JP4744230B2 - Sealant composition - Google Patents

Description

The present invention is related to sea ring member sets formed product to have a very stable thixotropic over time.

  Conventionally, a room temperature curable resin such as a modified silicone resin or an isocyanate group-containing prepolymer has been used as a resin component in sealing materials, adhesives, paints and the like for applications such as construction, civil engineering, and automobiles. In these applications, it is necessary to impart thixotropic properties to the room temperature curable resin because it is used on a vertical surface area or an inclined surface depending on the location used. For example, in a building application, a sealing material that is filled in a joint formed on an outer wall or a joint formed on a ceiling needs to prevent the sealing material from dripping (not slumping) during and after construction. Also in automobile applications, etc., it is necessary to prevent the member from shifting due to its own weight when the member is bonded. In order to prevent these from dripping (so as not to slump) or slipping, it is generally practiced to add thixotropic properties by blending surface-treated calcium carbonate or fine powdered silica with a room temperature curable resin. ing.

However, the conventionally known technique has the following various problems.
That is, in order to impart sufficient thixotropy to the room temperature curable resin, the use of fatty acid-treated calcium carbonate increases the amount used, reduces the degree of freedom of formulation, increases the stress during low elongation, and increases moisture. When blended with a curable room temperature curable resin, there is a problem that storage stability deteriorates due to its moisture content. In addition, when colloidal silica is used, sufficient thixotropy can be imparted with a relatively small amount, but on the other hand, the polarity of the room temperature curable resin or organic solvent to be blended is large, or a catalyst is added. Thus, if the curing speed is increased, there are problems that thixotropic properties disappear and sagging and slump are generated, and storage stability is deteriorated due to moisture content.
In order to improve these, a thixotropic polyurethane resin composition (see Patent Document 1) in which a hydrophobic colloidal silica and a polyisocyanate-aminosilane reaction product are blended with a polyurethane resin has been proposed. There is a problem that is insufficient. In addition, a urethane composition having a storage stability and thixotropy in which a terminal isocyanate group-containing urethane prepolymer is blended with a bisphenol derivative and colloidal silica has been proposed (see Patent Document 2). The effect of imparting modification is insufficient, and thixotropic properties are lost or storage stability is insufficient due to the incorporation of a highly polar solvent or catalyst. Furthermore, a moisture-curable water-swellable polyurethane composition (see Patent Document 3) containing a water-swellable polyurethane prepolymer having an isocyanate group at the terminal and a thixotropic agent for polyurea compounds having a specific chemical structure is also proposed. However, although the thixotropic effect of this composition is good, it is necessary to add a large amount of polyurea compound, and there is a problem that the storage stability of this composition is insufficient.
Japanese Unexamined Patent Publication No. 64-24851 JP 7-41537 A Japanese Patent Laid-Open No. 10-140001

The object of the present invention is to solve the above-mentioned problems of the prior art, and to impart thixotropic properties that are extremely stable for a long period of time even when a large amount of resin, organic solvent, plasticizer, or catalyst is used in a small amount. it can, as a result, it is possible to put together a variety of compositions in accordance with the needs of customers, is to provide Hisage Yu the Sea ring member sets Narubutsu the physical properties of the cured product. Another object of the present invention is to provide Hisage Sea ring member sets Narubutsu which as possible out to increase the curing rate it is possible to use a catalyst.

In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, in the system using finely divided silica as the thixotropic agent in the isocyanate group-containing urethane prepolymer, the thixotropic agent is substantially used as the thixotropic agent. or by using a specific compound having no hydroxyl group, it found that sea ring member sets formed product to have a very stable thixotropic long term is obtained, in which have reached the present invention.
That is, this invention is shown by the following (1)-( 4 ).

(1) A sealing material composition comprising an isocyanate group-containing urethane prepolymer, a finely divided silica having a BET specific surface area of 10 to 500 m ² / g, and a thixotropic agent, wherein the thixotropic agent is The said sealing material composition characterized by being the compound which does not contain an isocyanate group or a hydroxyl group substantially obtained by making the organic isocyanate compound and the compound which has the nitrogen atom couple | bonded with the hydroxyl group react.

(2) The sealing material composition according to (1), wherein the compound having a nitrogen atom bonded to the hydroxyl group is an oxime compound or a hydroxylamine compound.

(3) The sealing material composition according to (1) or (2), wherein the finely divided silica is hydrophilic colloidal silica that does not treat silanol groups on the surface .

(4) The sealing material composition according to any one of (1) to (3), further comprising an additive.

For the first time according to the present invention, extremely stable thixotropy can be imparted over a long period of time even when using a resin with a large polarity, an organic solvent, a plasticizer, or a catalyst with a small amount of formulation, and as a result, a variety according to customer needs can Crossed Do composition, it becomes possible to provide Hisage Sea ring member sets Narubutsu excellence in the physical properties of the cured product. Further, it became possible to provide Hisage Sea ring member sets Narubutsu which as possible out to increase the curing rate it is possible to use a catalyst.

The present invention will be described in detail below.
The isocyanate group-containing urethane prepolymer in the present invention is one in which an isocyanate group reacts with moisture (moisture) to form a urea bond to be crosslinked and cured, and an active hydrogen compound and an organic isocyanate are combined with active hydrogen (group). ) With an excess of isocyanate groups.
Specifically, the active hydrogen compound and the organic isocyanate have a total isocyanate group / active hydrogen (group) equivalent ratio of 1.3 to 10 / 1.0, more preferably 1.5 to 5.0 / 1. It can be preferably produced by reacting simultaneously or sequentially within a range of 0.0. When the equivalence ratio is less than 1.3 / 1.0, the resulting urethane prepolymer has too few cross-linking points, and the elongation and tensile strength after curing of the sealing material composition are lowered, resulting in rubber elastic properties and adhesiveness. When the equivalence ratio exceeds 10 / 1.0, the amount of carbon dioxide generated increases when reacting with moisture, which causes foaming.

Examples of the active hydrogen compound include polymeric polyols, amino alcohols, polyamines, and the like.
Examples of the polymer polyol include polyoxyalkylene polyols, polyester polyols, polyester amide polyols, polyether / ester polyols, polycarbonate polyols, poly (meth) acrylic polyols, hydrocarbon polyols, and the like. The number average molecular weight is 500 or more. belongs to.
Examples of the polyoxyalkylene-based polyol include those obtained by ring-opening addition polymerization of alkylene oxide, and those obtained by ring-opening addition polymerization of alkylene oxide in an initiator such as a compound containing two or more active hydrogens.
Examples of the initiator include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol, diglycerin and the like. Low molecular weight polyhydric alcohols, sorbitol, sucrose, glucose, lactose, low molecular weight polyhydric alcohols such as glucose, lactose, sorbitan, low molecular weight polyphenols such as bisphenol A and bisphenol F, low molecular weight such as ethylenediamine and butylenediamine Polyamines, low molecular amino alcohols such as monoethanolamine and diethanolamine, low molecular polycarboxylic acids such as adipic acid and terephthalic acid, and at least one of these is alkylene oxide Polyoxyalkylene polyol having a low molecular weight obtained by reacting the like.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran.
Specifically, polyoxyalkylene polyols are specifically polyoxyethylene polyol, polyoxypropylene polyol, polytetramethylene ether polyol, poly (oxyethylene) -poly (oxypropylene) -random or block copolymer polyol, poly (Oxypropylene) -poly (oxybutylene) -random or block copolymer polyols and the like, and these various polyols and organic polyisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. There may also be mentioned those having a hydroxyl group at the molecular end by reacting with an isocyanate group in excess of the hydroxyl group.
The polyoxyalkylene polyol preferably has a number average molecular weight of 500 to 100,000, more preferably 1,000 to 30,000, and particularly preferably 1,000 to 20,000 for reasons such as good workability. The average number of alcoholic hydroxyl groups per molecule is preferably 2 or more, more preferably 2 to 4, and particularly preferably 2 to 3.
Further, the polyoxyalkylene-based polyol is obtained by using a catalyst such as a double metal cyanide complex, and has a total unsaturation of 0.1 meq / g or less, further 0.07 meq / g or less, particularly 0.04 meq / g. The following are preferable, and the molecular weight distribution [ratio of polystyrene-equivalent weight average molecular weight (Mw) to number average molecular weight (Mn) by gel permeation chromatography (GPC) = Mw / Mn]] is 1.6 or less, particularly 1 A narrow one of 0.0 to 1.3 is preferable.
In the present invention, the polyoxyalkylene-based polyol 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 1 mol of hydroxyl group in the molecule. Means that the remaining part may be modified with ether, urethane, ester, polycarbonate, polyamide, polyacrylate, polyolefin, etc., but in the present invention, 95% by mass or more of the molecule excluding the hydroxyl group. Most preferred is a polyol consisting of polyoxyalkylene.
Examples of polyester polyols and polyester amide polyols include, for example, known dicarboxylic acids such as succinic acid, adipic acid, and terephthalic acid, their acid esters, acid anhydrides, and the like, and initiators for the synthesis of the above polyoxyalkylene polyols. Examples thereof include compounds obtained by a dehydration condensation reaction with a compound containing two or more active hydrogens to be used. Further examples include lactone polyester polyols obtained by cleavage polymerization of cyclic ester (ie, lactone) monomers such as ε-caprolactone.
Examples of the polyether ester polyol include compounds produced from the polyoxyalkylene polyol and the dicarboxylic acid, acid anhydride and the like.
Examples of the polycarbonate polyol include a dehydrochlorination reaction between low-molecular polyhydric alcohols used in the production of the polyoxyalkylene polyol and phosgene, or diethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and the like. Examples thereof include compounds obtained from transesterification and the like.
Examples of the poly (meth) acrylic polyol include those obtained by copolymerizing a hydroxyethyl (meth) acrylate containing a hydroxyl group with another (meth) acrylic acid alkyl ester monomer.
Examples of the hydrocarbon polyol include polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, hydrogenated polyisoprene polyol, chlorinated polyethylene polyol, and chlorinated polypropylene polyol.
Examples of the polyol further include low molecular weight polyhydric alcohols having a number average molecular weight of less than 500, which are listed as raw materials for producing the polyoxyalkylene polyol.
Examples of the polyamine include high-molecular polyamines such as polyoxyalkylene polyamines having a number average molecular weight of 500 or more and a polyoxyalkylene polyol terminal having an amino group, such as a terminal diaminated product of polypropylene glycol.
Examples of the polyamine further include low molecular weight polyamines having a number average molecular weight of less than 500, such as ethylenediamine, hexamethylenediamine, isophoronediamine, diaminodiphenylmethane, and diethylenetriamine.
Examples of amino alcohols include monoethanolamine, diethanolamine, N-methyldiethanolamine, N-methyldipropanolamine, and N-phenyldiethanolamine.
In addition, polyamide resins, polyester resins and the like having a number average molecular weight of 500 or more, which generally contain active hydrogen groups known in the polyurethane industry, are also included.
Any of these may be used alone or in combination of two or more.
Among these, since the viscosity of the isocyanate group-containing urethane prepolymer obtained is low and the physical properties after curing are good, the viscosity of the sealing material composition obtained therefrom is low and the workability is good, and the rubber elasticity after curing From the viewpoint of high physical properties and adhesiveness, a polymer polyol is preferable, a polyoxyalkylene polyol is more preferable, and a polyoxypropylene polyol is particularly preferable. In addition, high molecular monoalcohols such as polyoxyalkylene monoalcohol, butyl alcohol, and octadecyl monoalcohol, and low molecular monoalcohols can be used for modifying the isocyanate group-containing urethane prepolymer.

  Specific examples of the organic isocyanate include organic monoisocyanates, organic polyisocyanates, and mixtures thereof, with organic polyisocyanates being preferred.

  The organic monoisocyanate may contain one isocyanate group in the molecule, and the organic group other than the isocyanate group is preferably a hydrophobic organic group that does not contain moisture-curable functional groups such as moisture. Specifically, aliphatic monoisocyanates such as n-butyl monoisocyanate, n-hexyl monoisocyanate, n-tetradecyl monoisocyanate, n-hexadecyl monoisocyanate, octadecyl monoisocyanate, n-chloroethyl monoisocyanate, chlorophenyl monoisocyanate Isocyanate, 3,5-dichlorophenyl monoisocyanate, p-fluorophenyl monoisocyanate, 2,4-difluorophenyl monoisocyanate, o-trifluoromethylphenyl monoisocyanate, p-nitrophenyl monoisocyanate, p-isopropylphenyl monoisocyanate, 2 , 6-Diisopropyl monoisocyanate, p-toluenesulfonyl monoisocyanate, p-benzyloxyphenyl monoisocyanate Aromatic monoisocyanate such as, and other 2-methacryloyloxyethyl isocyanate. These can be used alone or in admixture of two or more.

The organic polyisocyanate is a compound containing two or more isocyanate groups in the molecule. Specifically, for example, toluene diisocyanates such as 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, 4,4′- Diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, diphenylmethane diisocyanates such as 2,2′-diphenylmethane diisocyanate, phenylene diisocyanates such as 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4,6-trimethylphenyl-1,3-diisocyanate, 2,4,6-triisopropylphenyl-1,3-diisocyanate, 1,4-naphthalene diisocyanate, Naphthalene diisocyanates such as 1,5-naphthalene diisocyanate, chlorophenylene-2,4-diisocyanate, 4,4'-diphenyl ether diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxydiphenyl Aromatic polyisocyanates such as -4,4'-diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,4,4 Aliphatic polyisocyanates such as 4-trimethyl-1,6-hexamethylene diisocyanate, decamethylene diisocyanate, lysine diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate Aroaliphatic polyisocyanates such as xylylene diisocyanates such as p-xylylene diisocyanate, 1,4-cyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. Isocyanates. Furthermore, organic polyisocyanates such as polymethylene polyphenyl polyisocyanate and crude toluene diisocyanate can also be used.
Also used are modified isocyanate compounds obtained by modifying these organic polyisocyanates and containing at least one uretdione bond, isocyanurate bond, allophanate bond, burette bond, uretonimine bond, carbodiimide bond, urethane bond, urea bond, etc. it can.
These can be used alone or in combination of two or more.
Of these, aromatic polyisocyanates are preferred.

In the synthesis of an isocyanate group-containing urethane prepolymer, metals such as zinc, tin, lead, zirconium, bismuth, cobalt, manganese, and iron, and organic materials such as octyl acid and naphthenic acid, such as tin octylate and zirconium octylate, are used. Organometallic chelate compounds such as salts with acids, dibutyltin diacetylacetonate, zirconium tetraacetylacetonate, titanium tetraacetylacetonate, EXCESTAR C-501 (manufactured by Asahi Glass Co., Ltd.), and organic metals such as dibutyltin dilaurate, dioctyltin dilaurate A known urethanization catalyst such as an organic metal compound such as a salt of an organic acid, an organic amine such as triethylenediamine, triethylamine, or tri-n-butylamine, or a salt thereof can be used. Of these, organometallic compounds and dibutyltin dilaurate are preferred.
Further, a known organic solvent can also be used.

  The isocyanate group content of the isocyanate group-containing urethane prepolymer is preferably 0.3 to 15.0 mass%, particularly preferably 0.5 to 5.0 mass%. When the isocyanate group content is less than 0.3% by mass, there are few crosslinking points in the prepolymer, so that sufficient adhesiveness cannot be obtained. When the isocyanate group content exceeds 15.0% by mass, the number of crosslinking points in the prepolymer increases and the rubber elasticity deteriorates, and the amount of carbon dioxide generated by the reaction with moisture increases and the cured product foams. It is not preferable in terms.

  The isocyanate group-containing urethane prepolymer is used as a one-component moisture-curing type by reaction curing with moisture (humidity) in the atmosphere at room temperature.

Examples of the finely divided silica in the present invention include natural silica obtained by finely pulverizing quartz, silica sand, and the like, and synthetic silica such as dry silica and wet silica. Of these, synthetic silica is preferable because of its high thixotropic effect.
Among synthetic silicas, dry silica is obtained by burning a silane-based gas such as silicon tetrachloride in an oxygen-hydrogen flame, and is also called fumed silica.
The wet silica is typically precipitated silica in which silica is precipitated in a solution by neutralizing sodium silicate with a mineral acid, and is also called white carbon.
The fine powdery silica has a BET specific surface area of 10 to 500 m ² / g , an average primary particle diameter of 1 to 1,000 nm, and an average agglomerated particle diameter of 0.01 to 50 μm, particularly a BET specific surface area. Colloidal silica having 50 to 500 m ² / g and an average primary particle diameter of 3 to 100 nm is preferable because of excellent thixotropic effect.
In addition, there are hydrophilic colloidal silica that does not treat silanol groups (—SiOH groups) on the surface of colloidal silica particles, and hydrophobic silica that is treated with trimethylsilane chloride, trimethylmethoxysilane, or the like. Is preferably a hydrophilic colloidal silica that does not treat silanol groups (—SiOH groups) on the particle surface because of its excellent thixotropic effect.
The amount of finely divided silica used is preferably 0.1 to 300 parts by mass, more preferably 1 to 100 parts by mass, and particularly preferably 1 to 50 parts by mass with respect to 100 parts by mass of the isocyanate group-containing urethane prepolymer. If the amount used is less than 0.1 parts by mass, the thixotropic effect is remarkably reduced, and if it exceeds 300 parts by mass, the viscosity increases and workability such as coating and extrusion deteriorates.

The thixotropy imparting aid in the present invention is used as an aid for strengthening and stabilizing thixotropy imparted by finely divided silica in a blended system of an isocyanate group-containing urethane prepolymer and finely divided silica. It is a compound which is obtained by reacting an organic isocyanate compound and a compound having a nitrogen atom bonded to a hydroxyl group, and substantially contains no isocyanate group or hydroxyl group.
Among these, in the molecule, it has at least one bond (atomic group) represented by the following general formula (1) or (2), further 2 or more, further 2 to 15, particularly 4 to 10, substantially A compound containing no isocyanate group or hydroxyl group is preferred.
These can be used alone or in combination of two or more.

Examples of the organic isocyanate compound include the same organic isocyanates used in the synthesis of the aforementioned isocyanate group-containing urethane prepolymer. Specific examples include organic monoisocyanates, organic polyisocyanates, and mixtures thereof. Organic polyisocyanates are preferable, and araliphatic polyisocyanates or aliphatic polyisocyanates are more preferable. In particular, aliphatic polyisocyanates are modified. A modified isocyanate compound containing a uretdione bond, an isocyanurate bond, an allophanate bond, a burette bond, a uretonimine bond, a carbodiimide bond, a urethane bond, a urea bond, and the like obtained by the above method is preferable. Of these modified isocyanate compounds, compounds having an isocyanurate bond or an allophanate bond are particularly preferred. Examples of general commercial products of modified isocyanate compounds containing allophanate groups include Coronate 2770 and Coronate 2785 manufactured by Nippon Polyurethane Industry, which are allophanate derivatives from hexamethylene diisocyanate and monools and polyols. Examples of the modified isocyanate compound containing an isocyanurate group include isocyanurate derivatives of isophorone diisocyanate such as Sumitomo Bayer Sumidur N3300, which is an isocyanurate derivative of hexamethylene diisocyanate, Nippon Polyurethane Industry Coronate HX, Coronate HK, etc. A certain Sumitomo Bayer-made death module Z4470 may be mentioned.
These can be used alone or in combination of two or more.

The compound having a nitrogen atom bonded to the hydroxyl group is preferably a compound having at least one group (atomic group) represented by the following general formula (3) or (4) in the molecule, specifically an oxime compound. Or a hydroxylamine compound can be used conveniently. These can be used alone or in combination of two or more. Specific examples include acetoaldoxime, acetone oxime, methyl ethyl ketone oxime, N, N-diethylhydroxylamine, and the like.

In the synthesis of the thixotropic agent (compound), the reaction equivalent ratio of isocyanate group to hydroxyl group is isocyanate group / hydroxyl group = 0.9 to 1.1 / 1.0, and further 1.0 / 1.0. Is preferred.
As a method of synthesizing the thixotropic agent (compound), the same method as in the synthesis of the isocyanate group-containing urethane prepolymer can be used, and the organic isocyanate compound and the hydroxyl group are bonded at room temperature or under heating. Obtained by reacting with a compound having a nitrogen atom.
When synthesizing the thixotropic agent (compound), a catalyst may not be used, but the same reaction catalyst as that used in the synthesis of the isocyanate group-containing urethane prepolymer can be used. Of these, organometallic compounds, dibutyltin dilaurate, and dibutyltin diacetylacetonate are preferred.
Furthermore, a known organic solvent inert with an isocyanate group can be used as a reaction solvent.
The molecular weight of the thixotropic agent (compound) is preferably 300 or more, more preferably 300 to 5,000, and particularly preferably 300 to 2,000. If the molecular weight is less than 300, the effect as a thixotropic agent is poor, which is not preferable.

In the present invention, the term “substantially does not contain an isocyanate group or a hydroxyl group” means that an isocyanate group or a hydroxyl group is selected by selecting a reaction equivalent ratio of the isocyanate group and the hydroxyl group when synthesizing the thixotropic agent. May remain in small amounts, but even if it is not contained, the effect as a thixotropic agent and the storage stability, adhesiveness, rubber elastic properties, etc. of the sealing material composition obtained by blending this It means that there is no adverse effect on various performances. Specifically, the isocyanate group or hydroxyl group content that does not adversely affect the thixotropic agent is preferably less than 0.05 mmol / g, more preferably 0 mmol / g.

  The reason why a compound containing substantially no isocyanate group or hydroxyl group obtained by reacting an organic isocyanate compound with a compound having a nitrogen atom bonded to a hydroxyl group is extremely effective as a thixotropic agent is as follows: Since the bond obtained by reacting with a compound having a nitrogen atom bonded to a hydroxyl group has a strong polarity and has good compatibility with the isocyanate group-containing urethane prepolymer (or dispersibility is extremely good), By forming dense and strong hydrogen bonds, even if a polar resin, solvent, amine catalyst, metal catalyst, or the like is present, these fine silica particles interact with each other and destroy the thixotropic structure. It is inferred to prevent this. This hydrogen bond is more easily formed by a thixotropic agent provided from an organic isocyanate compound having no steric hindrance in the vicinity of the isocyanate group.

  The amount of thixotropic imparting aid used is preferably 1 part by mass or more, more preferably 1 to 100 parts by mass, and particularly preferably 10 to 80 parts by mass with respect to 100 parts by mass of finely divided silica. If it is less than 1 part by mass, the effect of improving thixotropy is remarkably reduced, which is not preferable.

  Additives in the present invention include curing accelerators, weathering stabilizers, fillers, adhesion promoters, thixotropic agents other than finely divided silica, storage stability improvers (dehydrating agents), plasticizers, colorants, Examples include designability imparting agents and organic solvents.

The curing accelerating catalyst is a catalyst for accelerating the curing of the isocyanate group-containing urethane prepolymer. Specific examples include organometallic compounds, amines, etc., divalent organic tin compounds such as tin octylate and tin naphthenate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dimaleate, dibutyl Tetravalent organotin compounds such as tin distearate, dioctyltin dilaurate, dioctyltin diversate, dibutyltin oxide, dibutyltin bis (triethoxysilicate), reaction product of dibutyltin oxide and phthalate, dibutyltin diacetylacetonate, EXCESTAR C-501 manufactured by Asahi Glass Co., Ltd., zirconium tetrakis (acetylacetonate), titanium tetrakis (acetylacetonate), aluminum tris (acetylacetonate), 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, organic acid lead salts such as lead octylate, tetra-n-butyl Titanates such as titanate and tetrapropyl titanate, organic bismuth compounds such as bismuth octylate and bismuth versatate, triethylamine, tributylamine, triethylenediamine, hexamethylenetetramine, 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 the like salts such as these amines and carboxylic acids. Of these, organotin compounds and metal chelate compounds are preferred because of their high reaction rate and relatively low toxicity and volatility, and dibutyltin diacetylacetonate is particularly preferred.
It is preferable that the curing accelerating catalyst is blended in an amount of 0 to 10 parts by mass, particularly 0.01 to 2 parts by mass with respect to 100 parts by mass of the isocyanate group-containing urethane prepolymer, from the viewpoints of curing speed and physical properties of the cured product.

  The weathering stabilizer is used to prevent oxidation, photodegradation, and thermal degradation after curing of the isocyanate group-containing urethane prepolymer and further improve not only the weather resistance but also the heat resistance. Specific examples of the weather resistance stabilizer include an antioxidant, an ultraviolet absorber, and a photocurable compound.

Specific examples of the antioxidant include hindered amine and hindered phenol antioxidants. Examples of the hindered amine antioxidant include bis (1,2,2,6,6-pentamethyl-4 -Piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Examples include methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine. In addition to Sanyo LS-292, trade names manufactured by Sankyo Co., Ltd., trade names Adeka Stub series LA-52, LA-57, LA-62, LA-67, LA-77, LA- 82, LA-87 and other low molecular weight hindered amine antioxidants with a molecular weight of less than 1,000, also LA-63P, LA-68LD or Ciba Specialty Chemicals' product names CHIMASSORB series 119FL, 2020FDL, 944FD, 944LD And high molecular weight hindered amine antioxidants having a molecular weight of 1,000 or more.
As the hindered phenol-based antioxidant, 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-hydroxyphenylpropionamide)], benzenepropanoic acid 3, Examples include 5-bis (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester, 2,4-dimethyl-6- (1-methylpentadecyl) phenol, and the like.

  Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers such as 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (4,6-diphenyl-1, 3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol and other triazine-based UV absorbers, benzophenone-based UV absorbers such as octabenzone, 2,4-di-tert-butylphenyl-3 Benzoate-based ultraviolet absorbers such as 5-di-tert-butyl-4-hydroxybenzoate.

  Examples of the photocurable compound include a compound containing one or more groups that are reactively cured by light such as an acryloyl group or a methacryloyl group in the molecule. Specifically, a hydroxyl group-containing acrylate compound or an isocyanate group-containing urethane resin can be used. Urethane acrylate and urethane methacrylate reacted with a hydroxyl group-containing methacrylate compound, ester acrylate and ester methacrylate such as trimethylolpropane triacrylate and trimethylolpropane trimethacrylate, polyester acrylate and polyester methacrylate such as acrylate and methacrylate of polyethylene adipate polyol, polyether Polyether acrylate such as polyol acrylate or methacrylate, polyether methacrylate, or polysilica Examples thereof include vinyl acids and azide resins, and monomers and oligomers having a molecular weight of 10,000 or less, and further a molecular weight of 5,000 or less are preferable, and in particular, an average of two acryloyl groups and / or methacryloyl groups per molecule. What contains above is preferable.

  The weathering stabilizer is preferably blended in an amount of 0 to 30 parts by mass, particularly 0.1 to 10 parts by mass, with respect to 100 parts by mass of the isocyanate group-containing urethane prepolymer.

  Fillers, adhesion imparting agents, thixotropic imparting agents other than finely divided silica, storage stability improvers (dehydrating agents), plasticizers, colorants, designability imparting agents, etc. It can be used for improving thixotropic properties, improving storage stability, coloring, imparting design properties such as matting of the surface of a cured product and imparting unevenness (providing roughness).

  Fillers include mica, kaolin, zeolite, graphite, diatomaceous earth, white clay, clay, talc, slate powder, anhydrous silicic acid, aluminum powder, zinc powder, heavy calcium carbonate, light calcium carbonate, magnesium carbonate, alumina, calcium oxide , Inorganic powder fillers such as magnesium oxide, inorganic fillers such as fiber fillers such as glass fibers and carbon fibers, or fillers whose surfaces are treated with organic substances such as fatty acids, wood flour, walnut flour, Rice husk 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, melamine resin, etc. In addition to organic fillers such as curable resin or thermosetting resin powder, flame retardant imparting fillers such as magnesium hydroxide and aluminum hydroxide are also included, and those having a particle size of 0.01 to 1,000 μm Is preferred.

Examples of the adhesion imparting agent include a coupling agent, an epoxy resin, a phenol resin, an alkyd resin, and an alkyl titanate.
Examples of the coupling agent include various coupling agents such as silane, aluminum and zircoaluminate and / or partial hydrolysis condensates thereof. Of these, a silane coupling agent and / or a partially hydrolyzed condensate thereof is preferred because of its excellent adhesiveness.
As silane coupling agents, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane, ethyltrimethoxysilane, diethyldiethoxysilane, n-butyltrimethoxysilane, n-hexyltriethoxysilane , N-octyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, cyclohexylmethyldimethoxysilane and other hydrocarbon group-bonded alkoxysilanes, dimethyldiisopropenoxysilane, methyltriisopropenoxysilane and other hydrocarbon group-bonded Isopropenoxysilanes, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmeth Sisilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-glycidoxypropylmethyl Diisopropenoxysilane, 3-glycidoxypropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane , 3-acryloxypropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and other functional groups such as alkoxysilanes and isopropenoxysilanes having a molecular weight of 500 or less, preferably 400 or less. Compounds having a molecular weight 200 to 3,000 are exemplified in compound and / or one or more partially hydrolyzed condensate of the silane coupling agent.

  Thixotropic agents other than finely divided silica need not be essentially used in the present invention, but can be used in combination with the finely divided silica as required in practice. Examples of thixotropic agents other than finely divided silica include inorganic thixotropic agents such as calcium carbonate surface-treated with the above fatty acids, and organic thixotropic agents such as organic bentonites, modified polyester polyols, and fatty acid amides.

Examples of the storage stability improver include low molecular crosslinkable silyl group-containing compounds such as vinyltrimethoxysilane, calcium oxide, and p-toluenesulfonyl isocyanate that react with moisture present in the sealing material composition. .

  Plasticizers include non-aromatics such as phthalates such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate, butyl phthalyl butyl glycolate, dioctyl adipate, dioctyl sebacate, etc. Low molecular weight plasticizers having a molecular weight of less than 500, such as phosphoric acid esters such as group dibasic acid esters, tricresyl phosphate and tributyl phosphate, and halogenated aliphatic compounds such as chlorinated paraffins. Examples of molecular weight type plasticizers include polyester plasticizers such as polyesters from dicarboxylic acids and glycols, etherified or esterified derivatives of polyethylene glycol or polypropylene glycol, sucrose, etc. Polysaccharides such as saccharide-based polyethers obtained by addition polymerization of ethylene oxide or propylene oxide to saccharide polyhydric alcohols and further etherified or esterified, polystyrenes such as poly-α-methylstyrene, ) Acrylic acid ester-based copolymer. Among these, a high molecular weight type plasticizer having a molecular weight of 500 or more is preferable because it is difficult to migrate (bleed) to the surface of the cured product.

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

Designability-imparting agents can be used to aid in matting the surface of the cured product by blending it into the sealing material composition, or to give the appearance imitating natural rough rocks by matting the surface and providing irregularities. In order to exhibit the effect of imparting design properties, specifically, those that impart matte include various waxes such as beeswax, carnauba wax, montan wax, paraffin wax, stearamide, etc. Higher fatty acid amides, tetradecylamines, pentadecylamines, stearylamines and the like higher melting point amines having a melting point of 30 ° C. or higher, or ketimine compounds obtained by reacting and dehydrating these amines with carbonyl compounds such as acetone, methyl ethyl ketone, isobutyraldehyde, etc. And aldimine compounds.
Examples of the material that removes the gloss of the surface and imparts irregularities include granular materials and balloons, etc. The granular materials are the same as those mentioned as the filler, and large particles having a particle size of 50 μm or more are mentioned. It is done.
The balloon is a hollow material, like the shape is not only spherical, cubic, rectangular shape, there various like confetti-like, also obtained by slightly destroying the balloon to a degree that does not eliminate the unevenness imparting effect on sealant composition However, the spherical shape is preferred because of the good workability of the sealing material composition. Specifically, inorganic balloons such as glass balloons, shirasu balloons, silica balloons, ceramic balloons, organic balloons such as phenol resin balloons, urea resin balloons, polystyrene balloons, polyethylene balloons, saran balloons, or inorganic compounds and organic balloons Examples include a compound balloon in which compounds are mixed or laminated.
Also, those balloons coated or surface-treated can be used, inorganic balloons surface-treated with the silane coupling agent, etc., organic balloons coated with calcium carbonate, talc, titanium oxide, etc. There are also things.
Of these, from the viewpoint of the effect of imparting designability, granular materials and / or balloons are preferable, and granular inorganic fillers and / or inorganic balloons are more preferable, especially coarse heavy calcium carbonate and / or ceramics. A balloon is preferred.
The particle size of the granular material and / or balloon is preferably 50 μm or more, and more preferably 100 to 1,000 μm, from the viewpoint of the effect of providing designability.

  The total amount of filler, adhesiveness imparting agent, thixotropic imparting agent other than finely divided silica, storage stability improver (dehydrating agent), plasticizer, colorant and designability imparting agent is the isocyanate group-containing urethane prepolymer. 0 to 500 parts by mass, particularly 10 to 300 parts by mass are preferable with respect to 100 parts by mass.

Since the sealing material composition of the present invention has a low viscosity, it is not necessary to use an organic solvent, or even if it is used, only a very small amount is required, and environmentally hazardous substances are not released, so that safety is high.
Examples of the organic solvent include conventionally known organic solvents such as aliphatic solvents such as n-hexane, alicyclic solvents such as cyclohexane, aromatic solvents such as toluene and xylene, and the like. Anything that does not react to the above can be used. From the viewpoint of safety, the organic solvent is preferably used so that it is less than 10% by weight, more preferably less than 5% by weight, particularly less than 1% by weight, most preferably 0% by weight in the sealing material composition. Is not to.
In the present invention, each additive component can be used alone or in combination of two or more.

The sealing material composition of the present invention may be used as a one-pack type depending on the application, or as a two-pack type using the sealing material composition of the present invention as a main ingredient and water or an amine compound as a curing agent. However, it is preferable to use it as a one-component moisture-curing sealant composition because there is no trouble of mixing the main agent and the curing agent, and there is no inconvenience such as poor mixing and excellent workability.
In addition, as the material to which the sealing material composition of the present invention is applied, inorganic materials such as mortar and concrete, natural stone materials such as marble, siding such as ceramic siding and metal siding, ALC plates, tiles, etc. Good adhesive properties such as ceramic materials, sheet and plate materials made of various synthetic resins such as polyethylene and vinyl chloride, wood materials such as wood and plywood, and metal materials such as aluminum and galvanized steel Therefore, it is mentioned as a suitable thing. In particular, in that it can take advantage of the features of the present invention, in recent years use properties has increased, has the preferred use against the outer wall joints formed by siding or ALC plate.

Hereinafter, the present invention will be described in more detail with reference to examples.
Here Te smell and shows the one-moisture curable sealant sets Narubutsu, but not limited thereto.

[Synthesis of isocyanate group-containing urethane prepolymer]
Synthesis example 1
In a reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube and heating / cooling device, 457.6 g (OH) of polyoxypropylene diol (Exenol-3021 manufactured by Asahi Glass Co., Ltd., number average molecular weight 3,200) under a nitrogen stream Equivalent: 0.286), polyoxypropylene triol (MN-4000, number average molecular weight 4,000, Mitsui Chemicals), 291.7 g (OH equivalent: 0.219), and 44.7 g of toluene were charged and stirred. However, 4,5.4'-diphenylmethane diisocyanate (Millionate MT, manufactured by Nippon Polyurethane Industry Co., Ltd., molecular weight 250) 195.4 g (NCO equivalent: 1.56) (R value (NCO equivalent / OH equivalent) = 3.09) and dibutyltin dilaurate After adding 0.1 g, the mixture is heated and stirred at 70 to 80 ° C. for 2 hours, and the isocyanate group content is the theoretical value (4. The reaction was terminated at the time point when 9 wt%) or less, to produce an isocyanate group-containing polyoxypropylene urethane prepolymer.
This isocyanate group-containing polyoxypropylene-based urethane prepolymer was a viscous liquid transparent at room temperature with an isocyanate group content of 4.38% by mass measured by titration and a viscosity of 8,500 mPa · s / 25 ° C. This urethane prepolymer is referred to as U-1.

[Synthesis of thixotropic agent]
Synthesis example 2
217.6 g (NCO equivalent: 1) of allophanate group-containing modified polyisocyanate compound (Coronate-2785 manufactured by Nippon Polyurethane Industry Co., Ltd.) was added to the same reaction vessel as in Synthesis Example 1, and then 76.2 g of ethyl acetate was added. While cooling and stirring, 87.0 g of methyl ethyl ketone oxime (OH equivalent: 1) was further added, and the reaction was terminated when the isocyanate group content was less than the theoretical value (0% by mass). Manufactured.
The obtained reaction product was a liquid transparent at room temperature with an isocyanate group content of 0% by mass (0 mmol / g) measured by titration. This reaction product has 4.9 groups (atomic groups) represented by the general formula (1) in calculation. This reaction product is referred to as thixotropic agent A-1.

Synthesis example 3
217.6 g (NCO equivalent: 1) of allophanate group-containing modified polyisocyanate compound (Coronate-2785 manufactured by Nippon Polyurethane Industry Co., Ltd.) was added to the same reaction vessel as in Synthesis Example 1, and then 76.2 g of ethyl acetate was added. While cooling and stirring the mixture, 89.1 g (OH equivalent: 1) of N, N-diethylhydroxyamine was further added, and the reaction was terminated when the isocyanate group content was less than the theoretical value (0% by mass). The reaction product was prepared.
The obtained reaction product was a liquid transparent at room temperature with an isocyanate group content of 0% by mass (0 mmol / g) measured by titration. This reaction product has 4.9 groups (atomic groups) represented by the general formula (2) in calculation. This reaction product is referred to as thixotropic agent A-2.

Example 1
In a kneading vessel equipped with a heating and cooling device and a nitrogen seal tube under a nitrogen stream, 889.0 g of the isocyanate group-containing polyoxypropylene-based urethane prepolymer U-1 obtained in Synthesis Example 1 and a dryer at 90 to 100 ° C. in advance. After being charged with 100.0 g of heavy calcium carbonate having a moisture content of 0.05% by mass or less and 2.7 g of paratoluenesulfonyl isocyanate, the mixture was stirred and kneaded at 60 ° C. or lower for 1 hour until the contents became uniform. Then, 67.6 g of hydrophilic colloidal silica (Leosil QS-102 manufactured by Tokuyama Corporation) was charged, and further stirred and kneaded at 60 ° C. or lower for 1 hour until the contents became uniform. Next, 16.0 g of the thixotropic imparting aid O-1 obtained in Synthesis Example 2 and 2.0 g of dibutyltin diacetylacetonate (Neostan U-220 manufactured by Nitto Kasei Co., Ltd.) were sequentially charged until the contents became uniform. The mixture was stirred and kneaded at 60 ° C. or lower. Next, the mixture was degassed under reduced pressure at 30 to 100 hPa, filled in a container, and sealed to prepare a paste-like one-component moisture-curable sealant composition.

Example 2
In the same manner as in Example 1, except that 16.0 g of thixotropic agent A-2 obtained in Synthesis Example 3 was used instead of 16.0 g of thixotropic agent A-1 Type moisture curable sealant composition was prepared.

Comparative Example 1
In Example 1, a paste-like one-component moisture-curable sealant composition was prepared in the same manner except that the thixotropic agent A-1 was not used.

[Sealant performance test]
The following tests were conducted using each of the one-component moisture-curable sealant compositions prepared in Examples 1 and 2 and Comparative Example 1.
(1) Slump JIS A1439: (1997, revised 2002) “Testing method of sealing material for building” 4.1 Slump (vertical) immediately after production was measured at a test temperature of 23 ° C. by a slump test.
Separately from this, the obtained one-pack type moisture curable sealant composition was accelerated and stored at 50 ° C. for 5 days and then allowed to stand at 23 ° C. for 1 day, and the slump was measured in the same manner as described above.
(2) Hardness The sealant composition was applied to a slate plate so as to form a sheet having a thickness of about 10 mm, and cured and cured for 14 days at 23 ° C. and 50% relative humidity. K 6253 (1997, confirmation 2001) “Method of testing hardness of vulcanized rubber and thermoplastic rubber”; By the durometer hardness test, the hardness of the cured product was measured at a test temperature of 23 ° C. using a spring type hardness tester (durometer) type A.
The thing whose hardness is 30 or more was evaluated as (circle).
(3) Elongation The sealing material composition is applied onto a release paper so as to form a sheet having a thickness of about 2 mm, cured and cured at 23 ° C. and 50% relative humidity for 14 days, and then the release paper is peeled off. When the cured product was cut at a test temperature of 23 ° C. using a test piece as a test piece, and a test piece punched into a No. 3 dumbbell shape according to JIS K 6251 (1993, Confirmation 1999) “Vulcanized Rubber Physical Test Method” Elongation was measured.
Those having an elongation of 200% or more were evaluated as ◯.
Table 1 summarizes the raw material composition and performance of the one-component moisture-curable sealant composition.

Sealant composition of the present invention by utilizing its features, can be suitably used as a building, civil engineering, which Sea ring material for automotive. Furthermore, building exterior wall, as a Shirin ingredients of civil engineering, it is suited particularly high performance waterproof Shirin ingredients for building exterior walls.

Claims (4)

A sealing material composition comprising an isocyanate group-containing urethane prepolymer, a fine powdery silica having a BET specific surface area of 10 to 500 m ² / g, and a thixotropic agent,
The sealing of the thixotropic auxiliaries, obtained by reacting a compound having a nitrogen atom bonded to an organic isocyanate compound and a hydroxyl group, substantially be a compound containing no isocyanate group or hydroxyl group, and wherein Material composition. The sealing material composition according to claim 1, wherein the compound having a nitrogen atom bonded to the hydroxyl group is an oxime compound or a hydroxylamine compound. The sealing material composition according to claim 1 or 2, wherein the finely divided silica is hydrophilic colloidal silica that does not treat a silanol group on the surface . Furthermore, the sealing material composition as described in any one of Claims 1-3 formed by mix | blending an additive.