JP5794829B2 - Curable composition and sealing material using the same - Google Patents

Description

  The present invention relates to a 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, the one-component sealant, especially the one-component urethane sealant composed of a urethane-based prepolymer containing an isocyanate group at the end, does not require the mixing of the main agent and the curing agent, and is due to a measurement error between the main agent and the curing agent. Since there is no curing failure, it is excellent in workability and can be used with peace of mind (for example, see Patent Document 1). In addition, a one-component urethane sealant composed of a urethane prepolymer containing an isocyanate group at the terminal has a low modulus after curing, high elongation, good rubber elasticity, etc., and excellent adhesion and durability. As a result, usage is increasing year by year.

Japanese Patent Laid-Open No. 2005-314683

  However, the sealing material obtained by curing and curing a curable composition containing a urethane-based prepolymer containing an isocyanate group adheres dirt components such as mold and dust to the surface of the sealing material when exposed to the outdoors. Therefore, 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 view of the above problems, the present invention provides a curable composition excellent in stain resistance that can suppress adhesion of dirt components even when exposed outdoors for a long period of time, and a sealing material using the composition. Objective.

The present invention includes the following (1) to ( 7 ).
(1) A room temperature curable resin (A) that cures at room temperature, and a silicate oligomer (B),
The room temperature curable resin (A) is an isocyanate group-containing urethane prepolymer,
The silicate oligomer (B) is a condensate of an alkyl silicate, and is a silicate oligomer represented by the following formula (4) in which at least part of an alkoxy group bonded to a Si atom has 3 to 18 carbon atoms. ,
Content of the said silicate oligomer (B) is 2 mass parts or more and 20 mass parts or less with respect to 100 mass parts of said room temperature curable resin (A), The curable composition characterized by the above-mentioned.
R ² _n Si (OR ¹ ) _4-n (4)
(In the above formula (4), R ¹ and R ² each independently represents a propyl group or a butyl group. N is 0, 1 or 2.)
(2) The curable composition according to the above (1), wherein the polyisocyanate compound of the isocyanate group-containing urethane prepolymer is aliphatic or alicyclic.
(3) The curable composition according to (1) or (2), further including a latent curing agent (C) that reacts with moisture to generate an active hydrogen group.
(4) The curable composition according to (3), wherein the latent curing agent (C) is an oxazolidine compound.
(5) Further, as a reaction accelerator of the latent curing agent (C), a carboxylic acid silyl ester compound (D) is included,
The carboxylic acid silyl ester compound (D) 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 curable composition according to (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)
(Wherein 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.)
(6) The curable composition according to any one of (1) to (5), further including calcium carbonate (E) as a filler.
(7) A sealing material using the curable composition according to any one of (1) to (6) above.

  ADVANTAGE OF THE INVENTION According to this invention, even if it exposes to the outdoors over a long period of time, the curable composition excellent in stain resistance which can suppress adhesion of a dirt component, and a sealing material using the same can be provided.

  Hereinafter, the present invention will be described in detail. 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 curable composition according to the present embodiment (hereinafter referred to as “the composition of the present embodiment”) includes a room temperature curable resin (A) that cures at room temperature and a silicate oligomer (B), and the silicate The oligomer (B) is a condensate of an alkyl silicate, and is a curable composition characterized in that at least a part of the alkoxy group bonded to the Si atom is a silicate oligomer having 3 to 18 carbon atoms. .

<Room temperature curable resin (A)>
The room temperature curable resin (A) contained in the composition of the present embodiment is a urethane prepolymer containing a plurality of isocyanate groups in the molecule at the molecular ends. Hereinafter, the room temperature curable resin (A) of the present embodiment is referred to as “isocyanate group-containing urethane prepolymer (A) or urethane prepolymer (A)”. The urethane prepolymer (A) is preferably liquid at room temperature from the viewpoint of handling. In addition, the room temperature in this embodiment is 20 degreeC or more and 30 degrees C or less, Preferably it is the temperature of 25 degreeC vicinity. The production method of the urethane prepolymer (A) is not particularly limited, and conventionally known methods can be mentioned. The urethane prepolymer (A) is, for example, a reaction product obtained by reacting a polyisocyanate compound and a polyol compound so that an isocyanate group (NCO group) is excessive with respect to a hydroxy group (OH group). is there. The urethane prepolymer (A) generally contains 0.5% by mass or more and 10% by mass or less of NCO groups at the molecular ends.

(Polyisocyanate compound)
The polyisocyanate compound contained in the isocyanate group-containing urethane prepolymer which is a room temperature curable resin (A) is used in the production of a urethane-based prepolymer, and particularly has two or more isocyanate groups in the molecule. It is not limited. 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, tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (1,5-NDI), diphenyl ether diisocyanate, trif Such as methane triisocyanate. Aliphatic polyisocyanates include propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI), xylylene diisocyanate (XDI), tetramethyl. And xylylene diisocyanate (TMXDI). 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 the aromatic polyisocyanates, and among the aliphatic polyisocyanates, the viscosity becomes low after the reaction and the handling of the main agent containing the urethane-based prepolymer is easy. Among HDI, XDI and alicyclic polyisocyanate, IPDI is preferred.

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

(Polyol compound)
The polyol compound used when producing the isocyanate group-containing urethane prepolymer is not particularly limited as long as it has two or more hydroxy groups. Examples of polyol compounds include polyoxyalkylene polyols; polyester polyols; polymer polyols; polycarbonate polyols; polybutadiene polyols; hydrogenated polybutadiene polyols; acrylic polyols; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, and pentane. Examples thereof include low molecular weight polyols such as diol and hexanediol. Of these, polyoxyalkylene polyols are preferred from the viewpoints of better compatibility and foam resistance, and excellent strength and elongation of the cured product.

  Examples of the polyoxyalkylene polyol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, 1,1,1-trimethylolpropane, 1,2,5-hexanetriol, 1,3-butanediol, Polyol obtained by adding at least one selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and polyoxytetramethylene oxide to at least one selected from the group consisting of 1,4-butanediol and pentaerythritol Etc. Specifically, polyoxyethylene diol, polyoxyethylene triol, polyoxypropylene diol, and polyoxypropylene triol are preferably exemplified.

  A polyol compound can be used individually or in combination of 2 types or more, respectively. The polyol compound is preferably a polyoxyalkylene polyol, more preferably a polyoxypropylene diol or a polyoxypropylene triol, from the viewpoints of excellent compatibility and foam resistance, and excellent cured product strength and elongation. .

  The number average molecular weight of the polyol compound is preferably 400 or more and 10,000 or less, and more preferably 400 or more and 8000 or less, from the viewpoints of excellent compatibility and foam resistance and excellent strength and elongation of the cured product.

  The polyol compound used when preparing the urethane prepolymer is used when preparing the isocyanate group-containing polyether polymer from the viewpoint of excellent compatibility and foam resistance, and excellent strength and elongation of the cured product. The same as the polyoxyalkylene polyol is preferred.

In this embodiment, as a combination of the polyisocyanate compound and the polyol compound in producing the urethane prepolymer (A), norbornane diisocyanate (NBDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI) , Transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis (isocyanatomethyl) cyclohexane (H ₆ XDI), dicyclohexylmethane diisocyanate (H ₁₂ MDI) and hexamethylene diisocyanate (HDI) A combination of at least one kind and any one or both of polyoxypropylene diol and polyoxypropylene triol is preferably exemplified.

  The amount of the polyisocyanate compound and the polyol compound in producing the urethane prepolymer (A) is such that the equivalent ratio of the isocyanate group to the hydrosyl group (isocyanate group (NCO group) / hydrosyl group (OH group)) is 1. It is preferably 2 or more and 2.5 or less, and more preferably 1.5 or more and 2.0 or less. When the equivalence ratio is within such a range, the viscosity of the urethane prepolymer (A) to be obtained becomes appropriate, and the residual amount of the unreacted polyisocyanate compound in the urethane prepolymer (A) can be reduced.

  The method for producing the urethane prepolymer (A) is not particularly limited. For example, the polyol compound and the polyisocyanate compound having the above-described equivalent ratio (NCO group / OH group) are heated and stirred at 50 ° C. or higher and 130 ° C. or lower. Can be produced. Moreover, if necessary, for example, a urethanization catalyst such as an organic tin compound, organic bismuth, or amine can be used.

  A urethane prepolymer (A) can be used individually or in combination of 2 or more types, respectively.

<Silicate oligomer (B)>
The silicate oligomer (B) contained in the composition of the present embodiment is a condensate of alkyl silicate, and at least a part of alkoxy groups bonded to Si (silicon) atoms has 3 to 18 carbon atoms. It is a silicate oligomer represented by Formula (4).
R ² _n Si (OR ¹ ) _4-n (4)
In the above formula (4), R ¹ and R ² each independently represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, preferably a propyl group or a butyl group, preferably a butyl group. Is more preferable. n is 0, 1 or 2, preferably 0 or 1. Specific examples of the silicate ester represented by the above formula (4) include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, And methyltriisopropoxysilane.

  The silicate oligomer (B) has an isocyanate group-containing urethane prepolymer which is a room temperature curable resin (A) by having at least a part of the alkoxy group bonded to the Si atom having 3 to 18 carbon atoms. Since the compatibility is not so good and it comes out on the surface of the composition of the present embodiment, tack disappears quickly. In this way, the silicate oligomer (B) comes out on the surface of the composition of the present embodiment and stretches the film on the surface, thereby suppressing the adhesion of dirt and dust, thereby improving the stain resistance.

  The silicate oligomer (condensate of silicate ester) (B) may be used as it is. The degree of condensation of the condensate (number of molecules of the condensed silicate ester) is not particularly limited, but is preferably 2 or more and 20 or less, and more preferably 2 or more and 15 or less. A condensate may be used independently and may use 2 or more types from which a condensation degree and molecular structure differ. In the present embodiment, one or more of the above silicate oligomers (condensates of silicate esters) (B) can be used in combination.

  The content of the silicate oligomer (B) is preferably 0.05 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the room temperature curable resin (A). More preferably, they are 0.5 mass part or more and 20 mass parts or less, More preferably, they are 0.5 mass part or more and 5 mass parts or less.

<Latent curing agent (C)>
The composition of this embodiment can further contain an oxazolidine compound that is a latent curing agent (C) that reacts with moisture to generate an active hydrogen group. The latent curing agent (C) 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 under 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 viewpoints of shortening the curing time at room temperature and storage stability of the composition of the present invention, 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 one or more, preferably 2 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) in the atmosphere to undergo hydrolysis, and the oxazolidine ring generates (regenerates) a secondary amino group and an alcoholic hydroxyl group, thereby causing a latent curing agent for an isocyanate group-containing prepolymer. It functions as. When the isocyanate group of the isocyanate group-containing prepolymer reacts with moisture, it forms a urea bond and cures, but at this time, carbon dioxide gas is also generated, bubbles are generated in the cured product due to carbon dioxide gas, and the appearance is deteriorated. However, when a mixture of an isocyanate group-containing prepolymer and an oxazolidine compound is exposed to moisture, the oxazolidine ring of the oxazolidine compound will react before the moisture reacts with the isocyanate group. Hydrolysis by moisture regenerates secondary amino groups and alcoholic hydroxyl groups, and these active hydrogens react with isocyanate groups and cure without generating carbon dioxide gas, so that the carbonic acid of the composition of this embodiment can be obtained. It can prevent foaming due to gas.

  In addition, when an aliphatic polyisocyanate is used as the polyisocyanate compound in the synthesis of the isocyanate group-containing prepolymer described above, the curing rate will be extremely delayed if it is a reaction with only water, but an oxazolidine compound should be used in combination. Therefore, 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. It has the effect that the usage-amount of a catalyst 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 a hydroxyl group of a compound having a hydroxyl group and an oxazolidine ring with an isocyanate group of a polyisocyanate compound or a carboxyl group of an 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 mol or more, preferably 1.0 times mol with respect to 1.0 mol of the secondary amino group of alkanolamine. 1.5 times mol or less, more preferably 1.0 times mol or more and 1.2 times mol or less, and heating and refluxing in a solvent such as toluene, xylene, etc., dehydrating condensation while removing by-product water The method of performing 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 in terms of ease of production of the compound having a hydroxyl group and an oxazolidine ring, and excellent antifoaming properties when the resulting one-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 and the hydroxyl group of the compound having 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. 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 aforementioned isocyanate group-containing prepolymer, and among them, the crystallinity of the urethane bond-containing oxazolidine compound is lowered. In view of improving the workability of the sealing material, aliphatic polyisocyanates are preferred, and hexamethylene diisocyanate (HDI) is particularly preferred.

  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.

  The oxazolidine compound is a functional group containing an active hydrogen group such as an amino group or a hydroxyl group that reacts with an isocyanate group of a urethane-based prepolymer containing an isocyanate group at room temperature (or room temperature) of 5 ° C. to 35 ° C. in the molecule. Alternatively, it preferably has no isocyanate group. 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 invention is achieved. It can be regarded as not having above. 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 0.3 mol or more and 1.0 mol relative to 1.0 mol of the isocyanate group in the isocyanate group-containing prepolymer. It is preferable to use so that it may become below, and it is more preferable to use it so that it may become 0.5 mol or more and 1.0 mol or less.

  When the oxazolidine compound is used as the latent curing agent (C) from the viewpoint of adjusting the curing rate of the isocyanate group-containing prepolymer, the latent curing agent (C) is 2 with respect to 100 parts by mass of the isocyanate group-containing prepolymer. It is preferable to mix from 0.0 parts by mass to 20.0 parts by mass, more preferably from 5.0 parts by mass to 15.0 parts by mass, and from 7.0 parts by mass to 10.0 parts by mass. Is more preferable.

<Carboxylic acid silyl ester compound (D)>
The composition of the present embodiment can further contain a carboxylic acid silyl ester compound (D) as a reaction accelerator (ring-opening catalyst) of the latent curing agent (C). Moreover, in the composition of this embodiment, when combining the prepolymer containing an isocyanate group and an oxazolidine compound, it is preferable that a carboxylic acid silyl ester compound (D) is included. The carboxylic acid silyl ester compound (D) is used as a ring-opening catalyst of an oxazolidine compound when a prepolymer containing an isocyanate group and an oxazolidine compound are combined. The ring-opening catalyst promotes the reaction of the oxazolidine compound with moisture to hydrolyze and regenerate active hydrogen, and the reaction between the regenerated active hydrogen and the isocyanate group of the prepolymer containing the isocyanate group, It is added to accelerate the curing of the composition of this embodiment.

The carboxylic acid silyl ester compound (D) has a carboxylic acid silyl ester group represented by the following formulas (1) and (2), and has a number M of carboxylic acid silyl ester groups represented by the following formula (1): It is preferable that 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, 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. Represents.)

  Even if the carboxylic acid silyl ester compound (D) is used in combination with a compound having a carboxylic acid silyl ester group represented by the above formulas (1) and (2) 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 Si (silicon) atoms of the carboxylic acid silyl ester groups represented by the above formulas (1) and (2) are the same atom.

In the above formula (1), the monovalent hydrocarbon group having 13 to 21 carbon atoms of R ¹ is, for example, an unsaturated group such as an alkenyl group or a saturated monovalent aliphatic hydrocarbon group such as an alkyl group; And monovalent alicyclic hydrocarbon groups such as cyclohexyl group; monovalent aromatic-containing hydrocarbon groups such as phenyl group, tolyl group, benzyl group, and styryl group; 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 in R ^{2 in} the above formula (2) 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 group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, n-octyl group, n-nonyl group, n-undecyl group and the like. . Of these, a 1-ethylpentyl group and an n-undecyl group are preferable.

  On the other hand, as represented by the above formula (3), the ratio of the number M of the carboxylic acid silyl ester group represented by the above formula (1) and the number N of the carboxylic acid silyl ester group represented by the above formula (2). (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 (D) has a siloxane unit represented by the following formulas (5) and (6) including the carboxylic acid silyl ester groups represented by the above formulas (1) and (2). preferable.

In the above formulas (5) and (6), 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 monovalent hydrocarbon group having 1 to 8 carbon atoms which may have a hydrogen atom or a substituent.

Here, R ¹ in the above formula (5) and R ² in the above formula (6) are respectively R ¹ explained in the above formula (1) and R ² explained in the above formula (2). It is the same. In the above formulas (5) and (6), examples of the monovalent hydrocarbon group having 1 to 8 carbon atoms which may have a substituent of R ³ include, for example, an alkyl group, a vinyl group, and allyl. A monovalent aliphatic hydrocarbon group such as a group; a monovalent alicyclic hydrocarbon group such as a cyclohexyl group; a monovalent aromatic hydrocarbon group such as a phenyl group, a tolyl group, a benzyl group, and a styryl group; And a group combining these, 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, 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 (5), the siloxane unit represented by each formula of following formula (I) is illustrated suitably.

Specifically as a siloxane unit represented by the said Formula (6), the siloxane unit represented by each formula of following formula (II) is illustrated suitably.

  The siloxane units represented by the above formulas (5) and (6) can be used alone or in combination of two or more.

The carboxylic acid silyl ester compound (D) preferably further has an ether-containing silyl group represented by the following formula (7), and the carboxylic acid silyl ester (D) is represented by the above formulas (1) and (2). A compound having a carboxylic acid silyl ester group represented by formula (7) and an ether-containing silyl group represented by the following formula (7) in the same molecule is more preferred.
R ⁶ O— (R ⁵ O) _r —R ⁴ —Si≡ (7)
(In the above formula (7), 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 or more carbon atoms. Represents an alkyl group of 30 or less or an organic group represented by R ¹³ — (CO) — (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 may be the same or different from each other.)

In the above formula (7), specific examples of the alkylene group having 2 to 6 carbon atoms that may have a substituent of R ⁴ include, for example, an ethylene group, 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 (7) is the same as R ⁴ in the above formula (7), but when r is 2 or more, the plurality of R ⁵ may be the same or different. Good. In addition, in the above formula (7),-(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 above formula (7), 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 (7), 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 (D) preferably has a siloxane unit represented by the following formula (8) including the ether-containing silyl group represented by the above formula (7).

In the above formula (8), 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 substituted Represents an alkylene group having 2 to 6 carbon atoms which may have a group, 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 a hydrocarbon group having 1 to 30 carbon atoms.), 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 (8) is the same as R ³ as described in the above formula (5) and (6) in. Further, R ^4, R ⁵ and R ⁶ and r in the formula (8) are the same as R ^4, R ⁵ and R ⁶ and r described in the above formula (7) in.

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

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

  As the carboxylic acid silyl ester compound (D), the siloxane unit represented by the above formulas (5) and (6) and the siloxane unit represented by the above formula (8) It is preferable to use polysiloxane contained in

  In the present embodiment, the siloxane units represented by the above formulas (5), (6) and (8) are not particularly limited with respect to the arrangement thereof. 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 (5), (6) and (8). Examples of such a siloxane unit include the following formula (9): And siloxane units represented.

In the above formula (9), 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 (9), the siloxane unit represented by following formula (10) or (11) is illustrated suitably.

The molecular terminal of the polysiloxane is not particularly limited, and examples of the terminal group include -SiR ¹⁰ ₃ , -Si (0R 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 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 (5) and (6) include a polysiloxane represented by the following formula (12).

In the above formula (12), 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 or a substituent. 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 (12) are Each represents an integer of 1 or more.

Wherein, R ¹ and R ² in the formula (12) are each the same as R ² described in R ¹ and the formula (2) in which described in the above formula (1), the formula ( 12) ^{R 3} in is the same as R ³ as described in the above formula (5) and (6) in.

  A in the above formula (12) represents the number of repeating units of the siloxane unit having a carboxylic acid silyl ester group represented by the above formula (1), that is, the siloxane unit represented by the above formula (5). 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 (12) represents the number of repeating units of the siloxane unit having a carboxylic acid silyl ester group represented by the formula (2), that is, the siloxane unit represented by the formula (6). 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 (12), 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 (12) include polysiloxane represented by the following formula (13).

  In the above formula (13), 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.

  The production method of the polysiloxane having the siloxane unit represented by the above formulas (5) and (6) 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 (5) and (6) and siloxane units represented by the above formula (8) include the following formulas ( The organosiloxane represented by 14) is preferably exemplified.
(R ¹ COO) _a (R ² COO) _b R ³ _c R ⁷ _d SiO _{(4-a-bc-d) / 2} (14)
0.10 ≦ a / (a + b) ≦ 0.80 (15)
1 ≦ c <2 (16)
0.001 ≦ d <1 (17)
1.95 ≦ a + b + c + d ≦ 2.60 (18)

In the above formula (14), 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 or a substituent. 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 represents an alkylene group having 2 to 6 carbon atoms, 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 1 carbon atom). Represents a hydrocarbon group of 30 or less, 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. Moreover, a, b, c, and d in the above formulas (15) to (18) represent numbers satisfying the relations of the above formulas (15) to (18).

Wherein, R ¹ and R ² in the formula (14) are respectively the same as R ² described in R ¹ and the formula (2) in which described in the above formula (1). Further, ^{R 3} in the formula (14) is the same as R ³ as described in the above formula (5) and (6) 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 (14) are each represented by the above formula ( 8) The same as R ⁴ , R ^5, R ⁶ and r described in 8) above.

  A, b, c and d representing the numbers satisfying the relations of the above formulas (15) to (18) 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 (14), 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 0.70 or less, and 0.01 or more More preferably, it is 0.50 or less.

  Examples of such organosiloxane include polysiloxane represented by the following formula (19).

In the formula (19), 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 or a substituent. 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, R ⁶ is 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 (19), a, b and d each independently represent an integer of 1 or more.

Wherein, R ¹ and R ² in the formula (19) are each the same as R ² described in R ¹ and the formula (2) in which described in the above formula (1), the formula ( 19) R ³ in is the same as R ³ as described in the above formula (5) and (6) in, R ^4, R ⁵ and R ⁶ and r in the formula (19), respectively, the This is the same as R ⁴ , R ^5, R ⁶ and r described in formula (7).

  A and b in the above formula (19) are the same as a and b described in the above formula (12), respectively. Moreover, d in the said Formula (19) represents the number of repeating units of the siloxane unit which has an ether containing silyl group represented by the said Formula (7), ie, the siloxane unit represented by the said Formula (8), It is an integer of 1 or more, preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less.

  In the above formula (19), 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 (19) include polysiloxane represented by the following formula (20).

  In the above formula (20), 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 formula (20) are the same as a and b described in the formula (12), respectively, and d in the formula (20) is in the formula (19). It is the same as d explained in. In the formula (20), 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 (20), s and t have a relationship of r = s + t with r in the above formula (7) or (8). s + t is 1 or more, preferably 5 or more, and more preferably 10 or more and 100 or less. In the formula (20), -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 (20), 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 (20) includes a polysiloxane represented by the following formula (21).

  The production method of the polysiloxane having the siloxane unit represented by the above formula (5) and the above formula (6) and the siloxane unit represented by the above formula (8) is not particularly limited. The siloxane unit represented by the above formula (8) is formed by reacting the containing polysiloxane with the alkenyl ether, and then a predetermined carboxylic acid is reacted with this to represent the above formula (5) and the above formula (6). A method of producing a polysiloxane by forming a siloxane unit; a method of reacting a Si—H group-containing polysiloxane, an 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 alkylhydrogensiloxane unit represented by the following formula (22).

In said formula (22), R < ¹¹ > is a methyl group, an ethyl group, or a phenyl group.

  The polysiloxane having an alkylhydrogensiloxane unit represented by the above formula (22) 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 (23) is mentioned.
^{_{CH 2 = CH-R 12 -}} (OR 5) r -OR 6 ··· (23)

In the above formula (23), R ⁵ represents an optionally substituted alkylene group having 2 to 6 carbon atoms, R ⁶ is 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, 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.

Here, R ^5, R ⁶ and r in the formula (23) are the same as R ^5, R ⁶ and r described in the above formula (7) in.

  Examples of the alkenyl ether represented by the above formula (23) 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 equation (23) and s and t in the following equation are in 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 for 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 (5). (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 (6), 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 (5), a palmitic acid and a stearic acid are preferable, As carboxylic acid for forming the siloxane unit represented by the said Formula (6) Is preferably capric acid or lauric acid. These carboxylic acids can be used alone or in combination of two or more.

  As the reaction accelerator (ring-opening catalyst), in addition to the carboxylic acid silyl ester compound (D), a metal catalyst, an amine catalyst, an organic carboxylic acid catalyst, and a phosphoric acid ester catalyst are excellent in the effect of promoting 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, etc., mentioned as the additive for curing the isocyanate group-containing prepolymer described later as additives. And the like.

  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 the present embodiment, the carboxylic acid silyl ester compound (D) can be used alone, but one type of the ring-opening catalyst other than the carboxylic acid silyl ester compound (D) and the carboxylic acid silyl ester compound (D) is used. A combination of the above may also be used. The carboxylic acid silyl ester compound (D) can improve the storage stability of the sealing material, and the ring-opening catalyst other than the carboxylic acid silyl ester compound (D) 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 to 10 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the urethane-based prepolymer containing an isocyanate group. The following is preferred. 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 (E)>
In the composition of this embodiment, calcium carbonate (E) is used as a filler for the isocyanate group-containing prepolymer. The calcium carbonate (E) 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.

  The content of calcium carbonate (E) is preferably 30 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the isocyanate group-containing prepolymer described above.

(Organic surface treated calcium carbonate)
Organic surface-treated calcium carbonate surface-treated with resin acids such as fatty acids and rosin acids, fatty acid esters, higher alcohol-added isocyanate compounds, and 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 are included. 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 200 parts by mass or less, and more preferably 50 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the isocyanate group-containing prepolymer. 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 200 mass parts, since the viscosity of the composition of this embodiment will become high and workability | operativity will deteriorate, it is unpreferable.

<Anti-aging agent>
The composition of this embodiment can further contain an anti-aging agent. The anti-aging agent prevents oxidation, light deterioration and heat deterioration after curing of the isocyanate group-containing prepolymer, and further improves the weather resistance and heat resistance. Examples of the antioxidant include N, N′-diphenyl-p-phenylenediamine (DPPD), N, N′-dinaphthyl-p-phenylenediamine (DNPD), 2,2,4-trimethyl-1,3- Examples thereof include dihydroquinoline (TMDQ), N-phenyl-1-naphthylamine (PAN), tris (tridecyl) phosphite, hindered phenol compounds, hindered amine light stabilizers, hindered phenol antioxidants, and the like.

  As a hindered amine light stabilizer, 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. And high molecular weight hindered amine light stabilizers having a molecular weight of 1,000 or more such as 119FL, 2020FDL, 944FD, and 944LD of CHIMASSORB series manufactured by Ciba Specialty Chemicals.

  Examples of the hindered phenol antioxidant include pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propioamide], benzenepropanoic acid 3,5- Examples thereof include bis (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester, 2,4-dimethyl-6- (1-methylpentadecyl) phenol, and the like.

  These anti-aging agents 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 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 isocyanate group-containing prepolymer, and 0.5 parts by mass or more and 5.0 parts by mass or less. It is more preferable to blend it by mass part 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 anti-aging agent exceeds 10 parts by mass.

<Resin for dilution>
The composition of the present embodiment can further contain a dilution resin in addition to the above components. This dilution resin is used to dilute the composition of the present invention 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 preferably 500 or more and 100,000 or less, more preferably 500 or more and 50,000 or less, still more preferably 500 or more and 20,000 or less, and particularly preferably 500 or more and 10, Preferable examples include a diluent resin having a high molecular weight of 000 or less and a polar group and liquid at room temperature. 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 the polar group include an ester group, an ether group (oxyalkylene group), and a urethane group that have good compatibility with the isocyanate group-containing prepolymer. The type and number of these groups are each independently in the molecule. You may have, and you may have more than one. 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 isocyanate group-containing prepolymer is good. Further, the dilution resin is preferably a dilution resin having substantially no functional group reactive with the functional group of the isocyanate group-containing prepolymer 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, a polyoxyalkylene resin is preferable in terms of low viscosity, good compatibility with the isocyanate group-containing prepolymer, good workability of the composition of the present embodiment, and good movement followability during curing. Further, alkyl etherified or alkyl esterified derivative resins of polyoxyalkylene resins of saccharide polyhydric alcohols and polyoxyalkylene urethane resins that are liquid at room temperature are preferred, and polyoxyalkylene urethane resins that are liquid at room temperature are particularly 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.

  Note that “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 synthesized. However, depending on the molar ratio of the raw materials, a small amount of hydroxyl group or isocyanate group may remain in the molecule, but in order to achieve the object of the present invention, it does not cause any inconvenience even if it is regarded as not containing an isocyanate group or hydroxyl group. Means.

  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 a molecular weight distribution (Mw / Mn) of 1.6 or less, particularly 1.0 to 1.3 or less. Is preferred. 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 isocyanate group-containing prepolymer, and among them, the 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 isocyanate group-containing prepolymer, from the viewpoint of curing speed, physical properties of the cured product, and the like. Less than the mass part is more preferable.

  Moreover, the composition of this embodiment can contain various additives as needed in addition to the components described above as long as the object of the present invention is not impaired. Examples of the additive include fillers other than calcium carbonate (E), a curing accelerating catalyst, an adhesion-imparting agent, a storage stability improving agent (dehydrating agent), a coloring agent, and an antifungal material. Each additive can be used in combination as appropriate.

  Examples of fillers other than calcium carbonate (E) 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, and alumina; fibrous fillers such as glass fiber and carbon fiber Wood powder, walnut flour, rice bran powder, pulp powder, cotton chips, rubber powder, polyamide resin, polyester resin, polyurethane resin, silicone resin, vinyl chloride resin, vinyl acetate resin, polyolefin resin such as polyethylene and polypropylene, acrylic Resin, epoxy resin, phenol resin, urea resin, thermoplastic resin such as melamine resin or organic fillers such as thermosetting resin powder, flame retardant filler such as magnesium hydroxide and aluminum hydroxide, etc. The particle size is 0.01 μm or more and 1,000 μm The following are preferred.

The curing accelerating catalyst accelerates the reaction between the isocyanate group or crosslinkable silyl group of the urethane prepolymer and moisture (moisture), promotes the internal curing of the one-component room temperature curable sealing material, and cures the surface and the interior. It is used to prevent cracks and the like from occurring in the cured product by reducing the difference in speed and reducing the difference in stress caused by the movement during curing. 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) Tonert), 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 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 isocyanate group-containing prepolymer. Furthermore, 10 parts by mass or more and 300 parts by mass or less, particularly 10 parts by mass or more and 200 parts by mass or less are preferable.

  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 the present embodiment, in addition to the additives described above, an organic solvent can be used for the purpose of reducing the viscosity of the sealing material and improving workability. The amount used is preferably suppressed as much as possible, and it is preferably used in a one-component room temperature curable sealing material so as to be less than 10% by mass, and further less than 5% by mass.

  A method for producing the composition of the present embodiment is not particularly limited. For example, each of the above components can be used in a roll, a kneader, an extruder, a universal agitator, a mixing mixer, etc. under reduced pressure or in an inert gas atmosphere such as nitrogen. Examples of the method include mixing by sufficiently kneading using a stirrer and uniformly dispersing.

  Thus, the composition of the present embodiment includes a room temperature curable resin (A) that cures at room temperature, and a silicate oligomer (B), and the silicate oligomer (B) is a condensate of an alkyl silicate. The curable composition is characterized in that at least a part of the alkoxy group bonded to the Si atom is a silicate oligomer having 3 to 18 carbon atoms.

  Cured products obtained by curing a curable composition containing a urethane-based prepolymer having an isocyanate group at the terminal, which has been used in the past, have dirt components such as mold and dust attached to the surface of the cured product or deteriorated. As a result, cracks and discoloration occurred. Therefore, a cured product obtained by using a urethane-based prepolymer having an isocyanate group at a terminal which has been conventionally used has to apply a coating material on the surface of the cured product. 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, the composition of the present embodiment is a condensate of room temperature curable resin (A) that cures at room temperature and alkyl silicate, and at least a part of the alkoxy groups bonded to Si atoms has 3 carbon atoms. Since it contains 18 or less silicate oligomers (B), it is possible to suppress the adhesion of dirt components to the surface of the cured product obtained by curing the composition of this embodiment. 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.

  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 this embodiment can suppress adhesion of dirt components even when exposed outdoors for a long period of time, and is excellent in stain resistance, so what is called a so-called architectural working joint or stone joint, tile joint, etc. As an object of construction, the composition of the present embodiment can be suitably used as a sealing material.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
<1. Synthesis example>
[Synthesis of room temperature curable resin (isocyanate group-containing urethane prepolymer) (A)]
In a reaction vessel equipped with a stirrer, thermometer, nitrogen introduction 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 to synthesize an isocyanate group-containing urethane prepolymer (A). The obtained isocyanate group-containing urethane prepolymer (A) was a viscous liquid at room temperature with an isocyanate group content of 2.15% by mass by titration.

[Synthesis of latent curing agent (urethane bond-containing oxazolidine compound) (C)]
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 (C) having a urethane bond and two oxazolidine rings in the molecule. The obtained urethane bond-containing oxazolidine compound (C) was a translucent liquid at room temperature.

[Synthesis of Reaction Accelerator (Carboxylic Acid Silyl Ester Compound) (D)]
After adding toluene to a concentration of 50% by mass to 133.3 parts by mass of stearic acid as the carboxylic acid component of formula (1) and 219.0 parts by mass of lauric acid as the carboxylic acid component of formula (2). 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 (D) was obtained by distilling toluene off.

<2. Preparation of composition>
[Example 1]
In a kneading vessel equipped with a stirrer, a nitrogen introduction tube and a heating / cooling device, 100 g of the room temperature curable resin (A) obtained in the synthesis example was charged in a nitrogen gas stream and dried in advance at 100 to 110 ° C. while stirring. 25 g of heavy calcium carbonate having a moisture content of 0.05% by mass or less by drying in the machine and 10 g of titanium oxide were charged and mixed until the contents were uniform. Next, 8 g of a solution prepared by dissolving 1.5 g of anti-aging agent 1 and 1.5 g of anti-aging agent 2 in 5 g of dimethyl carbonate in advance, 0.2 g of reaction accelerator (D), and 15 g of silicate compound (B4) Then, 100 g of organic surface-treated calcium carbonate, 8 g of latent curing agent (C), 32 g of dilution resin, and 18 g of solvent were charged, and further mixed until the contents were uniform. Subsequently, it degassed under reduced pressure at 50 hPa to 70 hPa, filled in a paper cartridge container, and sealed to prepare a composition. The resulting composition was a white pasty liquid that cured at room temperature.

[Example 2-6, Example 1-5, Comparative Example 1-2]
In each component used in Example 1 described above, each of the Examples, Reference Examples, and Comparative Examples was the same as Example 1 except for the combination of the type of silicate compound (B) and the addition amount (parts by mass). A composition was prepared. Table 1 shows the addition amount (parts by mass) of each component in each Example, Reference Example, and Comparative Example.

<3. Evaluation>
About each obtained composition, the tack was evaluated as follows by the method shown below. The results are shown in “Table 1”.
(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 on the applied primer was placed using a caulking gun to a thickness of 5 mm, flattened with a spatula, and in an environment of 23 ° C. and 50% RH. The composition was allowed to cure for 2 days, 5 days, and 7 days. 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.
Judgment standard “◯”: Tack is hardly felt.
“△”: Tack is slightly felt.
“×”: Tack is felt.

Details of each component of each example and comparative example shown in Table 1 are as follows.
Room temperature curable resin (A): Isocyanate group-containing urethane prepolymer (A) synthesized above
Anti-aging agent 1: hindered amine light stabilizer, TINUVIN 765, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, manufactured by Ciba Specialty Chemicals, Inc. Anti-aging agent 2: hinder Dophenol-based antioxidant, IRGANOX 1010, pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by Ciba Specialty Chemicals, Ltd., silicate oligomer (B1): MSK silicate MS51, manufactured by Mitsubishi Chemical Corporation ・ Silicate oligomer (B2): MSK silicate MS56, manufactured by Mitsubishi Chemical Corporation ・ Silicate oligomer (B3): MSK silicate MS56S, manufactured by Mitsubishi Chemical Corporation ・ Propyl silicate: monomer, Si (OC ₃ H ₇ ) _4, Tama chemicals -Silicate oligomer (B4): MSK silicate MS58B15, manufactured by Mitsubishi Chemical Corporation-Silicate oligomer (B5): MSK silicate MS58B30, manufactured by Mitsubishi Chemical Corporation-Latent curing agent (C): urethane bond-containing oxazolidine compound synthesized above ( C)
Reaction accelerator (D): Carboxylic acid silyl ester compound (D) synthesized above
Calcium carbonate (E1): Heavy calcium carbonate, manufactured by Maruo Calcium Co., Ltd. Organic surface treated calcium carbonate (E2): Viscolite MBP, manufactured by Shiraishi Calcium Co., Ltd. Titanium oxide: R-820, manufactured by Ishihara Sangyo Co., Ltd. Dimethyl carbonate: DMC, manufactured by Mitsui Chemicals Fine Co., Ltd. ・ Diluting resin: terminal esterified polyfunctional polyether, Sunflex GPA3000, manufactured by Sanyo Chemical Co., Ltd. ・ Solvent: Exol D40, manufactured by ExxonMobil

As shown in Table 1, it was confirmed that the compositions of Examples 1 to 6 hardly felt any tack on the surface of the test piece after 2 days from the start of the test. Further, in the compositions of Reference Examples 1 and 2, the tack was slightly felt on the surface of the test piece after 2 days from the start of the test, but the tack was hardly felt on the surface of the test piece after 5 days. confirmed. Further, it was confirmed that the compositions of Examples 1 to 6 and Reference Examples 1 and 2 were in a clean state with almost no dust adhering to the surface of the test piece. On the other hand, in the compositions of Reference Examples 4 and 5 in which a part of the alkoxy group has less than 3 carbon atoms, tack was slightly felt on the surface of the test piece after 5 days from the start of the test, but after 7 days. It was confirmed that almost no tack was felt on the surface of the test piece. In Reference Example 3 , it was confirmed that tack was slightly felt on the surface of the test piece even 7 days after the start of the test. Further, it was confirmed that the compositions of Comparative Examples 1 and 2 were tacky on the surface of the test piece even after 7 days from the start of the test.

  Therefore, a room temperature curable resin (A) that cures at room temperature, and a Kate oligomer (B) that is a condensate of alkyl silicate, and at least part of the alkoxy groups bonded to the Si atom has 3 to 18 carbon atoms. It has been found that the composition containing the has excellent tack and stain resistance. It has been found that the composition of this embodiment can be suitably used for a sealing material, an adhesive, and the like because both the tack and the stain resistance are excellent.

Claims (7)

A room temperature curable resin (A) that cures at room temperature;
A silicate oligomer (B),
The room temperature curable resin (A) is an isocyanate group-containing urethane prepolymer,
The silicate oligomer (B) is a condensate of an alkyl silicate, and is a silicate oligomer represented by the following formula (4) in which at least part of an alkoxy group bonded to a Si atom has 3 to 18 carbon atoms. ,
Content of the said silicate oligomer (B) is 2 mass parts or more and 20 mass parts or less with respect to 100 mass parts of said room temperature curable resin (A), The curable composition characterized by the above-mentioned.
R ² _n Si (OR ¹ ) _4-n (4)
(In the above formula (4), R ¹ and R ² each independently represents a propyl group or a butyl group. N is 0, 1 or 2.)   The curable composition according to claim 1, wherein the polyisocyanate compound of the isocyanate group-containing urethane prepolymer is aliphatic or alicyclic.   Furthermore, the curable composition of Claim 1 or 2 containing the latent hardening | curing agent (C) which reacts with a water | moisture content and produces | generates an active hydrogen group.   The curable composition according to claim 3, wherein the latent curing agent (C) is an oxazolidine compound. Further, as a reaction accelerator of the latent curing agent (C), a carboxylic acid silyl ester compound (D) is included,
The carboxylic acid silyl ester compound (D) 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 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.)   Furthermore, the curable composition of any one of Claim 1 to 5 which contains calcium carbonate (E) as a filler.   A sealing material using the curable composition according to any one of claims 1 to 6.