnamic acid ester compounds. As the (meth) acrylic acid ester, epoxy (meth) acrylate, polyvalent aromatic isocyanate, polyvalent aliphatic isocyanate and 2 obtained from a reaction between a bifunctional or higher functional epoxy resin and a carboxylic acid having an ethylenically unsaturated bond. Examples thereof include urethane (meth) acrylates obtained by reacting (meth) acrylic acid monoesters of polyhydric alcohols and (meth) acrylates of polyhydric alcohols. Examples of the allyl compound include diallyl esters such as phthalic acid, adipic acid, and malonic acid. As a vinyl ether compound, the vinyl ether compound of a polyhydric alcohol is mentioned. Examples of the vinyl ester compound include divinyl succinate and divinyl phthalate. A so-called monofunctional monomer having one ethylenically unsaturated bond can also be used in combination as appropriate. These may be used alone or in combination of two or more.

  The photocurable unsaturated compound (J) is preferably blended in an amount of 1.0 to 10 parts by mass with respect to 100 parts by mass of the polysulfide-containing prepolymer (E), and 2.0 to 8.0 parts by mass. More preferably, it is blended in an amount of 4.0 parts by mass or more and 6.0 parts by mass or less.

[Photoinitiator (K)]
The main component of the composition of the present embodiment can further contain a photopolymerization initiator. The photopolymerization initiator (K) contained in the composition of the present embodiment is not particularly limited as long as the monomer can be polymerized by light. Examples of the photopolymerization initiator (K) include acetophenone compounds, benzoin ether compounds, benzophenone compounds, sulfur compounds, azo compounds, peroxide compounds, phosphine oxide compounds, and the like. Specifically, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone , Methylphenylglyoxylate, ethylphenylglyoxylate, 4,4'-bis (dimethylaminobenzophenone), 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1 , 2-diphenylethane-1-one, carbonyl compounds such as 1-hydroxycyclohexyl phenyl ketone represented by the following formula (27); tetramethylthiuram monosulfide, tetramethylthiuram disulfide Which sulfur compounds; azobisisobutyronitrile, azo compounds such as azobis-2,4-dimethylvaleronitrile; benzoyl peroxide, peroxide compounds such as di -t- butyl peroxide; and the like. These can be used alone or in combination of two or more.

  Of these, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1 are preferred in terms of photostability, high efficiency of photocleavage, surface curability, compatibility with resins, low volatility, and low odor. -Phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one are preferred. Examples of commercially available 1-hydroxycyclohexyl phenyl ketone include Irgacure 184 (manufactured by BASF).

  The content of the photopolymerization initiator (K) is preferably 0.01 parts by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass of the polysulfide-containing prepolymer (E). It is more preferable to add 0.0 part by mass or less. This is because when the content of the photopolymerization initiator (K) is less than 0.01 parts by mass, it takes time to remove tack of the cured product obtained by curing the composition of the present embodiment, and 2.0 mass. This is because the storage stability of the composition of the present embodiment tends to deteriorate if the amount exceeds 50 parts.

<Curing agent>
The curing agent contained in the composition of the present embodiment includes water. The curing agent of the present embodiment is preferably an aqueous solution having a combustible liquid amount of less than 60% by mass and a flash point exceeding the flash point of a 60% by mass aqueous solution of ethyl alcohol. Moreover, it is preferable that a hardening | curing agent contains water and an alkylene oxide polymer at least.

[water]
The water contained in the curing agent of the composition of the present embodiment reacts with isocyanate groups contained in the molecules of the polysulfide-containing prepolymer (E) contained in the main agent to form urea bonds and crosslink. As long as it is cured, it is not particularly limited. The hardener of this embodiment can speed up the deep curability of the composition of this embodiment by mixing water with the main agent and the hardener. Therefore, since deep part sclerosis | hardenability is quick compared with 1 component type curable composition, the time until it progresses to the next process can be shortened, and a construction work period can be shortened.

[Alkylene oxide polymer]
The curing agent of the composition of the present embodiment can further contain an alkylene oxide polymer. Moreover, it is preferable that the alkylene oxide polymer contained in a hardening | curing agent contains an ethylene oxide polymer. Examples of the alkylene oxide polymer contained in the curing agent include a polymer obtained by reacting an alkylene oxide with water using an acid as a catalyst. Specifically, for example, ethylene glycol (HOCH ₂ CH ₂ OH) can be obtained by reacting ethylene oxide with water using an acid as a catalyst. And the polyethylene glycol (PEG) can be produced | generated by reducing the quantity of water by this reaction. Also, polyalkylene glycol (polyol compound) is synthesized by, for example, addition polymerization of alkylene oxide (alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide (tetramethylene oxide), tetrahydrofuran, etc.) to an active hydrogen-containing compound. Can do. Examples of the active hydrogen-containing compound include polyhydric alcohols, amines, alkanolamines, and polyhydric phenols. Examples of the polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, diethylene glycol, glycerin, hexanetriol, trimethylolpropane, and pentaerythritol. Specific examples of the alkylene oxide polymer include polyether polyols such as polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene ether glycol (PTMEG), polyoxypropylene glycol, and polyoxybutylene glycol, ethylene oxide / Examples include propylene oxide copolymers and sorbitol-based polyols. These can be used alone or in combination of two or more.

  Since the curing agent of the present embodiment improves the compatibility by including the alkylene oxide polymer, the main agent and the curing agent can be mixed uniformly, and the deep curability of the composition of the present embodiment is accelerated. Can do.

  The curing agent of this embodiment includes at least water and an alkylene oxide polymer, the amount of flammable liquid is less than 60% by mass, and the flash point is an aqueous solution exceeding the flash point of a 60% by mass aqueous solution of ethyl alcohol. Therefore, the content of the alkylene oxide polymer is preferably more than 0% by mass and less than 60% by mass with respect to the total volume of water and the alkylene oxide polymer. When the curing agent of this embodiment is, for example, a mixture of water and ethylene glycol, the flash point of ethylene glycol is about 111 ° C., and the flash point of a 60% by mass aqueous solution of ethylene glycol is about 111 ° C. or higher. Therefore, it is an aqueous solution exceeding the flash point (about 22 ° C., where the flash point of ethyl alcohol is about 13 ° C.) of a 60% by mass aqueous solution of ethyl alcohol. For example, when the curing agent is a mixture of water and propylene glycol, the flash point of propylene glycol is about 110 ° C., and the flash point of a 60% by mass aqueous solution of propylene glycol is about 110 ° C. or higher. It is an aqueous solution exceeding the flash point of a 60% by mass aqueous solution of alcohol.

  The curing agent of the present embodiment is an aqueous solution having a combustible liquid amount of less than 60% by mass and a flash point exceeding the flash point (about 22 ° C.) of a 60% by mass aqueous solution of ethyl alcohol. Since it does not correspond to Class 4 dangerous goods, there are no restrictions on storage and it is safe to handle.

<Resin for dilution>
In addition to the above components, the main component and the curing agent of the composition of the present embodiment can further contain a dilution resin. This dilution resin is used to dilute the composition of the present embodiment to lower the viscosity and improve workability, and to adjust the elastic properties of rubber such as modulus and elongation after curing. The dilution resin has a number average molecular weight (Mn) of 500 or more and 100,000 or less, preferably 500 or more and 50,000 or less, more preferably 500 or more and 20,000 or less, and further preferably 500 or more and 10,000 or less. Preferable examples include dilution resins which are liquid at room temperature and have a high molecular weight and polar groups. When the number average molecular weight (Mn) is less than 500, after the composition of the present embodiment is cured, it easily migrates (bleeds) to the surface of the cured product, adheres to the surface of the cured product, and is contaminated by adhesion of dust or the like. This is not preferable. Examples of polar groups include ester groups, ether groups (oxyalkylene groups), urethane groups, and the like, which have good compatibility with polysulfide-containing prepolymers. You may have, and you may have two or more. Among these, an ether group (oxyalkylene group) and a urethane group are preferable because the viscosity of the dilution resin is low and the compatibility with the polysulfide-containing prepolymer (E) is good. Further, the dilution resin is preferably a dilution resin that does not substantially have a functional group reactive with the functional group of the polysulfide-containing prepolymer (E) in the molecule.

  Specific examples of the dilution resin include polyoxyalkylene resins, polyester resins from dicarboxylic acids and glycols, low-viscosity (meth) acrylic acid alkyl ester copolymer resins, and mixtures thereof. Etc. Examples of the polyoxyalkylene resin include alkyl etherification and alkyl esterification derivative resins of polyoxyalkylene monools such as polyoxyethylene monool and polyoxypropylene monool, and polyoxyalkylene resins of saccharide polyhydric alcohols. Examples include alkyl etherified and alkyl esterified derivative resins, and polyoxyalkylene urethane resins that are liquid at room temperature. Any of these may be used alone or in combination of two or more. Among these, the polyoxyalkylene resin is low in viscosity, has good compatibility with the polysulfide-containing prepolymer (E), has good workability of the composition of the present embodiment, and good movement followability during curing. Further, alkyl etherified or alkyl esterified derivative resins of polyoxyalkylenated resins of saccharide polyhydric alcohols and polyoxyalkylene urethane resins which are liquid at room temperature are preferred, especially polyoxyalkylene urethane resins which are liquid at room temperature Is preferred.

  Examples of alkyl etherified or alkyl esterified derivative resins of polyoxyalkylenated resins of saccharide polyhydric alcohols include ethylene oxide and hydroxyl group of saccharide polyhydric alcohols such as sucrose (sucrose), glucose, mannitol and sorbitol. Examples include addition-polymerization of alkylene oxides such as propylene oxide, alkyl etherification or alkyl esterification, and end-capping with an alkyl group, and resins having substantially no hydroxyl groups. SPX-80 manufactured by Sanyo Kasei Kogyo Co., Ltd. is an example of a general commercial product of an alkyl ester derivative of an alkylene resin. Any of these may be used alone or in combination of two or more.

  The polyoxyalkylene urethane resin that is liquid at room temperature is obtained by reacting a polyoxyalkylene alcohol and an organic isocyanate, contains a polyoxyalkylene group and a urethane group in the molecule, and is substantially an isocyanate group or a hydroxyl group. High molecular weight resins that do not contain any are preferred. The conventional urethane-based diluent has a wide molecular weight distribution, and the low molecular weight region is easy to bleed, so the anti-contamination property is poor, and the high molecular weight region is difficult to bleed, but the viscosity is high and the workability is poor. It was difficult to achieve both contamination prevention performance and workability. However, the polyoxyalkylene urethane resin that is liquid at room temperature can be obtained by narrowing the molecular weight distribution of the polyoxyalkylene urethane resin that is liquid at room temperature to 1.6 or less, particularly preferably 1.0 to 1.3. Even if it has a high molecular weight, the viscosity can be kept low, and it is possible to achieve both excellent workability and anti-bleed antifouling performance after curing, particularly excellent antifouling performance at high temperatures in summer. The molecular weight distribution of the polyoxyalkylene urethane resin is determined from the ratio (Mw / Mn) of polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) by GPC.

  Specifically, polyoxyalkylene alcohol and organic isocyanate (preferably polyoxyalkylene monool and organic polyisocyanate, or polyoxyalkylene polyol and organic monoisocyanate) have an isocyanate group / hydroxyl group equivalent ratio. In the range of 0.9 / 1.0 to 1.1 / 1.0, the reaction can be preferably carried out by preferably reacting at 1/1. When the equivalent ratio is less than 0.9 / 1.0, the hydroxyl group content increases, so when used in the composition of the present embodiment containing the polysulfide-containing prepolymer (E), at the time of production or storage, This hydroxyl group and the isocyanate group of the polysulfide-containing prepolymer (E) react with each other to increase the viscosity and deteriorate workability. On the other hand, if the equivalent ratio exceeds 1.1 / 1.0, the isocyanate group content increases, and the influence of the cured product on the rubber elastic properties cannot be ignored.

  The above “substantially does not contain an isocyanate group or a hydroxyl group” means that an alkyl etherified or alkyl esterified derivative of a polyoxyalkylene resin of a saccharide polyhydric alcohol or a liquid polyoxyalkylene urethane resin is used. When synthesizing, a small amount of hydroxyl group or isocyanate group may remain in the molecule depending on the molar ratio of the raw materials. However, in order to achieve the object of the present invention, it is inconvenient even if it is regarded as containing no isocyanate group or hydroxyl group. Does not occur.

  Specific examples of the polyoxyalkylene alcohol include polyoxyalkylene monools, polyoxyalkylene polyols, and mixtures thereof. Examples of the polyoxyalkylene monool include those obtained by ring-opening addition polymerization of alkylene oxide to an initiator such as an alkyl compound containing one active hydrogen. The number average molecular weight (Mn) of the polyoxyalkylene monool is preferably 500 or more and 100,000 or less, more preferably 1,000 or more and 30,000 or less, and still more preferably 1,000 or more and 10,000 or less. . When the number average molecular weight (Mn) is less than 500, the polyoxyalkylene urethane resin which is liquid at room temperature tends to bleed, and the workability of the sealing material is deteriorated. On the other hand, when the number average molecular weight (Mn) exceeds 100,000, the viscosity of the polyoxyalkylene urethane resin that is liquid at room temperature increases, and the workability of the sealing material deteriorates.

  Specific examples of the initiator include methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, tert-butanol, cyclohexanol, phenol, and a mixture of two or more thereof. Can be mentioned. Of these, compounds having 5 or less carbon atoms such as methanol and ethanol are preferred.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, and a mixture of two or more thereof. Of these, propylene oxide is preferred. Specifically, polyoxyethylene monool, polyoxypropylene monool, polyoxybutylene monool, polyoxytetramethylene monool, poly (oxyethylene)-(oxypropylene) random or block copolymerization Examples include monools, poly (oxypropylene)-(oxybutylene) -based random or block copolymerized monools, and the like.

  Furthermore, the polyoxyalkylene monool has a total unsaturation of 0. 0, which is obtained by using the same catalyst as that used in the production of the polyoxyalkylene polyol described above as the catalyst used in the production thereof. 1 meq / g or less, more preferably 0.07 meq / g or less, particularly preferably 0.04 meq / g or less, and molecular weight distribution (Mw / Mn) of 1.6 or less, particularly narrow one of 1.0 to 1.3 preferable. In particular, in order to obtain a polyoxyalkylene urethane resin that is liquid at room temperature with low viscosity, it is preferable to use a polyoxyalkylene monool having a narrow molecular weight distribution.

  The polyoxyalkylene monool is composed of 50% by mass or more, more preferably 80% by mass or more, particularly preferably 90% by mass or more of the portion excluding the hydroxyl group in 1 mol of the molecule. For example, it means that the remaining part may be modified with urethane, ester, polycarbonate, polyamide, polyacrylate, polyolefin, etc., but 95% by mass or more of the molecule excluding the hydroxyl group is a monool composed of polyoxyalkylene. Is most preferred.

  Examples of the polyoxyalkylene polyol include the same compounds as those used in the synthesis of the polysulfide-containing prepolymer (E), and among these, a polyoxypropylene polyol is preferable. Any of these may be used alone or in combination of two or more. Of these, the polyoxyalkylene urethane resin, which is liquid at room temperature, has a low viscosity and does not bleed, so a polyoxyalkylene monool is preferred, and a polyoxypropylene monool is particularly preferred.

  Specific examples of the organic isocyanate include organic monoisocyanates, organic polyisocyanates, and mixtures thereof, and more specifically, those used in the synthesis of urethane prepolymers containing isocyanate groups. And the like. These can be used alone or in admixture of two or more. Of these, aliphatic polyisocyanates, alicyclic polyisocyanates, and araliphatic polyisocyanates are preferred, and araliphatic polyisocyanates are more preferred, because the viscosity of the resulting polyoxyalkylene urethane resin that is liquid at room temperature is low. In particular, xylylene diisocyanate is preferable, and m-xylylene diisocyanate is most preferable.

  The amount of the dilution resin used is preferably greater than 0 parts by mass and less than or equal to 200 parts by mass with respect to 100 parts by mass of the polysulfide-containing prepolymer (E) from the viewpoints of curing speed and physical properties of the cured product. More preferred is 100 parts by mass or less.

  Moreover, the main ingredient and hardening | curing agent of the composition of this embodiment can contain various additives other than each component mentioned above as needed in the range which does not impair the objective of this invention. Examples of the additive include fillers other than calcium carbonate (H), a curing accelerating catalyst, an adhesion-imparting agent, a storage stability improving agent (dehydrating agent), a colorant, a solvent, and an antifungal material. Each additive can be used in combination as appropriate.

  Examples of fillers other than calcium carbonate (H) include organic and inorganic substances having various shapes. For example, inorganic powder fillers such as mica, kaolin, zeolite, graphite, diatomaceous earth, white clay, clay, talc, slate powder, aluminum powder, zinc powder, magnesium carbonate, alumina, titanium oxide; fibers such as glass fiber and carbon fiber Fillers: wood flour, walnut flour, rice bran flour, pulp powder, cotton chips, rubber powder, and polyamide resins, polyester resins, polyurethane resins, silicone resins, vinyl chloride resins, vinyl acetate resins, polyolefins such as polyethylene and polypropylene In addition to organic fillers such as resin, acrylic resin, epoxy resin, phenol resin, urea resin, melamine resin and other thermoplastic resins or thermosetting resin powders, flame retardancy such as magnesium hydroxide and aluminum hydroxide Examples include fillers, and particle diameters from 0.01 μm , Those of 000μm is preferred.

Curing accelerating catalyst accelerates the reaction between the isocyanate group of the prepolymer and moisture (moisture), accelerates the internal curing of the two-component room temperature curing type sealing material, and reduces the difference between the surface and the internal curing rate. It is used in order to prevent cracks and the like from occurring in the cured product by reducing the difference in stress caused by the movement on the way.
Specific examples include organometallic compounds and amines. Examples of organometallic compounds include divalent organotin compounds such as tin octylate and tin naphthenate, dibutyltin dioctoate, dibutyltin dilaurate, and dibutyltin. Tetravalent organic tin such as diacetate, dibutyltin dimaleate, dibutyltin distearate, dioctyltin dilaurate, dioctyltin diversate, dibutyltin oxide, dibutyltin bis (triethoxysilicate), reaction product of dibutyltin oxide and phthalate Compound, dibutyltin bis (acetylacetonate), tin-based chelate compound EXCESTAR C-501 manufactured by Asahi Glass Co., Ltd., zirconium tetrakis (acetylacetonate), titanium tetrakis (acetylacetonate), aluminum tris (acetylacetate) Tonerate), aluminum tris (ethyl acetoacetate), acetylacetone cobalt, acetylacetone iron, acetylacetone copper, acetylacetone magnesium, acetylacetone bismuth, acetylacetone nickel, acetylacetone zinc, acetylacetone manganese, and other metal chelate compounds, tetra-n-butyl titanate, tetra Titanate esters such as propyl titanate, other metals such as manganese, iron, cobalt, copper, zinc, zirconium, lead, bismuth, and other metals such as lead octylate and zirconium octylate, octyl acid, stearic acid, Examples thereof include metal organic acid salts with various organic acids such as naphthenic acid. Examples of amines include triethylamine, tributylamine, triethylenediamine, and hexamethylamine. Lentetamine, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), 1,4-diazabicyclo [2,2,2] octane (DABCO), N-methylmorpholine, N-ethylmorpholine, etc. Tertiary amines, or salts of these amines and carboxylic acids, etc. may be mentioned.
Of these, organometallic compounds are preferred because of their high reaction rate and relatively low toxicity and volatility, more preferred are organic tin compounds and metal chelate compounds, and particularly preferred is dibutyltin dilaurate.

  Examples of the adhesion-imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins, epoxy resins, alkyl titanates, and organic polyisocyanates.

  Examples of the storage stability improving agent (dehydrating agent) include calcium oxide, magnesium oxide, p-toluenesulfonyl monoisocyanate, which react with moisture present in the sealing material.

  Examples of the colorant include inorganic pigments such as titanium oxide and iron oxide, organic pigments such as copper phthalocyanine, and carbon black.

  The total blending amount of the curing accelerating catalyst, filler, adhesion promoter, storage stability improver (dehydrating agent) and colorant is 0 to 500 parts by mass with respect to 100 parts by mass of the polysulfide-containing prepolymer (E). Parts by mass or less, more preferably 10 parts by mass or more and 300 parts by mass or less, and particularly preferably 10 parts by mass or more and 200 parts by mass or less.

  As the solvent, those having good compatibility with the solvent contained in the synthesis of other components in the composition of the present embodiment are preferable. For example, carbonate solvents such as dimethyl carbonate, acetone, methyl ethyl ketone (MEK) and the like. Ketone solvents, ester solvents such as ethyl acetate and butyl acetate, aliphatic solvents such as n-hexane, alicyclic solvents such as cyclohexane, aromatic solvents such as toluene, xylene and cellosolve acetate, mineral spirits Conventionally known solvents such as petroleum fraction solvents such as industrial gasoline and organic solvents, organic solvents, and organic solvents. Any organic solvent may be used as long as it is inert with respect to the reactive functional group of the urethane prepolymer such as an isocyanate group, a crosslinkable silyl group or a mercapto group. A solvent can be used individually or in combination of 2 or more types. The solvent is preferably used after sufficiently dehydrated and dried. In this embodiment, an organic solvent can be used for the purpose of lowering the viscosity of the curable composition and improving workability in addition to the above-mentioned additives. The amount of use is preferably suppressed as much as possible, and is preferably used so that the total amount of the two-component curable composition is less than 10% by mass, and further less than 5% by mass.

  The method for producing the composition of the present embodiment is not particularly limited. For example, a main agent containing a polysulfide-containing prepolymer (E) and a curing agent containing water are separately used under reduced pressure or in an inert gas atmosphere such as nitrogen, rolls, kneaders, extruders, universal stirrers, mixing mixers, etc. Examples of the method include mixing by sufficiently kneading using a stirrer and uniformly dispersing. The composition of the present embodiment can be stored by filling the prepared main agent in a container substituted with nitrogen gas or the like and filling the prepared curing agent in another container. The composition of this embodiment can be used by sufficiently mixing the main agent and the curing agent.

  As described above, the composition of the present embodiment is prepared by mixing a polysulfide polymer (A) having a hydroxyl group, a polyoxyalkylene polyol (B), and a hydroxyl group-containing (meth) acrylic monomer (C) with a polysiloxane. A two-component curable composition comprising a main agent containing a prepolymer (E) obtained by reacting an isocyanate compound (D) and a curing agent containing water. Conventionally used cured products obtained by curing a one-component curable composition containing a prepolymer having an isocyanate group at the end have a slow deep-curing property after construction and require a curing period. In addition, dirt components such as mold and dust adhered to the surface of the cured product, or cracks and discoloration occurred due to deterioration. Therefore, the hardened | cured material obtained using the urethane type prepolymer which has an isocyanate group at the terminal used conventionally has a long construction construction period, and had to apply | coat a coating material on the surface of hardened | cured material. In addition, a tack is generated on the surface of the cured product, and due to this tack, dust adheres to the surface of the cured product and contaminates the surface of the cured product.

  On the other hand, in the composition of this embodiment, since it has the main ingredient containing a prepolymer (E) and the hardening | curing agent containing the water which reacts with a prepolymer (E), by mixing a main ingredient and a hardening | curing agent, Deep section curability can be accelerated and the construction period can be shortened. In the composition of the present embodiment, when the polysulfide-containing prepolymer (E) is prepared, the polysulfide polymer (A) having a hydroxyl group, the polyoxyalkylene polyol (B), and a hydroxyl group-containing (meth) acrylic monomer Since the mixture with the body (C) is used, it is possible to prevent the dirt component from adhering to the surface of the cured product obtained by curing the composition of the present embodiment, and to crack the surface of the cured product. And the occurrence of discoloration can be suppressed. For this reason, the hardened | cured material obtained by hardening the composition of this embodiment does not need to be limited to the use which apply | coats a coating material on the surface. If the composition of this embodiment is used, the weather resistance after hardening and surface tack | tuck will be improved, and the curable composition with little deterioration of the surface of a hardened | cured material and a stain | pollution | contamination can be provided over a long period of time. As described above, according to the composition of the present embodiment, deep part curability can be accelerated, and a cured product excellent in weather resistance, stain resistance, and tack can be provided over a long period of time.

  Although the use of the composition of the present embodiment is not particularly limited, the composition of the present embodiment has the excellent properties as described above, so it is for civil engineering, concrete, wood, metal, glass, It is suitably used for applications such as plastics, sealing materials, sealing agents, potting agents, elastic adhesives, coating materials, lining materials, adhesives, structural adhesives in concrete and mortar, and cracking injection materials. In particular, the composition of the present embodiment can be suitably used as a sealing material and an adhesive.

  The composition of the present embodiment can accelerate the deep section curability and shorten the work period, suppress the adhesion of dirt components even when exposed outdoors for a long time, and generate cracks and discoloration on the surface of the composition (sealing material). Therefore, the composition of the present embodiment can be suitably used as a sealing material for so-called architectural working joints, stone joints, tile joints, or the like.

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these. Note that Example 2-4 is a reference example.
<Synthesis Example 1>
[Synthesis of Isocyanate Group-Containing Polymer (P-1)]
In a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet tube and heating / cooling device, 220 g of polyoxypropylene diol (Excenol 3020, number average molecular weight 3,200, manufactured by Asahi Glass Co., Ltd.) under a nitrogen gas stream, 100 g of oxypropylene triol (Excenol 5030, number average molecular weight 5,100, manufactured by Asahi Glass Co., Ltd.) was charged, and 33.5 g of hexamethylene diisocyanate (Desmodur H, molecular weight 168, manufactured by Sumika Bayer Urethane Co., Ltd.) and dibutyl were stirred. After adding 0.05 g of tin dilaurate, the mixture was heated and stirred at 70 ° C. to 80 ° C. for 2 hours for reaction. When the isocyanate group content became the theoretical value (2.37% by mass) or less, the reaction was terminated by cooling to room temperature, and an isocyanate group-containing polymer (P-1) was synthesized. The resulting isocyanate group-containing polymer (P-1) was a viscous liquid at room temperature with an isocyanate group content of 2.15 mass% by titration.

<Synthesis Example 2>
[Synthesis of polysulfide-containing terminal isocyanate polymer (P-2)]
In a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet tube and heating / cooling device, 220 g of polyoxypropylene diol (Excenol 3020, number average molecular weight 3,200, manufactured by Asahi Glass Co., Ltd.) under a nitrogen gas stream, 100 g of oxypropylene triol (Excenol 5030, number average molecular weight 5,100, manufactured by Asahi Glass Co., Ltd.), 5 g of pentaerythritol triacrylate (M-305, molecular weight 298.3, manufactured by Toagosei Co., Ltd.), THIOPLAST HTPS-350 ( 3 g of number average molecular weight 2700, manufactured by AKZO NOBEL) was added, and 35.6 g of hexamethylene diisocyanate (Desmodur H, molecular weight 168, manufactured by Sumika Bayer Urethane Co., Ltd.) and 0.05 g of dibutyltin dilaurate were added while stirring. After heating, 70 to 80 ° C The reaction was allowed to stir for 2 hours. When the isocyanate group content became the theoretical value (2.44% by mass) or less, the reaction was terminated by cooling to room temperature, and a polysulfide-containing terminal isocyanate polymer (P-2) was synthesized. The obtained polysulfide-containing terminal isocyanate polymer (P-2) was a viscous liquid at ordinary temperature with an isocyanate group content of 2.08 mass% by titration.

<Synthesis Example 3>
[Synthesis of polysulfide-containing terminal isocyanate polymer (P-3)]
In a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet tube and heating / cooling device, 220 g of polyoxypropylene diol (Excenol 3020, number average molecular weight 3,200, manufactured by Asahi Glass Co., Ltd.) under a nitrogen gas stream, 100 g of oxypropylene triol (Excenol 5030, number average molecular weight 5,100, manufactured by Asahi Glass Co., Ltd.), 15 g of pentaerythritol triacrylate (M-305, molecular weight 298.3, manufactured by Toagosei Co., Ltd.), THIOPLAST HTPS-350 ( 6 g of number average molecular weight 2700, manufactured by AKZO NOBEL) was added, and 39.6 g of hexamethylene diisocyanate (Desmodur H, molecular weight 168, manufactured by Sumika Bayer Urethane Co., Ltd.) and 0.05 g of dibutyltin dilaurate were added while stirring. Then, heat to 70 ° C to 80 ° C In reaction was allowed to stir for 2 hours. When the isocyanate group content became the theoretical value (2.58% by mass) or less, the reaction was terminated by cooling to room temperature, and a polysulfide-containing terminal isocyanate polymer (P-3) was synthesized. The resulting polysulfide-containing terminal isocyanate polymer (P-3) was a viscous liquid at room temperature with an isocyanate group content of 2.15% by mass.

<Synthesis Example 4>
[Synthesis of Reaction Accelerator (G) (Carboxylic Acid Silyl Ester Compound (CS-1))]
After adding toluene to a concentration of 50 mass% to 133.3 parts by mass of stearic acid as the carboxylic acid component of the above formula (5) and 219.0 parts by mass of lauric acid as the carboxylic acid component of the above formula (6). A predetermined amount (10 μL with respect to 100 g of Si-H group-containing polysiloxane) of a 3% by mass platinum chloride isopropyl alcohol solution was added to prepare an 80 ° C. carboxylic acid mixed solution. Next, 100.0 parts by mass of an equivalent Si—H group-containing polysiloxane (KF99, Si—H 0.0156 equivalent / g, manufactured by Shin-Etsu Chemical Co., Ltd.) is slowly added dropwise to the prepared carboxylic acid mixed solution. The reaction temperature was raised to 90 ° C., and stirring was continued until generation of hydrogen was not observed. Then, the carboxylic acid silyl ester compound (CS-1) was obtained by distilling toluene off.

<Synthesis Example 5>
[Synthesis of latent curing agent (F) (urethane bond-containing oxazolidine compound (O-1))]
A reaction vessel equipped with a stirrer, thermometer, ester tube and heating / cooling device was charged with 435 g of diethanolamine (molecular weight 105) and 183 g of toluene, and 328 g of isobutyraldehyde (molecular weight 72.1) was added while stirring. The mixture was heated to 110 ° C. to 150 ° C. for 3 hours, and by-product water was removed from the system to perform reflux dehydration reaction. The amount of water removed was 74.5 g. Subsequently, heating was performed while reducing the pressure from 50 hPa to 70 hPa to remove toluene and unreacted isobutyraldehyde, thereby obtaining 2-isopropyl-3- (2-hydroxyethyl) oxazolidine as an intermediate reaction product. 348 g of hexamethylene diisocyanate (molecular weight 168) was further added to 659 g of the obtained 2-isopropyl-3- (2-hydroxyethyl) oxazolidine, and reacted at 80 ° C. for 8 hours. The point at which the measured NCO content by titration was 0.0% by mass was determined as the reaction end point to obtain a urethane bond-containing oxazolidine compound (O-1) having a urethane bond and two oxazolidine rings in the molecule. The obtained urethane bond-containing oxazolidine compound (O-1) was a translucent liquid at room temperature.

<1. Preparation of composition>
[Example 1]
(Preparation of main agent)
In a kneading vessel equipped with a stirrer, a nitrogen introduction tube and a heating / cooling device, 100 g of the polysulfide-containing terminal isocyanate polymer (P-2) obtained in Synthesis Example 2 was charged under a nitrogen gas stream, and each of them was previously stirred from 100 ° C. in advance. 25 g of heavy calcium carbonate having a moisture content of 0.05% by mass or less by drying in a dryer at 110 ° C. and 10 g of titanium oxide were charged and mixed until the contents were uniform. Next, 8 g of a solution obtained by dissolving 1.5 g of the following hindered amine light stabilizer and 1.5 g of a hindered phenol antioxidant in 5 g of dimethyl carbonate in advance, 0.2 g of a carboxylic acid silyl ester compound (CS-1), photocuring Unsaturated compound (Aronix M-8030, manufactured by Toagosei Co., Ltd.), photopolymerization initiator (IRGACURE184, manufactured by BASF) 0.1 g, organic surface treated calcium carbonate (Viscolite MBP, manufactured by Shiroishi Kogyo Co., Ltd.) 100 g, urethane 8 g of bond-containing oxazolidine compound (O-1), 32 g of polyoxyalkylene resin for dilution (GPA3000, manufactured by Sanyo Chemical Industries), and 18 g of organic solvent (Exsol D40, manufactured by ExxonMobil) were added, and the contents were uniform. Mix until. Next, the mixture was degassed under reduced pressure at 50 hPa to 70 hPa, filled in a paper cartridge container and sealed to prepare a main ingredient component. The obtained main ingredient component was a white pasty liquid that hardens at room temperature. Table 1 shows the parts by mass of each component.

(Preparation of curing agent)
A curing agent component was prepared by uniformly mixing 5.0 g of water and 5.0 g of polyoxyethylene-dimethyl ether (Uniox MM-500, average molecular weight 550, manufactured by NOF Corporation). Table 1 shows the parts by mass of each component.

[Example 2]
In each component used in Example 1 described above, except that the curing agent was prepared by uniformly mixing 5.0 g of water and 5.0 g of acetone, The composition of this example was produced. Table 1 shows parts by mass of each component in the composition of this example.

[Example 3]
In each component used in Example 1 described above, the composition of this example was prepared in the same manner as in Example 1 except that the curing agent component was prepared using only 5.0 g of the curing agent as water. Table 1 shows parts by mass of each component in the composition of this example.

[Example 4]
In each component used in Example 1 described above, the curing agent is uniformly mixed and cured with 5.0 g of water and 5.0 g of polypropylene glycol (Uniol D-400, average molecular weight 400, manufactured by NOF Corporation). A composition of this example was produced in the same manner as in Example 1 except that the agent component was prepared. Table 1 shows parts by mass of each component in the composition of this example.

[Example 5]
In each component used in Example 1 described above, the same as Example 1 except that the prepolymer (E) used in the main agent was changed to the polysulfide-containing terminal isocyanate polymer (P-3) obtained in Synthesis Example 3. Thus, the composition of this example was produced. Table 1 shows parts by mass of each component in the composition of this example.

[Comparative Example 1]
In each component used in Example 1 described above, a composition was prepared in the same manner as in Example 1 except that no curing agent was blended. Table 1 shows parts by mass of each component in the composition.

[Comparative Example 2]
In each component used in Example 1 described above, the same procedure as in Example 1 was conducted except that the prepolymer (E) used in the main agent was the isocyanate group-containing polymer (P-1) obtained in Synthesis Example 1. A composition was prepared. Table 1 shows parts by mass of each component in the composition.

<2. Evaluation>
About each composition which mixed the main ingredient and the hardening | curing agent, the weather resistance, stain resistance, tack, and sclerosis | hardenability were evaluated as follows by the method shown below. The results are shown in “Table 1”.

[Weatherability]
The obtained composition is made into a sheet and cured by curing for 14 days at 23 ° C. and 50% relative humidity to produce a sheet having a thickness of 5 mm. A metal halide lamp type weather resistance tester (trade name: Metal Weather, A weather resistance test for 50 hours and 100 hours was performed using a die plastic win tes), and the surface state (crack) of the cured product after the weather resistance test was visually observed. The test results were evaluated according to the following criteria, and the test results are shown in Table 1. After 50 hours and 100 hours, it was judged that the weather resistance was good if there were no or few hair cracks on the surface of the test piece of the cured product.
(Criteria)
“◯”: No or few hair cracks on the test piece surface “×”: Many hair cracks on the test piece surface

[Contamination resistance]
A joint having a depth of 5 mm, a width of 20 mm, and a length of 100 mm is formed on the surface of a slate plate having a thickness of 5 mm. The joint is filled with a composition in which the main agent and the curing agent are mixed, and an excess sealing material is removed with a spatula. A test piece was prepared by flattening the scraped surface. After placing the test body in a room at 23 ° C. and 50% RH for one day, it was exposed to an outdoor place with a lot of dust with the surface of the joint facing south and the length direction being vertical. After 1 month, the state of contamination due to dust adhering to the surface of the test specimen was visually observed, the contamination resistance of the surface of the sealing material was evaluated according to the following criteria, and the test results are shown in Table 1. If the surface of the test specimen was almost free of dust and was clean, it was judged that the stain resistance was good.
(Criteria)
“○”: clean state with almost no dust adhering to the surface “×”: dirty surface with dust adhering

[tack]
Using a slate plate of width 50 mm x length 50 mm x height 5 mm, a primer (No. 40, manufactured by Yokohama Rubber Co.) is applied within a predetermined range (width 30 mm x length 30 mm) of the surface of the slate plate, It was left at 23 ° C. and 50% RH for 1 hour. Next, each composition obtained by mixing the main agent and the curing agent is placed on the applied primer so as to have a thickness of 5 mm using a caulking gun, and flattened with a spatula at 23 ° C., 50 The composition was cured for 7 days in a% RH environment. The cured composition was placed outdoors on the south side and exposed for 7 days. After completion of the exposure, the surface of the cured composition was judged to be tacky by touch, the surface tack of the cured composition was evaluated according to the following criteria, and the test results are shown in Table 1. If almost no tack was felt on the surface of the cured composition, it was judged that the tack was good.
(Criteria)
“○”: Tack is hardly felt “△”: Tack is slightly felt “×”: Tack is felt

[Curing property]
About each composition which mixed the main ingredient and the hardening | curing agent, the Asker C (ASKER C) hardness was measured according to Japan Rubber Association Standard (SRIS) 0101. Asker C hardness was measured by using an Asker C-type hardness meter (manufactured by Kobunshi Keiki Co., Ltd.) after curing each cured composition by curing at 20 ° C. for 3 days. Were evaluated according to the following criteria, and the test results are shown in Table 1. If Asker C hardness was 18 or more, it was judged that curability was excellent.
(Criteria)
“◯”: Asker C hardness of 18 or more “×”: Asker C hardness of less than 18

Each component shown in Table 1 is as follows.
Prepolymer (E1): isocyanate group-containing polymer (P-1) obtained in Synthesis Example 1 manufactured by Yokohama Rubber Co., Ltd. Prepolymer (E2): polysulfide-containing terminal isocyanate polymer obtained in Synthesis Example 2 (P-2), manufactured by Yokohama Rubber Co., Ltd. Prepolymer (E3): Polysulfide-containing terminal isocyanate polymer (P-3) obtained in Synthesis Example 3 above, manufactured by Yokohama Rubber Co., Ltd. Latent curing agent (F) : Urethane bond-containing oxazolidine compound (O-1) obtained in Synthesis Example 5 above, manufactured by Yokohama Rubber Co., Ltd. Reaction accelerator (G): Ring-opening catalyst, carboxylic acid silyl ester compound obtained in Synthesis Example 4 above (CS-1), manufactured by Yokohama Rubber Co., Ltd. ・ Calcium carbonate (H1): Heavy calcium carbonate, manufactured by Maruo Calcium Co., Ltd. ・ Calcium carbonate (H ): Organic surface treated calcium carbonate, trade name “Viscolite MBP”, manufactured by Shiraishi Calcium Co., Ltd. • Anti-aging agent (I1): hindered amine light stabilizer, bis (1,2,2,6,6-pentamethyl sebacate) -4-piperidyl), trade name “TINUVIN 765”, manufactured by Ciba Specialty Chemicals Co., Ltd. • Anti-aging agent (I2): hindered phenol antioxidant, pentaerythritol-tetrakis [3- (3,5-di -Tert-butyl-4-hydroxyphenyl) propionate], trade name "IRGANOX 1010", manufactured by Ciba Specialty Chemicals Co., Ltd., photocurable unsaturated compound (J): trade name "Aronix M-8030", Toa Gosei -Photopolymerization initiator (K): Trade name "Irgacure 184", BA Made by F Japan Corporation ・ Titanium oxide: Trade name “R-820”, made by Ishihara Sangyo Co., Ltd. ・ Dimethyl carbonate: Trade name “DMC”, made by Mitsui Chemical Fine Co., Ltd. ・ Dilution resin: Trade name “Sunflex GPA3000”, Terminal esterified polyfunctional polyether, manufactured by Sanyo Chemical Industries, Ltd. ・ Solvent: Trade name “Exsol D40”, manufactured by ExxonMobil Co., Ltd. ・ Water: tap water ・ Alkylene oxide polymer 1: Polyoxyethylene-dimethyl ether, trade name “ UNIOX MM-500 ”, average molecular weight 550, manufactured by NOF Corporation ・ alkylene oxide polymer 2: polypropylene glycol (diol), trade name“ Uniol D-400 ”, average molecular weight 400, manufactured by NOF Corporation ・ Acetone: Reagent, manufactured by Kanto Chemical Industry Co., Ltd.

  As shown in Table 1, it was confirmed that the compositions of Examples 1 to 5 were good with little or no hair cracks on the surface of the test piece until 100 hours after the start of the test. Further, it was confirmed that the compositions of Examples 1 to 5 were in a clean state with almost no dust adhering to the surface of the test piece. In addition, it was confirmed that the compositions of Examples 2 to 4 slightly felt tack on the surface of the test piece, but the compositions of Examples 1 and 5 showed almost no tack on the surface of the test piece. It was done. In addition, the compositions of Examples 1 to 5 had an Asker C hardness of 18 or more after 3 days, and were confirmed to be excellent in curability.

  On the other hand, the composition of Comparative Example 1 is good with little or no hair cracks on the surface of the test piece until 100 hours after the start of the test, and the adhesion of dust is hardly observed on the surface of the test piece. It was confirmed that almost no tack was felt on the surface of the test piece, but it was confirmed that the Asker C hardness was less than 18 and inferior in curability. The composition of Comparative Example 2 had an Asker C hardness of 18 or more and was confirmed to be excellent in curability, but after 50 hours from the start of the test, many hair cracks were observed on the surface of the test piece, It was confirmed that the surface was dusty and dirty, and that the surface of the test piece was tacky.

  Therefore, a prepolymer obtained by reacting a polyisocyanate compound (D) with a mixture of a polysulfide polymer (A) having a hydroxyl group, a polyoxyalkylene polyol (B), and a hydroxyl group-containing (meth) acrylic monomer (C). It was found that weather resistance, stain resistance, tack and curability were excellent by using a two-component curable composition having a main agent containing polymer (E) and a curing agent containing water. It has been found that the composition of this example can be suitably used for a sealing material, an adhesive, and the like because it is excellent in weather resistance, stain resistance, tack and curability.

Claims (11)

Formula (4) represented Ru of compound and (A), the polyoxyalkylene polyol (B), a mixture of hydroxyl group-containing (meth) acrylic monomer (C), the polyisocyanate compound (D) Containing a prepolymer (E) in which the molar ratio of isocyanate group / active hydrogen (group) is 1.2 to 1.0 to 10.0 to 1.0,
A curing agent comprising water for crosslinking and curing by a urea bond formed by reacting with an isocyanate group contained in the main agent, and an ethylene oxide polymer;
Two-component curable composition characterized by having

(Wherein the average value of X is 1 to 5, n is greater than 50 an integer .R ₁ is 2 to 16 Al Killen group or an ether bond-containing Al Killen group carbon atoms there .R ₂ is an Al Killen group or an ether bond-containing Al Killen group having 1 to 100 carbon atoms).   The two-component curable composition according to claim 1, wherein the curing agent is an aqueous solution having a combustible liquid amount of less than 60% by mass and a flash point exceeding the flash point of a 60% by mass aqueous solution of ethyl alcohol. The two-component curable composition according to claim 1 or 2 , wherein the main agent further comprises a latent curing agent (F) that reacts with moisture to generate an active hydrogen group. The two-component curable composition according to claim 3 , wherein the latent curing agent (F) is an oxazolidine compound. The main agent further contains a carboxylic acid silyl ester compound (G) as a reaction accelerator of the latent curing agent (F),
The carboxylic acid silyl ester compound (G) includes a carboxylic acid silyl ester group represented by the following formulas (1) and (2), and the number M of the carboxylic acid silyl ester group represented by the following formula (1): The two-component curable composition according to claim 3 or 4 , wherein the number N of carboxylic acid silyl ester groups represented by the following formula (2) satisfies the relationship of the following formula (3).
R ¹ COO-Si≡ (1)
R ² COO-Si≡ (2)
0.10 ≦ M / (M + N) ≦ 0.80 (3)
(In the formula, R ¹ represents a monovalent hydrocarbon group having 13 to 21 carbon atoms, and R ² represents an alkyl group having 5 to 11 carbon atoms.) The two-component curable composition according to any one of claims 1 to 5 , wherein the main agent further contains calcium carbonate (H) as a filler. The two-component curable composition according to any one of claims 1 to 6 , wherein the main agent further contains an anti-aging agent (I). The two-component curable composition according to any one of claims 1 to 7 , wherein the main agent further contains a photocurable unsaturated compound (J). The two-component curable composition according to any one of claims 1 to 8 , wherein the main agent further contains a photopolymerization initiator (K). The two-component curable composition according to any one of claims 1 to 9 , wherein the polyisocyanate compound (D) is aliphatic or alicyclic. A sealing material comprising the two-component curable composition according to any one of claims 1 to 10 .