JP6519148B2 - 1 liquid moisture curable resin composition - Google Patents

Description

  The present invention relates to a one-part moisture curable resin composition.

  Sealing materials are widely used for the purpose of providing water tightness and airtightness by filling joints and gaps of various building members. However, when the sealing material is used for a long time, mold may be generated on the surface. As the cause of this, the surface of the sealing material is considered to be in a mold-prone state due to the supply of nutrients from the dust adhering to the surface and the replenishment of water by the water absorption effect of the sealing itself. .

The occurrence of such molds contaminates the surface of the sealing material and impairs the appearance, so that the application of the sealing material has to be repeated. In addition, mold that has propagated on the surface of the sealing material does not stay on the surface, and mycelium of mold enters inside, causing peeling and cracking in the sealing material and causing major damage such as breakage or water leakage in the building etc. There was a problem to bring. Therefore, there is a strong demand for a technology that can protect the sealing material from mold deterioration over a long period of time.
As an antimicrobial sealing material composition relevant to this, the thing of patent document 1 is proposed, for example.

  In addition, with regard to a urethane-based one-component moisture-curable sealing material that can be preferably used as a sealing material conventionally, in order to increase the hardness after curing, the distance between the crosslinking points of the urethane prepolymer is shortened or Either way of increasing was taken. However, when using this method, the isocyanate concentration inevitably increases, so carbon dioxide gas is likely to be generated during the curing process, bubbles are generated in the cured product, and there is a problem that appearance defects due to strength reduction or swelling occur. The

JP-A-6-227912

  The present invention aims to solve the above-mentioned problems. That is, the object of the present invention is that the tack disappears at an early stage, and moreover, it is excellent in the stain resistance performance against mold and dust even after long-term outdoor exposure, additionally, it hardens in a short time to have high hardness and is difficult to foam; It is an object of the present invention to provide a urethane-based one-component moisture-curable resin composition that can be preferably used as a material.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to solve the said subject, and completed the composition of this invention.
The composition of the present invention comprises a terminal isocyanate group-containing urethane prepolymer (A) that reacts with an amine compound, an imine compound (B) that reacts with water in the atmosphere to form an amine compound, and calcium carbonate treated with fatty acid ( C), an aminosilane compound (d1) and a trifunctional or higher polyisocyanate compound (d2), the imino group (NH) of the aminosilane (d1) to the isocyanate group (NCO) of the polyisocyanate (d2) before the reaction The hydrolyzable alkoxy group-containing silane compound (D) obtained by reacting to have an equivalent ratio (NH / NCO) of 0.2 to 0.8, and an antifungal agent (E) are mainly used. Containing urethane prepolymer (A), imine compound (B), calcium carbonate treated with fatty acid (C), silane compound (D) One-component moisture-curable resin composition having a proportion (content ratio) of the fungicide (E) to the total amount of non-volatile components (solids) in each of the fungicides (E) is 0.1% by mass or more It is.

  According to the present invention, as a sealing material, the tack disappears at an early stage, and moreover, it is excellent in the anti-staining ability against mold and dust even after long-term outdoor exposure, and additionally, it hardens in a short time to become high hardness and hardly foams. It is possible to provide a urethane-based one-component moisture-curable resin composition that can be preferably used.

  Each component which the composition of this invention contains is demonstrated.

<Urethane Prepolymer (A)>
The composition of the present invention contains a terminal isocyanate group-containing urethane prepolymer (A) (hereinafter, also simply referred to as "urethane prepolymer (A)") to be reacted with an amine compound.

  The urethane prepolymer (A) contains, at the molecular terminal, an isocyanate group that reacts with an amine compound in the molecule. The urethane prepolymer (A) is preferably one that is liquid at room temperature from the viewpoint of handling. The method for producing the urethane prepolymer (A) is not particularly limited, and a conventionally known method may be mentioned. The urethane prepolymer (A) is, for example, a reaction product obtained by reacting a polyisocyanate compound and a polyol compound such that an isocyanate group (NCO group) is in excess with respect to a hydroxyl 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 molecular ends.

The polyisocyanate compound used when producing a urethane prepolymer (A) will not be specifically limited if it has 2 or more of isocyanate groups in a molecule | numerator. As a polyisocyanate compound, for example, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4′-diphenylmethane diisocyanate (4,4 ′ -MDI), 2,2'-diphenylmethane diisocyanate (2,2'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, tolidine Aromatic polyisocyanates such as diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), xylylene diisocyanate (XDI), tetramethyl xylylene diisocyanate (TMXDI), triphenylmethane triisocyanate; Aliphatic polyisocyanates such as xamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI); transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis (isocyanate methyl) ) Alicyclic polyisocyanates such as cyclohexane (H ₆ XDI), dicyclohexylmethane diisocyanate (H ₁₂ MDI); polyisocyanate compounds such as polymethylene polyphenylene polyisocyanate; carbodiimide-modified polyisocyanates of these isocyanate compounds; these isocyanate compounds Isocyanurate modified polyisocyanates; these isocyanates Urethane prepolymer obtained a polyol compound to be described later compound is reacted; and the like. As the polyisocyanate compound, 4,4′-diphenylmethane diisocyanate is particularly preferable in view of easy availability and low cost.

  The polyisocyanate compounds can be used alone or in combination of two or more.

  If the polyol compound which produces | generates a urethane prepolymer is a compound which has 2 or more of OH groups, the molecular weight, frame | skeleton, etc. will not be specifically limited, As the specific example, low molecular polyhydric alcohol, polyether polyol, Examples include polyester polyols, other polyols, and mixed polyols thereof.

  Specific examples of low molecular weight polyhydric alcohols include ethylene glycol (EG), diethylene glycol, propylene glycol (PG), dipropylene glycol, (1,3- or 1,4-) butanediol, pentanediol. , Low molecular weight polyols such as neopentyl glycol, hexanediol, cyclohexanedimethanol, glycerin, 1,1,1-trimethylolpropane (TMP), 1,2,5-hexanetriol, pentaerythritol, etc. sugars such as sorbitol; Can be mentioned.

  The polycarbonate polyol is obtained, for example, by a transesterification reaction of a polyol compound and a dialkyl carbonate. Specifically, among the various low molecular weight polyhydric alcohols exemplified above, 1,6-hexanediol, 1,4-butanediol, 1,5-pentanediol and the like are suitable as the polyol compound. Can be mentioned. Moreover, as this dialkyl carbonate, the dialkyl carbonate represented, for example by following formula (1) can be used.

In formula (1), R ¹ and R ² are each independently an alkyl group having 12 or less carbon atoms.

  Specifically as a dialkyl carbonate represented by the said Formula (1), a dimethyl carbonate and a diethyl carbonate are mentioned suitably, for example.

  Specific examples of the catalyst suitable for the transesterification reaction of the above-mentioned polyol compound with the above-mentioned dialkyl carbonate include, for example, hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide and potassium hydroxide; And metal alcoholates such as potassium methylate, titanium tetraisopropylate, and zirconium tetraisopropylate. Among these, titanium tetraisopropylate and zirconium tetraisopropylate are preferable.

  As polyether polyols and polyester polyols, those derived from the above low molecular weight polyhydric alcohols are generally used, but those derived from aromatic diols, amines, and alkanolamines can also be suitably used. .

  Specific examples of the aromatic diols include, for example, xylylene glycol, 1,4-benzenedimethanol, styrene glycol, 4,4′-dihydroxyethylphenol; bisphenol A structure as shown below (4,4 '-Dihydroxyphenylpropane), bisphenol F structure (4,4'-dihydroxyphenylmethane), brominated bisphenol A structure, hydrogenated bisphenol A structure, bisphenol S structure, bisphenol AF structure having bisphenol skeleton; Be

  Specific examples of the amines include ethylene diamine and hexamethylene diamine. Specific examples of alkanolamines include ethanolamine and propanolamine.

  The polyether polyol includes, for example, ethylene oxide, propylene oxide, butylene oxide (tetra-oxide) in at least one selected from the compounds exemplified as the above-mentioned low molecular weight polyhydric alcohols, the above aromatic diols, amines and alkanolamines. The polyol etc. which are obtained by adding at least 1 sort (s) chosen from alkylene oxides, such as methylene oxide), tetrahydrofuran, etc., and a styrene oxide etc. are mentioned.

  Specific examples of such polyether polyols include polyethylene glycol, polypropylene glycol (PPG), ethylene oxide / propylene oxide copolymer, polytetramethylene ether glycol (PTMEG), sorbitol-based polyol and the like.

  Specific examples of polyether polyols having a bisphenol skeleton include polyether polyols obtained by adding ethylene oxide and / or propylene oxide to bisphenol A (4,4'-dihydroxyphenylpropane).

  Similarly, as the polyester polyol, for example, a condensation product of any of the above low molecular weight polyhydric alcohols, the above aromatic diols, amines and alkanolamines with a polybasic carboxylic acid (condensed polyester polyol); And lactone-based polyols;

  Specific examples of polybasic carboxylic acids that form the above-mentioned condensation type polyester polyols include, for example, glutaric acid, adipic acid, azelaic acid, pimelic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid, Other low molecular weight carboxylic acids, oligomeric acids, castor oil, hydroxycarboxylic acids such as a reaction product of castor oil and ethylene glycol, and the like can be mentioned.

  Specific examples of the lactone-based polyol include ring-opening polymers such as propionolactone and valerolactone.

  Examples of polyester polyols having a bisphenol skeleton include condensed polyester polyols obtained by using a diol having a bisphenol skeleton in place of the low molecular weight polyhydric alcohols or together with the low molecular weight polyhydric alcohols. Specific examples thereof include polyester polyols obtained from bisphenol A and castor oil, and polyester polyols obtained from bisphenol A, castor oil, ethylene glycol and propylene glycol.

  Specific examples of the other polyols include, for example, acrylic polyols; polybutadiene polyols; polymer polyols having a carbon-carbon bond in the main chain such as hydrogenated polybutadiene polyols; and the like.

  In the urethane prepolymer (A), one of the various polyol compounds exemplified above may be used alone, or two or more thereof may be used in combination.

  As described above, the urethane prepolymer (A) is obtained by reacting a polyol compound with an excess of a polyisocyanate compound, and specific examples thereof include various polyol compounds exemplified above and various polyisocyanates. A thing by the combination with a compound is mentioned.

  The viscosity of the urethane prepolymer (A) is generally 50 Pa · s or less, preferably 3 Pa · s or more and 20 Pa · s or less, and more preferably 5 Pa · s or more and 15 Pa · s or less.

  The mass average molecular weight of the urethane prepolymer (A) is preferably 2,000 or more and 100,000 or less, and more preferably 3,000 or more and 30,000 or less. When the mass average molecular weight of the urethane prepolymer is in the above range, the workability of the composition of the present invention obtained is favorable, which is preferable. In the composition of the present invention, the number average molecular weight is measured by gel permeation chromatography (GPC).

  The ratio of mixing of the polyisocyanate compound and the polyol compound in producing the urethane prepolymer (A) is the ratio of the number of isocyanate (NCO) groups in the polyisocyanate compound to the hydroxy (OH) group in the polyol compound (NCO / OH) is preferably 1.05 or more and 2.50 or less, and more preferably 1.1 or more and 2.3 or less. In such a range, the viscosity of the urethane prepolymer (A) is appropriate, and the elongation of the cured product is excellent.

  The reaction between the polyol compound and the polyisocyanate compound is not particularly limited, and, for example, a method of producing by heating and stirring the polyol compound and the polyisocyanate compound in the above-described ratio by weight at 50 ° C. or more and 130 ° C. or less Can be mentioned.

  The method for producing the urethane prepolymer (A) is not particularly limited, and the urethane prepolymer (A) may be, for example, a polyol compound having a predetermined amount ratio (NCO / OH) and a polyisocyanate compound, It can produce by heating and stirring at 50 degreeC or more and 130 degrees C or less. In addition, if necessary, urethanization catalysts such as organic tin compounds, organic bismuth, and amines can be used.

<Imine compound (B)>
The composition of the present invention contains an imine compound (B) (hereinafter also referred to simply as “imine compound (B)”) which reacts with moisture in the air to produce an amine compound.
The imine compound (B) is not particularly limited as long as it can be used for a curable resin such as a urethane prepolymer (A). The imine compound (B) is used as a latent curing agent, and is excellent in the curability with respect to the urethane prepolymer (A), the workability from compounding to coating, and the storage stability.

  The imine compound (B) is a compound derived from a carbonyl compound such as a ketone or an aldehyde and an amine. Specifically, ketimines and enamines which are reaction products of carbonyl compounds and polyamines; oxazolidine compounds which are reaction products of amino alcohols and carbonyl compounds, and the like can be mentioned. It is preferred to use an oxazolidine compound as the imine compound (B).

  By using the oxazolidine compound as the imine compound (B), the composition of the present invention obtained can be cured by moisture at normal temperature, and is excellent in storage stability and excellent in curability, and the curing rate is adjusted. And the curing time can be significantly reduced. In addition, the composition of the present invention becomes more difficult to foam.

  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 ring heterocycle containing an oxygen atom and a nitrogen atom. The oxazolidine compound reacts with moisture (moisture) in the air to undergo hydrolysis, and the oxazolidine ring forms (regenerates) a secondary amino group and an alcoholic hydroxyl group, thereby curing the urethane prepolymer (A) latently. It functions as an agent. When the isocyanate group of the urethane prepolymer (A) reacts with moisture, it forms a urea bond and cures, but at this time, carbon dioxide gas is also generated, and bubbles occur due to carbon dioxide gas in the cured product to deteriorate appearance and cure When the mixture of the urethane prepolymer (A) and the oxazolidine compound is exposed to moisture, the oxazolidine compound of the oxazolidine compound is reacted before the moisture and the isocyanate group react with each other. The composition of the present invention is that the ring is hydrolyzed by moisture to regenerate the secondary amino group and the alcoholic hydroxyl group, and these active hydrogens react with the isocyanate group to cure while suppressing the generation of carbon dioxide gas. It is possible to suppress foaming due to carbon dioxide gas.

  In addition, when aliphatic polyisocyanate is used as the polyisocyanate compound in the synthesis of the above urethane prepolymer (A), the curing speed is extremely delayed if it is a reaction of only water, but the oxazolidine compound is used in combination Thus, the reaction between the secondary amino group to be regenerated by the reaction with water and the isocyanate group derived from the aliphatic polyisocyanate has a higher reaction rate than the reaction with water, so the curing rate is accelerated, and the curing described later This has the effect of reducing the amount of promoting catalyst used.

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

  Specific examples of the compound having a hydroxyl group and an oxazolidine ring include N-hydroxyalkyl oxazolidine obtained by the dehydration condensation reaction of a secondary amino group of an alkanolamine and a carbonyl group of a ketone compound or an aldehyde compound.

  As a method of 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 mol, per 1.0 mol of the secondary amino group of the alkanolamine. It is heated and refluxed in a solvent such as toluene and xylene, more preferably 1.5 times mol or less, more preferably 1.0 times mol to 1.2 times mol, and dehydration condensation is performed while removing by-produced water. The method of performing reaction is mentioned. The excess aldehyde compound and ketone compound may be removed by distillation.

  Examples of alkanolamines 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, cyclohexanone and the like. Examples of aldehyde compounds include acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, 2-methylbutyraldehyde, n-hexylaldehyde, 2-methylpentyl aldehyde, n-octylaldehyde, 3,5 Aliphatic aldehyde compounds such as 5-trimethylhexyl aldehyde; and aromatic aldehyde compounds such as benzaldehyde, methyl benzaldehyde, trimethyl benzaldehyde, ethyl benzaldehyde, isopropyl benzaldehyde, isobutyl benzaldehyde, methoxy benzaldehyde, dimethoxy benzaldehyde, trimethoxy benzaldehyde and the like . Any of these may be used alone or in combination of two or more.

  Among these, as the alkanolamine, diethanolamine is preferable, and among the ketone compound or the aldehyde compound, an aldehyde compound is preferable, and isobutyraldehyde, 2-methylpentyl aldehyde and benzaldehyde are more preferable from the viewpoint of availability.

  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 etc. are mentioned.

  As the urethane bond-containing oxazolidine compound, the molar ratio of isocyanate group / hydroxyl group is 0.9 or more and 1.2 or less, preferably 0, of the hydroxyl group of the compound having a hydroxyl group and an oxazolidine ring and the isocyanate group of the organic isocyanate compound. What is obtained by reacting at a temperature of 50 ° C. or more and 120 ° C. or less in the presence or absence of an organic solvent is preferably used.

  Examples of the organic isocyanate compound used for the synthesis of the urethane bond-containing oxazolidine compound include the same as those used for the synthesis of the polysulfide-containing prepolymer described above, among which the crystallinity degree of the urethane bond-containing oxazolidine compound is decreased Aliphatic polyisocyanates are preferred, and hexamethylene diisocyanate is particularly preferred, from the viewpoint that the workability of the sealing material can be improved.

  The imine compound (B) is not particularly limited as to its production method. For example, heating and refluxing a carbonyl compound such as a ketone or an aldehyde and an amine in the absence of a solvent or in the presence of a solvent such as benzene, toluene, or xylene, and reacting while removing azeotropically removed water by azeotropic distillation It can be obtained by

  In the content of the imine compound (B), the ratio of the number of active hydrogens that can be generated from the imine compound (B) to the number of isocyanate groups of the urethane prepolymer (A) is 0.01 or more and 4.0 or less It is preferable that the amount be in the range of 0.05 to 2.0, more preferably in the range of 0.05 to 1.5. When the content of the imine compound (B) is in this range, the curing reaction proceeds by the hydrolysis reaction of the imine compound (B), and the composition of the present invention obtained is excellent in the curability.

<Fatty acid-treated calcium carbonate (C)>
The composition of the present invention contains fatty acid-treated calcium (C) (hereinafter also referred to as “surface-treated calcium carbonate (C)”).
Surface-treated calcium carbonate (C) is obtained by surface-treating calcium carbonate using a surface treatment agent containing fatty acid. By including surface-treated calcium carbonate (C) in the urethane prepolymer (A), excellent thixotropy can be imparted. The content of the surface-treated calcium carbonate (C) is preferably 30 parts by mass or more and 300 parts by mass or less, and more preferably 50 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the urethane prepolymer (A). If the content of the surface-treated calcium carbonate (C) is 30 parts by mass or more, the viscosity of the composition of the present invention is high and the workability is excellent. Moreover, it is because the viscosity of the composition of this invention does not become high too much that content of a surface treatment calcium carbonate (C) is 300 mass parts or less, and it is excellent in workability.

The calcium carbonate used for producing surface-treated calcium carbonate (C) is not particularly limited, and for example, calcium carbonate precipitated by introducing CO ₂ gas into an aqueous slurry of Ca (OH) ₂ is mechanically produced as limestone. Any calcium carbonate of ground calcium carbonate obtained by crushing and classification may be used. In general, precipitated calcium carbonate can be preferably used in that finer particles can be easily obtained.

  As the fatty acid, at least one selected from the group consisting of saturated fatty acids, unsaturated fatty acids, alicyclic carboxylic acids, ammonium salts or amine salts of resin acids or sodium salts can be preferably used as the surface treating agent. The saturated fatty acid, the unsaturated fatty acid, the alicyclic carboxylic acid and the resin acid are not particularly limited, but the number of carbon atoms is preferably large, and the number of carbon atoms is preferably 8 or more. By increasing the carbon number, the composition of the present invention can have high thixotropy in addition to storage stability.

  Specific examples of saturated fatty acid, unsaturated fatty acid and ammonium salt or unsaturated sodium salt of saturated unsaturated fatty acid include caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid and myristin. Acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, myristic acid, 2-ethylbutyric acid, 2-ethylhexanoic acid, isononanoic acid, isodecanoic acid, neodecanoic acid, isotridecanoic acid, iso Palmitic acid, isostearic acid, myristoleic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, cetoleic acid, sorbic acid, beef tallow stearic acid, palm kernel fatty acid, coconut fatty acid, palm fatty acid, palm stearic acid, beef tallow fatty acid, soybean Fatty acid, partially cured Ammonium fatty acid, partially hardened coconut fatty acid, partially hardened beef tallow fatty acid, partially hardened soy fatty acid, extremely hardened palm kernel fatty acid, extremely hardened coconut fatty acid, extremely hardened beef tallow fatty acid, ammonium or amine salt or sodium salt such as extremely hardened soybean fatty acid It can be mentioned. Moreover, as an ammonium salt or amine salt or sodium salt of alicyclic carboxylic acid, ammonium salts or amine salts or sodium salts, such as naphthenic acid, benzoic acid, and phenylacetic acid, are mentioned, for example. Moreover, as an ammonium salt or amine salt or sodium salt of resin acid, for example, ammonium salt or amine salt or sodium salt of resin acid such as abietic acid, pimaric acid, parastronic acid, neoabietic acid and the like can be mentioned. These can be used alone or in combination of two or more.

  Among the above-mentioned saturated fatty acid, unsaturated fatty acid, alicyclic carboxylic acid, ammonium salt of resin acid or amine salt or sodium salt, particularly preferred are lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, beef tallow Stearic acid, palm kernel fatty acid, partially cured palm kernel fatty acid, extremely cured palm kernel fatty acid, coconut fatty acid, partially cured coconut fatty acid, extremely cured coconut fatty acid, palm fatty acid, palm stearic acid, beef tallow fatty acid, partially cured beef tallow fatty acid, extremely cured tallow Fatty acid, soybean fatty acid, partially hardened soybean fatty acid, extremely hardened soybean fatty acid, naphthenic acid, saturated fatty acid such as abietic acid, neoabietic acid, unsaturated fatty acid, alicyclic carboxylic acid, ammonium salt or amine salt of resin acid or sodium salt Can be mentioned.

  Examples of water-soluble amine compounds used as saturated fatty acids, unsaturated fatty acids, alicyclic carboxylic acids, and amine salts of resin acids include alkyl-substituted amines and alkanolamines. Specifically, as the amine compound substituted with an alkyl group having 1 to 4 carbon atoms, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, propylamine, isopropylamine, isopropylamine, dipropylamine, diisopropylamine, butylamine And isobutylamine and sec-butylamine. Examples of the alkanolamine substituted with an alkanol group having 1 to 3 carbon atoms include monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine and isopropanolamine. Examples of alkyl alkanolamines substituted with an alkyl group having 1 to 4 carbon atoms and an alkanol group having 1 to 3 carbon atoms include dimethyl ethanolamine and diethyl ether. Ruamin, N- butyl diethanolamine. Other water soluble amine compounds include N, N-dimethyl-1,3-diaminopropane, N, N-diethyl-1,3-diaminopropane and the like, and among them, monoethanolamine, diethanolamine or triethanolamine Ethanolamine is generally and preferably used, and in particular, triethanolamine is most preferably used.

  As a method of surface treatment of calcium carbonate, for example, since it is a gas-liquid reaction in the case of precipitated calcium carbonate, fatty acids are added to a water slurry of precipitated calcium carbonate or stirred, or in a hydrous cake of precipitated calcium carbonate The surface treatment agent containing a metal soap is made to adsorb | suck to the surface of a calcium carbonate by knead | mixing to a method. Alternatively, an aqueous ammonia solution or an amine compound may be added in advance in a water slurry or in a water-containing cake, and after uniformly stirring and mixing, saturated fatty acid, unsaturated fatty acid, alicyclic carboxylic acid and resin acid may be added. . Alternatively, an aqueous ammonia solution or an amine compound may be added after or simultaneously with the addition of a saturated fatty acid, unsaturated fatty acid, alicyclic carboxylic acid and resin acid. In the case of heavy calcium carbonate, dry type surface treatment is preferable since it is often ground by dry type. In the case of dry grinding, for example, a heating and stirring apparatus such as a Henschel mixer may be used.

The aqueous slurry of precipitated calcium carbonate in the case of surface treatment in a water slurry preferably has a concentration of 10 g CaCO ₃ / L or more and 300 g CaCO ₃ / L or less. When the concentration is lower than 10 g CaCO ₃ / L, it is disadvantageous in terms of productivity. On the other hand, when the concentration is higher than 300 g CaCO ₃ / L, the viscosity of the water slurry becomes high and the workability becomes worse. Moreover, as for the density | concentration of a fatty acid, 0.5% or more and 30% or less (acid conversion) are preferable. If the concentration of the fatty acid is lower than 0.5%, a large amount of water is required, which is disadvantageous in productivity, while if it is higher than 30%, the viscosity of the aqueous fatty acid solution becomes high, and it becomes difficult to dissolve uniformly. It may be worse.

  The surface treatment temperature in the case of surface treatment in water slurry is preferably 20 ° C. or more and 98 ° C. or less, more preferably 40 ° C. or more and 90 ° C. or less, and further preferably 50 ° C. or more and 80 ° C. or less. When the surface treatment temperature is lower than 20 ° C., adsorption bonding to calcium carbonate is less likely to occur, which is not preferable because the surface treatment becomes uneven. If the temperature is higher than 98 ° C., although the effect of the composition of the present invention can be sufficiently obtained, it is not only dangerous because it is likely to boil, but it is not preferable because it is necessary to prepare a pressure resistant device.

  In the case of a water-containing cake or dry treatment, it is preferably 20 ° C. or more and 150 ° C. or less, more preferably 40 ° C. or more and 130 ° C. or less, and still more preferably 50 ° C. or more and 120 ° C. or less. When the surface treatment temperature is lower than 20 ° C., it is not preferable because adsorption bonding to calcium carbonate is difficult to occur and the surface treatment may be uneven. If the temperature is higher than 150 ° C., the fatty acid may be thermally degraded and degraded, which is not preferable.

The surface-treated calcium carbonate (C) surface-treated with calcium carbonate, which is a raw material before surface treatment, and a fatty acid, has a specific surface area Sw of 3 m ² / when measured by a BET method using a nitrogen adsorption method. g or more and 100 m ² / g or less is preferable, 8 m ² / g or more and 60 m ² / g or less is more preferable, and 10 m ² / g or more and 40 m ² / g or less is more preferable. When the specific surface area is less than 3 m ² / g (particles are large), even if it is a resin composition containing surface-treated calcium carbonate (C) surface-treated with a fatty acid as a surface treatment agent, excellent storage stability, Although adhesion is obtained, thixotropy may be insufficient. Also, if the specific surface area is larger than 100 m ² / g (small particles), particle aggregation is strong, and even if fatty acid is used as a surface treatment agent, the dispersibility in the resin composition is deteriorated. The desired performance may not be exhibited. Usually, the specific surface area tends to be slightly reduced before and after the surface treatment, but when sufficiently dispersed, the specific surface area is almost the same.

The surface treatment amount of the surface treatment agent containing fatty acid is, as shown by the following formula (i), the surface treatment agent amount As [mg / m ² ] per unit specific surface area to the specific surface area (particle size) Sw of calcium carbonate It is preferable to vary accordingly. Here, for convenience, Sw uses the specific surface area of calcium carbonate after surface treatment.
As = Tg / Sw [mg / m ² ] (i)
Sw is a BET specific surface area (m ² / g) by a nitrogen adsorption method, and Tg is a heat loss (mg / g) per 1 g of surface-treated calcium carbonate at 200 ° C. or more and 500 ° C. or less.

Generally, in the above formula (i), the surface treatment agent amount As is preferably 0.20 mg / m ² or more and 7.50 mg / m ² or less, more preferably 0.80 mg / m ² or more and 7.00 mg / m ² Or less, more preferably 1.50 mg / m ² or more and 6.00 mg / m ² or less. In the case of 0.20 mg / m ² or more, the effect of surface treatment is sufficient, and it is economically excellent by setting it as 7.50 mg / m ² or less.

<Silane compound (D)>
The composition of the present invention comprises an aminosilane compound (d1) and a trifunctional or higher polyisocyanate compound (d2), and an imino group of the aminosilane (d1) to the isocyanate group (NCO) of the polyisocyanate (d2) before the reaction. A silane compound (D) containing a hydrolyzable alkoxy group obtained by reacting such that the equivalent ratio (NH / NCO) of (NH) is 0.2 to 0.8 (hereinafter simply referred to as “silane compound (D Also referred to as “)”.

  The aminosilane compound (d1) preferably has a structure represented by the following formula (2).

In Formula (2), R ¹ is a linear or branched hydrocarbon group having 1 to 12 carbon atoms. R ² and R ³ are each independently a linear or branched hydrocarbon group having 1 to 12 carbon atoms. m is an integer of 1 to 3;

R ¹ of the aminosilane compound (d1) of the above formula (2) is a linear or branched hydrocarbon group having 1 to 12 carbon atoms. Specific examples of R ¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group and a butyl group. Among these hydrocarbon groups, methyl group, ethyl group and butyl group are preferable. It is because it is easy to control reaction of an aminosilane compound (d1) and the polyisocyanate compound (d2) mentioned later as it is such a hydrocarbon group. More preferably, they are a methyl group and an ethyl group.

R ² and R ³ in the above-mentioned formula (2) are each independently a linear or branched hydrocarbon group having 1 to 12 carbon atoms. Specific examples of R ² and R ³ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group and a butyl group. Among these hydrocarbon groups, methyl group and ethyl group are preferable. When it is set as such a hydrocarbon group, in addition to becoming heat resistance, water resistance, and a thing excellent in weather resistance, when it is set as the composition of this invention, adhesive expression is quick. More preferably, it is a methyl group.

  M of the silyl group in said Formula (2) is an integer of 1-3. That is, at least one alkoxy group which is a substituent bonded to a silicon atom may be present. Therefore, all may be an alkoxy group, one may be an alkyl group and two may be an alkoxy group, or one may be an alkoxy group and two may be an alkyl group. This alkoxy group is hydrolyzable. Preferably it is 2 or 3 as m. When it is set as the composition of this invention as it is such a silyl group, it is easy to control the crosslinking density of a composition. In addition to this, there is also an effect that the expression of adhesion is quick.

  The aminosilane compound (d1) is more preferably one having a structure represented by the following formula (3).

  As a specific example of an aminosilane compound (d1) provided with the structure represented by said Formula (3), Silquest A-Link15 made from Momentive is mentioned.

  Next, the polyisocyanate compound (d2) will be described. The polyisocyanate compound (d2) is not particularly limited as long as it is a compound having three or more isocyanate groups. It is preferable that the isocyanate group which a polyisocyanate compound (d2) has is three to four.

  Examples of the polyisocyanate compound (d2) include alicyclic, aromatic and aliphatic polyisocyanates.

As a specific polyisocyanate compound (d2), the thiophosphate which has 3 or more of isocyanate groups is mentioned, for example.
The thiophosphate can be linked to the isocyanate group via a hydrocarbon group. As a hydrocarbon group, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group (for example, phenylene group), these combinations are mentioned, for example.
Examples of thiophosphate include those represented by the following formula.
S = P-(OR) ₃
In the formula, R is a hydrocarbon group having an isocyanate group.

Examples of the thiophosphate having three or more isocyanate groups include tris (isocyanatophenyl) thiophosphate.
The polyisocyanate compound (d2) preferably contains tris (isocyanatophenyl) thiophosphate, and more preferably tris (p-isocyanatophenyl) thiophosphate.
Tris (p-isocyanatophenyl) thiophosphate is represented by the following formula (4).

  Moreover, as a polyisocyanate compound (d2), an isocyanurate body is mentioned, for example. Examples of the isocyanurate include isocyanurate of tolylene diisocyanate, isocyanurate of hexamethylene diisocyanate, isocyanurate of isophorone diisocyanate, and isocyanurate of tolylene diisocyanate and hexamethylene diisocyanate.

  As an isocyanurate of tolylene diisocyanate (TDI), what is represented by following structure (5) is mentioned, for example.

  As an isocyanurate of hexamethylene diisocyanate (HDI), what is represented by following structure (6) is mentioned, for example.

  As an isocyanurate of isophorone diisocyanate (IPDI), what is represented by following formula (7) is mentioned, for example.

  Examples of the isocyanurate of tolylene diisocyanate and hexamethylene diisocyanate include those represented by the following formula (8).

  The polyisocyanate can be used alone or in combination of two or more.

  The polyisocyanate compound (d2) is preferably one including a biuret bond represented by the following formula (9).

In the formula (9), R ¹ , R ² and R ³ each are a chain aliphatic hydrocarbon group or an alicyclic hydrocarbon group which may have an oxygen atom of 2 to 6 carbon atoms, Each may be the same or different.

  As a compound represented by Formula (9) and which contains a biuret bond in a molecule | numerator, HDI biuret represented by following Formula (10) is mentioned as a suitable example.

  The polyisocyanate compound (d2) is preferably one containing an allophanate bond represented by the following formula (11).

In the formula (11), R ¹ , R ² and R ³ each are a chain aliphatic hydrocarbon group or an alicyclic hydrocarbon group which may have an oxygen atom of 2 to 6 carbon atoms, Each may be the same or different.

  As a compound which is represented by Formula (11) and which contains a biuret bond in a molecule | numerator, HDI allophanate represented by following Formula (12) is mentioned as a suitable example.

  Further, the polyisocyanate compound (d2) is preferably an adduct. The adduct is, for example, a difunctional or higher isocyanate compound obtained by reacting an isocyanate monomer with a low molecular weight active hydrogen-containing compound having two or more functions, specifically, a reaction of trimethylolpropane and hexamethylene diisocyanate. Compound, a compound obtained by reacting trimethylolpropane with tolylene diisocyanate, a compound obtained by reacting trimethylolpropane with xylylene diisocyanate, a compound obtained by reacting trimethylolpropane with isophorone diisocyanate, 1,6-hexanediol And the compound etc. which made it react with hexamethylene diisocyanate.

  As a polyisocyanate compound (d2), an adduct (TMP HDI adduct) of TMP (trimethylolpropane) and HDI (tolylene diisocyanate) represented by the following formula (13) can be mentioned as a preferred example.

  Further, as a polyisocyanate compound (d2), an adduct of TMP (trimethylolpropane) and XDI (xylylene diisocyanate) represented by the following formula (14) (TMP XDI adduct) can be mentioned as a preferable example.

  Furthermore, as a polyisocyanate compound (d2), an adduct of TMP (trimethylolpropane) and hydrogenated XDI (xylylene diisocyanate) represented by the following formula (15) (TMP hydrogenated XDI adduct) is a preferred example. It can be mentioned.

  The silane compound (D) is a compound obtained by reacting the aminosilane compound (d1) with the polyisocyanate compound (d2). In this reaction, the imino group (NH) in the aminosilane compound (d1) and the at least one isocyanate group (NCO) of the polyisocyanate compound (d2) are added together to give only one compound as a molecular structure. It does not have to be done. That is, various compounds may be generated depending on the number of molecules of the aminosilane compound (d1) to be reacted with the site and the number of isocyanate groups of the polyisocyanate compound (d2) to be reacted. All such compounds are silane compounds (D). Accordingly, the silane compound (D) has one silyl group and at least one isocyanate group in one molecule.

  At this time, the equivalent ratio (NH / NCO) of the imino group (NH) of the aminosilane (d1) to the isocyanate group (NCO) of the polyisocyanate (d2) before the reaction is 0.2 to 0.8. Let it react. The equivalent ratio is preferably 0.3 to 0.8. When the equivalent ratio is in such a range, the composition of the present invention is cured in a short time to have high hardness and is difficult to foam.

  There is no restriction | limiting in particular in the method to synthesize | combine a silane compound (D), A well-known method can be used. Specifically, a method of adding the above-mentioned polyisocyanate compound (d2) to the aminosilane compound (d2) can be mentioned.

  More specifically, the addition reaction is carried out by adding the aminosilane compound (d1) dropwise to the polyisocyanate compound (d2) and performing the addition reaction, adding the aminosilane compound (d1) to the polyisocyanate compound (d2) and further adding a catalyst Method of adding and reacting, method of reacting while adding aminosilane compound (d1) dropwise to a solution in which polyisocyanate compound (d2) is dissolved in a solvent, aminosilane in a solution in which polyisocyanate compound (d2) is dissolved in a solvent The method of adding a compound (d1), and also adding a condensation catalyst and making it react is mentioned.

  It is preferable that it is 1-50 mass parts with respect to 100 mass parts of urethane prepolymers (A), and, as for content of a silane compound (D), it is more preferable that it is 3-30 mass parts.

<Antifungal agent (E)>
The composition according to the invention contains a fungicide (E).
The antifungal agent (E) is not particularly limited as long as it is a substance that exhibits antifungal properties, and is not particularly limited to acids and alkalis, halogens and halides, sulfur and sulfur compounds, arsenic and arsenic compounds, and boron and boron compounds. , Ozone, hydrogen peroxide, oxidant system, metal, metal salt system, organic metal compound system, hydrocarbon, tar system, halogenated hydrocarbon system, nitrated hydrocarbon, chloronitrated hydrocarbon system, alcohol system, phenol system Chlorophenol, ether, cyclic ether, aldehyde, ketone, carboxylic acid, soap, ester, lactone, acid amide, carbamic acid, amino carboxylic acid, cyan, nitrile, amidine, guanidine, Quaternary ammonium salts, pyridine, quinoline, acridine, diazines, triazines, pyrrols, imidazoles, oxazos Le-oxazine type, Thiooxane-Thiosansone type, Thiazole-Thiathiazine type, Thiocyan-Isothiocyan type, Thiourea-Thiosemicarbabit type, dithiocarbamate, Thiuram disulfide type, Sulfide sulphoxide, Sulfone type, Sulfonic acid type, Sulfamide type And phosphate esters and thiophosphate esters, and antibiotics.

  Specifically, hexadisylviridinium, chlorhexazine, propionic acid, sorbic acid, ethanol, benzyl alcohol, formalin, gludaraldehyde, 2,3-dichloro 1,4-naphthoquinone, biosol, p-chlor-m -Kylelenol, N-chlorsacinimide, chlornaphthaline, 5-bromosalicylic-4-bromoanilide, 2- (4-thiazolyl) benzimidazole (thiobendazole), 4'-trichloro-2 'hydroxydiphenyl ether, 2 ( Benzimidazole) methyl carbamate, 5-chloro-2-methyl-4-isothiazolin-1-one, N- (fluorodichloromethylthio) phthalamide, 2-n-octyl-4-isothiazolin-1-one, N, N- Dimethyl-N- (fluorodimethylethio) -N Phenylsulfamide, α-bromocinnamaldehyde, orthophenylphenol, joodemethyl-p-tolylsulfone, parachlorometakirynol, tributyltin phthalate, 2,4,5,6-tetrachloroisophthalonitrile, 10,10 ' -Oxybis phenoxy aludin etc. are mentioned.

In addition, as isothiazoline compounds, 2-n-octyl-4-isothiazolin-3-one, 5-dichloro-2-n-octyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one , N-n-butyl-1,2-benzisothiazolin-3-one and the like.
In addition, as urea-based compounds, 3- (3,4-dichlorophenyl) -1,1-dimethylurea (DCMU), 3- (3,4-dichlorophenyl) -1-methyl-1-methoxyurea, 3- (3- 3,4-Dichlorophenyl) -1- (2-methylcyclohexyl) urea, 3-phenyl-1- (2-methylcyclohexyl) urea, 3- (phenyldimethylmethyl) -1- (4-methylphenyl) urea and the like It can be mentioned.
Further, as triazines, 2-chloro-4,6-bis (ethylamino) -1,3,5-triazine, 2-chloro-4-ethylamino-6-isopropylamino-1,3,5- Triazine, 2-methylthio-4,6-bis (ethylamino) -S-triazine, 2-methylthio-4-ethylamino-6-isopropylamino-S-triazine, 2-methylthio-4,6-bis (isopropylamino) ) -S-triazine, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-S-triazine, N'-tert-butyl-N-cyclopropyl-6- (methylthio) -1,3,5 -Triazine-2, 4- diamine etc. are mentioned.

Further, as thiuram disulphide-based ones, tetramethyl thiuram disulphide, tetraethyl thiuram disulphide, tetraisopropyl thiuram disulphide, dipyrrolisol tiuram disulphide, polyethylene thiuram disulphide and the like can be mentioned.
Moreover, as an imidazole type thing, the cyclic compound derivative of a benzimidazole carbamic-acid compound, a sulfur atom containing benzimidazole compound, benzimidazole, etc. can be mentioned. Examples of benzimidazole carbamates include methyl 1H-2-benzimidazolecarbamate, methyl 1-butylcarbamoyl-2-benzimidazolecarbamate, methyl 6-benzoyl-1H-2-benzimidazolecarbamate, 6- (2 And -thiophenecarbonyl) -1H-2-benzimidazole carbamate methyl and the like. Examples of sulfur atom-containing benzimidazole compounds include 2,4-bis (4-thiazolyl) benzimidazole, 2- (4-thiazolyl) benzimidazole (TBZ) and the like.
Moreover, as a pyridine type thing, 2,3,5,6- tetrachloro- 4- (methylsulfonyl) pyridine etc. are mentioned.
Moreover, zinc 2-pyritin thiol 1-oxide etc. are mentioned as a zinc pyrithione type thing.

In addition, as a thiazole system, 2- (4-thiocyanomethylthio) benzothiazole, 4,5-benzoisothiazol-3-one, 4- (n-octyl) isothiazolin-3-one, 4-methyl-5 -Chloroisothiazolin-3-one, 4-methylisothiazolin-3-one, 4,5-dichloro-4-cyclohexylisothiazolin-3-one, 2- (thiocyanomethylthio) benzothiazole, 2-mercaptobenzothiazole sodium, 2 -Mercaptobenzothiazole zinc etc. are mentioned.
Moreover, N, N- dimethyl- N'- (fluoro dimethyl thio) -N'- phenyl sulfamide etc. are mentioned as a thing of haloalkyl thio type | system | group.
Moreover, N- (trichloromethylthio) phthalimide etc. are mentioned as a phthalimide type thing.
Moreover, diaide methyl-p-trisulphone etc. are mentioned as an iodine type thing.
In addition, organic halogen-based (organic NS halogen-based etc.), organic metal-based, and phenylphenol-based ones can be mentioned.

The fungicide (E) may be an inorganic compound. As inorganic compounds, for example, salts or oxides of metal ions exhibiting antibacterial and antifungal properties of silver, copper and zinc on various carriers, such as activated carbon, activated alumina, apatite, zeolite, silica gel, zirconium phosphate, etc. And those supported on titanium phosphate and the like.
There is no particular limitation on the method of supporting these metal ions on the inorganic compound, and any supporting methods known so far can be adopted. For example, a method of supporting by physical adsorption or chemical adsorption, supporting by ion exchange reaction Examples include a method, a method of supporting with a binder, and a method of forming a thin layer on the surface of an inorganic compound and supporting it by a thin film forming method such as vapor deposition, dissolution precipitation reaction, sputtering or the like.

  The fungicide (E) may be an inorganic compound as described above, but is preferably an organic compound.

  In the composition of the present invention, nonvolatile components (solid content) in each of urethane prepolymer (A), imine compound (B), fatty acid-treated calcium carbonate (C), silane compound (D) and fungicide (E) The ratio (content ratio) of the fungicide (E) to the total amount of) is 0.1 mass% or more, preferably 0.1 to 10 mass%, and 0.2 to 5 mass%. Is more preferred. It is because the contamination resistance performance with respect to mold | fungi and dust will improve more in such a range.

The composition of the present invention contains, as main components, a urethane prepolymer (A), an imine compound (B), surface-treated calcium carbonate (C), a silane compound (D) and a fungicide (E).
Here, “main component” means that the content is 50% by mass or more as a ratio (content ratio) to the total amount of non-volatile components (solid content) contained in the composition of the present invention. That is, in the composition of the present invention, the total amount of the urethane prepolymer (A), the imine compound (B), the surface-treated calcium carbonate (C), the silane compound (D) and the fungicide (E) The ratio (content ratio) to the total amount of total non-volatile components (solid content) contained in the composition is 50% by mass or more. The content is preferably 55% by mass or more, more preferably 60% by mass or more, more preferably 65% by mass or more, more preferably 70% by mass or more, and 75% by mass It is more preferable that it is more than.

<Additives>
The composition of the present invention contains various additives as needed, in addition to the above-mentioned components, as long as the object of the present invention is not impaired (specifically, for example, in the range of 50% by mass or less). be able to. As the additive, for example, a filler, a plasticizer, a silane coupling agent, a pigment, a dye, an antiaging agent, an antioxidant, an antistatic agent, a flame retardant, an adhesion imparting agent, a stabilizer, a dispersing agent, a mildew Agents, ring-opening catalysts for imine compounds, and the like.

  The filler may be organic or inorganic in various forms. For example, pyrogenic clay, kaolin clay, calcined clay; silica sand, fumed silica, calcined silica, precipitated silica, crushed silica, fused silica; diatomaceous earth; heavy calcium carbonate, iron oxide, zinc oxide, titanium oxide, titanium oxide, barium oxide, Magnesium oxide; magnesium carbonate, zinc carbonate; organic or inorganic fillers such as carbon black; these fatty acids, resin acids, fatty acid ester treated products, fatty acid ester urethane compound treated products.

  As a plasticizer, for example, polypropylene glycol (B), diisononyl phthalate (DINP), dioctyl phthalate (DOP), dibutyl phthalate (DBP); dioctyl adipate, isodecyl succinate; diethylene glycol dipensoate, pentaerythritol Ester; butyl oleate, methyl acetyl ricinoleate; tricresyl phosphate, trioctyl phosphate; propylene glycol adipate polyester, butylene glycol adipate polyester; alkyl sulfonic acid phenyl ester (for example, mezamol manufactured by Bayer); chain transfer agent An acrylic polymer polymerized at a polymerization temperature of 150 ° C. or more and 350 ° C. or less and having a number average molecular weight of 500 or more and 5000 or less; a polymer plasticizer; The polymer plasticizer has a number average molecular weight (Mn) of 500 to 100,000, preferably 500 to 100,000, more preferably 500 to 50,000, and still more preferably 500 to 20,000. Particularly preferred is a resin for dilution which is liquid at room temperature and which has a polar group and a high molecular weight of 500 or more and 10,000 or less. The amount of the dilution resin used is preferably more than 0 parts by mass and 200 parts by mass or less, and 10 parts by mass or more, with respect to 100 parts by mass of the urethane prepolymer (A), from the viewpoint of curing speed and physical properties of the cured product. 100 parts by mass or less is more preferable. 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 of polyoxyalkylene monool such as polyoxyethylene monool and polyoxypropylene monool, alkyl esterified derivative resin, and polyoxyalkylenated resin of saccharide type polyhydric alcohol Examples thereof include alkyl etherified and alkyl esterified derivative resins, and polyoxyalkylene based urethane resins which are liquid at room temperature. Any of these may be used alone or in combination of two or more. In the composition of the present invention, a plasticizer is used to dilute the composition of the present invention to lower the viscosity and improve the workability, as well as to control rubber elastic properties such as modulus and elongation after curing. In particular, it is preferable to use a polymer plasticizer from the viewpoint of being a polymer. When a polymeric plasticizer is included in the composition of the present invention, the polymeric plasticizer is used as a diluent resin.

  As a silane coupling agent, for example, trimethoxyvinylsilane and γ-glycidoxypropyltrimethoxysilane are particularly preferable because they are excellent in the effect of improving the adhesion to a wet surface, and are general-purpose compounds.

  The pigment may be either an inorganic pigment or an organic pigment or both. For example, titanium oxide, zinc oxide, ultramarine blue, bengala, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, inorganic pigments of sulfates, organic pigments such as azo pigments, copper phthalocyanine pigments and the like can be used.

  The dye is not particularly limited, and conventionally known dyes can be used. For example, black dye, yellow dye, red dye, blue dye and brown dye can be mentioned.

  As an antiaging agent, a hindered phenol type compound, a hindered amine type compound, a benzotriazole type compound is mentioned, for example.

  Antioxidants include, for example, butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).

  Examples of the antistatic agent include quaternary ammonium salts; and hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

  Flame retardants include, for example, chloroalkyl phosphates, dimethyl methyl phosphonates, bromine and phosphorus compounds, ammonium polyphosphates, neopentyl bromide-polyethers, brominated polyethers.

  Examples of the adhesion promoter include terpene resin, phenol resin, terpene-phenol resin, rosin resin, and xylene resin.

  As a stabilizer, fatty acid silyl ester, fatty acid amido trimethyl silyl compound etc. are mentioned, for example.

  The dispersant is a substance which makes solid particles fine and disperses them in a liquid, and examples thereof include sodium hexametaphosphate, sodium condensed naphthalene sulfonate, surfactant and the like.

  The method for producing the composition of the present invention is not particularly limited, but, for example, a roll, a kneader, an extruder, a universal stirrer, or the like under the reduced pressure or in an inert gas atmosphere such as nitrogen. The method of fully knead | mixing fully using stirring apparatuses, such as a mixing mixer, and making it disperse | distribute uniformly etc. is mentioned.

  The composition of the present invention is moisture-curable, and can be used as a one-component curable composition which is compounded and stored in advance and sealed with all the compounding components and is cured by moisture in the air after application. In addition, as a curing agent, components such as a curing catalyst, a filler, a plasticizer, water and the like are separately blended in advance and used as a two-component type in which the blending agent (material) and the polymer composition are mixed before use. It can also be done.

  The composition of the present invention is a one-component type, and all the compounding components are compounded in advance. Therefore, the compounding components containing water are dehydrated and dried in advance, or they are dewatered by pressure reduction during compounding and kneading. Is preferred. The composition of the present invention is excellent in curability because, when exposed to moisture, the imine compound (B) undergoes a curing reaction by hydrolysis to form an amino group. Therefore, the obtained composition of the present invention can be stored in a closed container, and at the time of use, the cured product can be obtained at room temperature by the moisture in the air. In addition, the curing reaction can be progressed by appropriately supplying water.

  Although the application of the composition of the present invention is not particularly limited, since it has the above-mentioned excellent properties, sealing materials for civil engineering and construction, concrete, wood, metal, glass, plastic etc., adhesives It is suitably used for applications such as sealing agents, potting agents, elastic adhesives, coating materials, lining materials, structural adhesives in concrete and mortar, and crack injection materials.

  Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the examples.

Synthesis Example 1
[Synthesis of Urethane Prepolymer (A)]
In a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet tube and heating / cooling device, 220 g of polyoxypropylene diol (Asaken Glass Co., Ltd., Exenol 3020, number average molecular weight 3,200) under a nitrogen gas stream, Charge 100 g of oxypropylene triol (Asahi Glass Co., Ltd., Exenol 5030, number average molecular weight 5, 100), and while stirring, 33.5 g of hexamethylene diisocyanate (Desmodur H, molecular weight 168, manufactured by Sumika Bayer Urethane Co., Ltd.), dibutyl After adding 0.05 g of tin dilaurate, the mixture was heated and reacted at 70 to 80 ° C. with stirring for 2 hours. When the isocyanate group content became equal to or less than the theoretical value (2.37 mass%), the reaction was terminated by cooling to room temperature to synthesize a urethane prepolymer (A).
The obtained urethane prepolymer (A) had an isocyanate group content of 2.15% by mass by titration, and was a viscous liquid at normal temperature.

Synthesis Example 2
[Synthesis of imine compound (B)]
In a reaction vessel equipped with a stirrer, thermometer, ester tube and heating / cooling device, charge 435 g of diethanolamine (molecular weight 105) and 183 g of toluene, and add 328 g of isobutyraldehyde (molecular weight 72.1) while stirring. The mixture was heated to 110 to 150 ° C. for 3 hours, and a reflux dehydration reaction was carried out while removing by-produced water out of the system. The amount of water removed was 74.5 g. Subsequently, heating was carried out while reducing the pressure to 50 to 70 hPa to remove toluene and unreacted isobutyraldehyde to obtain an intermediate reaction product, 2-isopropyl-3- (2-hydroxyethyl) oxazolidine.
Further, 348 g of hexamethylene diisocyanate (molecular weight: 168) was added to 659 g of the obtained 2-isopropyl-3- (2-hydroxyethyl) oxazolidine, followed by reaction at 80 ° C. for 8 hours. The reaction end point was the time when the NCO content actually measured by titration became 0.0 mass%, to obtain an imine compound (B) having a urethane bond and two oxazolidine rings in the molecule.
The obtained imine compound (B) was a translucent liquid at room temperature.

Synthesis Example 3
[Synthesis of Silane Compound (D ₁ )]
A compound represented by the above formula (3) (Silquest A-Link 15, manufactured by Momentive) and an HDI isocyanurate (Sumidur N3300, manufactured by Sumika Bayer Urethane), an imino group (NH) / isocyanate group ( NCO) = 1/2 and blended reacted so to give a silane compound (D _1).
This silane compound (D ₁ ) corresponds to the silane compound (D) contained in the composition of the present invention.

Synthesis Example 4
[Synthesis of Silane Compound (D ₂ )]
An imino group (NH) / a compound represented by the above formula (3) (Silquest A-Link 15, manufactured by Momentive) and an HDI biuret (number of functional groups 2, Sumidur N3200, manufactured by Sumika Bayer Urethane Co., Ltd.) compounded reacted so that the isocyanate group (NCO) = 1/2, to give a silane compound (D _2).
This silane compound (D ₂ ) corresponds to the silane compound (D) contained in the composition of the present invention.

Example 1
100 g of the urethane prepolymer (A) obtained in Synthesis Example 1 is charged in a stirrer, a nitrogen introducing pipe, and a kneading container with a heating / cooling device under a nitrogen gas stream, and the drier has a temperature of 100 to 110 ° C. while stirring. Twenty-five grams of ground calcium carbonate having a water content of 0.05 mass% or less and 10 g of titanium oxide were added and dried until the contents were uniform. Next, 8 g of a solution prepared by previously dissolving 1.5 g of a hindered amine-based light stabilizer and 1.5 g of a hindered phenol-based antioxidant in 5 g of dimethyl carbonate, 100 g of surface-treated calcium carbonate (C), and the imine compound obtained in Synthesis Example 2 (B) 8 g, 32 g of a polyoxyalkylene resin for dilution, and 18 g of an organic solvent (1) were charged, and further mixed until the contents became uniform. Thereafter, a mixture of 3 g of the silane compound (D ₁ ) obtained in Synthesis Example 3, 10 g of a plasticizer and 10 g of an organic solvent (2) was added, and the contents were further mixed until it became uniform. Then, 3 g of antifungal agent (E ₁ ) was added, and the contents were further mixed until uniform.
The composition was then prepared by vacuum degassing at 50-70 hPa, filling into a paper cartridge container and sealing.
The resulting composition was in the form of a white paste that cures at room temperature.

[Examples 2 to 4]
The antifungal agent (E ₁ ) was used in Example 1, but the same operation as in Example 1 was carried out except using the antifungal agent (E ₂ ) or the antifungal agent (E ₃ ) instead. The compositions according to Examples 2 and 3 were obtained.

Example 4
The silane compound (D ₁ ) was used in Example 1. However, except that the silane compound (D ₂ ) obtained in Synthesis Example 4 was used instead, the same operation as in Example 1 was performed, and the composition was changed. Obtained.

Comparative Example 1
Although the antifungal agent (E ₁ ) was used in Example 1, the same operation as in Example 1 was carried out except that this was not used, to obtain a composition.

Comparative Example 2
Although 3 g of the silane compound (D ₁ ) was used in Example 1, 3 g of HDI isocyanurate (Sumidur N 3300, manufactured by Sumika Bayer Urethane Co., Ltd., described as “silane compound (X ₁ )” in Table ₁ ) is used instead. The same operation as in Example 1 was carried out except using, to obtain a composition.

Comparative Example 3
Although the silane compound (D ₁ ) was used in Example 1, the same operation as in Example 1 was carried out except that this was not used, to obtain a composition.

Comparative Example 4
In Example 1, 3 g of the silane compound (D ₁ ) was used, but instead a compound represented by the above formula (3) (Silquest A-Link 15, manufactured by Momentive, Inc., “Silane compound (X ₂ ) in Table 1 The same operation as in Example 1 was carried out except using 3 g of Note) to obtain a composition.

Comparative Example 5
Although 8 g of the imine compound (B) was used in Example 1, the same operation as in Example 1 was carried out except that this was not used, to obtain a composition.

The compounding quantity of each component in each of Examples 1-4 and Comparative Examples 1-5 is shown in Table 1.
In addition, each component will be specifically described below.
Surface-treated calcium carbonate (C): Calfoseal 15B, manufactured by Maruo Calcium Co., Ltd. Antifungal agent (E ₁ ): Biocide 733, manufactured by Taisho Technos, Inc. Antifungal agent (E ₂ ): Biocide 7662 DN, manufactured by Taisho Technos Antifungal agent (E ₃ ): Biocide CF-10, manufactured by Taisho Technos Co., Heavy calcium carbonate: Super S, manufactured by Maruo Calcium Co., Ltd. Titanium oxide: R-820, manufactured by Ishihara Sangyo Co., Ltd. hindered amine light stabilizer: Ciba · Svechalty Chemicals, TINUVIN 765, bis sebacate (1,2,2,6,6-pentamethyl-4-piperidyl)
-Hindered phenolic antioxidant: manufactured by Ciba Specialty Chemicals, IRGANOX 1010, pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
-Dimethyl carbonate: DMC, manufactured by Mitsui Chemicals Fine, Inc.-Polyoxyalkylene resin for dilution: Sanflex GPA 3000, manufactured by Sanyo Chemical Industries, Ltd.-Organic solvent (1): Exsol D40, manufactured by Exxon Mobil-Plasticizer: DINP, J-plus Manufactured organic solvents (2): Mineral spirit, JX Nippon Oil & Energy Corporation

  Next, the curability, tackiness, foamability, hardness, mold resistance and stain resistance of each of the compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 5 were evaluated. The evaluation method is described below.

<Curable>
The curing time of the surface of the resin composition was the time during which the surface tackiness of the resin composition existed after the initiation of the curing reaction, that is, the tack free time was taken as the curing time. Each composition obtained in Examples 1 to 4 and Comparative Examples 1 to 5 was poured into a polyethylene frame of 10 cm long × 1 cm wide × 1 cm high so as to prevent air bubbles from entering into the upper end atmosphere. Create a test specimen with the surface you are touching flat. This specimen is placed at 20 ° C. and 55% humidity, and this time is taken as the start time for measuring the curing time. Next, lightly touch the surface with a polyethylene film after 24 hours, and if the test body does not adhere to the film, set the curing property to ○, and the test body adheres to the film. The curability was x.

<Tack>
Using a slate plate 50 mm wide x 50 mm long x 5 mm high, apply a primer (No. 40, manufactured by Yokohama Rubber Co., Ltd.) within the range of 30 mm wide x 30 mm long on the surface of the slate plate, 23 ° C And left at 50% RH for 1 hour.
Next, each composition obtained on the applied primer is placed to a thickness of 5 mm using a caulking gun, flattened with a spatula, and at 23 ° C., 50% RH. The composition was allowed to cure for 2 days, 5 days and 7 days. Then, after the exposure was completed, the tack was determined by finger touch.
The judgment criteria are as follows.
"○": Tack is hardly felt.
"△": Tack is felt somewhat.
"X": Tack is felt.

<Effervescent property>
The mortar form (50 mm × 50 mm × depth 25 mm) is left in an atmosphere of 23 ± 2 ° C. × 50 ± 5% RH for 24 hours or more. After that, cover the side of mortar form with a 50mm wide gum tape (made of cloth) and cover it, and further cover the side with a 25mm wide gum tape (made of cloth) so that 5 to 7 mm will be left on the upper side of the form. Do. Next, the composition is filled in the mortar form so as not to contain air, and immediately cured in an oven at 40 ° C. for 3 days. Thereafter, a cut is made with a cutter knife, the hardened composition is manually peeled off from the mortar-made mold, and the interface is visually observed to confirm the presence or absence of foaming. And the thing of 0-1 was evaluated as (circle), the thing of 2-3 two (triangle | delta), and four or more thing was evaluated as x of the number of foam | bubbles.

<Hardness>
Asker C (ASKER C) hardness was measured according to Japan Rubber Association Standard (SRIS) 0101. The Asker C hardness is obtained by leaving each of the obtained compositions in an atmosphere of 40 ° C. × 95% RH for 5 days for curing, using an Asker C hardness tester (manufactured by Kobunshi Keiki Co., Ltd.). Each was measured. And, if the Asker C hardness is 40 or more, it is judged that the hardness is high, and if it is less than 40, the hardness is not high and it is evaluated as x.

Mold resistance
Each composition is formed into 40 mm long × 40 mm wide × 3 mm thick, and cured by standard curing (curing for 14 days under conditions of 23 ° C., 50% RH, and then curing for 14 days under conditions of 30 ° C.) and curing The For each test body obtained in this manner, five types of compositions were applied on the surface of the composition coated in a sterile room at 30 ° C. and 85% RH based on the provisions of JIS Z 2911 (mold resistance test). After spraying mold fungi, the cells were cultured for 28 days, and the presence or absence of mold on the surface of each test sample was visually observed and evaluated based on the following evaluation criteria.
(Mold resistance)
O: mold was not observed on the surface of the coating film and the surface of the composition.
X: mold was observed on the coating film surface and the composition surface.

<Stain resistance>
Using a slate plate 50 mm wide x 50 mm long x 5 mm high, apply a primer (No. 40, manufactured by Yokohama Rubber Co., Ltd.) within the range of 30 mm wide x 30 mm long on the surface of the slate plate, 23 ° C And left at 50% RH for 1 hour.
Next, each composition obtained on the applied primer was placed to a thickness of 5 mm using a caulking gun, flattened with a spatula, and exposed outdoors under Hiratsuka Outdoor North Surface Environment . Then, after half an exposure, the stain was judged visually.
The judgment criteria are as follows.
"○": Almost no dirt is felt.
"△": Some dirt is felt.
"X": The stain is clearly felt.

  The evaluation results of the curability, tackiness, foamability, hardness, mold resistance and stain resistance are shown in Table 1.

  The compositions in Examples 1 to 4 exhibited excellent results in curability, tackiness, foamability, hardness, mold resistance and stain resistance. On the other hand, the compositions in Comparative Examples 1 to 5 were inferior in at least one of curability, tackiness, foamability, hardness, mold resistance and stain resistance.

Claims (1)

Terminal isocyanate group-containing urethane prepolymer (A) which reacts with an amine compound,
An oxazolidine compound (B) which reacts with moisture in the air to form an amine compound,
Fatty acid-treated calcium carbonate (C),
The equivalent ratio of the imino group (NH) of the aminosilane (d1) to the isocyanate group (NCO) of the polyisocyanate (d2) before the reaction of the aminosilane compound (d1) and the trifunctional or higher polyisocyanate compound (d2) A silane compound (D) containing a hydrolyzable alkoxy group obtained by reacting such that NH / NCO) becomes 0.2 to 0.8,
Antifungal agent (E),
Containing as a main ingredient,
Fungus for total amount of non-volatiles (solids) in each of urethane prepolymer (A), oxazolidine compound (B), calcium carbonate (C) treated with fatty acid, silane compound (D) and fungicide (E) The proportion (content rate) of the agent (E) is 0.1% by mass or more,
The content of the oxazolidine compound (B), wherein the urethane prepolymer (A) is the ratio of the number of the oxazolidine compound (B) active hydrogen that may be generated from the relative number of isocyanate groups is 0.01 to 2.0 with One-part moisture curable resin composition, which is an amount of