JP6856244B2 - Sealant composition - Google Patents

Description

The present invention relates to a sealing material composition capable of suppressing deterioration for a long period of time even in an environment of high temperature and strong acidity.

Conventionally, waste liquid discharged from palm oil manufacturing plants, which are the main industries of Indonesia and Malaysia, is treated in an outdoor lagoon (anaerobic treatment pond), and most of its organic content is released into the atmosphere in the form of methane. However, there were problems with atmospheric emission of methane, which is a greenhouse gas, and water pollution. In recent years, as a method of treating palm waste liquid (POME: Palm Oil Mill Effect) discharged in the process of manufacturing palm oil, POME is methane-fermented in a closed tank, and the methane and carbon dioxide generated by this are mainly contained. It is made to recover the biogas.

Therefore, in order to improve the recovery efficiency of biogas, the amount of low-temperature raw water to be treated that is cooled by the cooling means is supplied to the methane fermentation tank through the first supply path, and the amount of low-temperature raw water to be treated and cooling. High-temperature methane fermentation in the methane fermentation tank by adjusting the supply amount of high-temperature treatment target raw water that is not cooled by means and is supplied to the methane fermentation tank through the second supply path. A methane fermentation treatment apparatus that adjusts to a predetermined temperature suitable for the above has been proposed (Patent Document 1).

In such equipment, steel plates are often used as storage tanks for raw water to be treated and methane fermentation tanks, and there are welding type and bolt type assembling methods for steel plates, but ease of construction, cost, etc. Therefore, bolt-type assembly is desired. However, when a storage tank or fermenter is assembled with a bolt type, it is necessary to place a sealing material at the connection part for the purpose of preventing liquid leakage and corrosion of the steel plate part that cannot be coated. Stores highly acidic liquids that are high in temperature and contain a large amount of volatile fatty acids and lower fatty acids. In such an environment, the sealant deteriorates several months after being placed, and there is a problem that liquid leakage from a storage tank or a fermenter or corrosion of an uncoated steel sheet occurs.

In addition, there is a sabo dam as one of the equipment to prevent sediment-related disasters, but granite is used for the formwork for the purpose of landscape and acid resistance for the retaining wall of the sabo dam. Joint material is placed on the back of the formwork, and concrete is poured into the formwork. When the sabo dam is installed near a hot spring area with high acidity, the retaining wall is exposed to the highly acidic river water peculiar to hot spring water for a long period of time. There was a problem that it deteriorated in a few years.

In addition, the concrete storage tank of the sewage treatment facility is provided with an anticorrosion sheet and anticorrosion paint for the purpose of anticorrosion and the like. Sealants are placed at the ends and joints around pipes, but the quality standards are set by the Japan Sewage Works Agency, and their performance is required to have high acid resistance.

Japanese Patent No. 6049937

The present invention has been made to solve such a problem, and provides a sealing material composition capable of obtaining a sealing material capable of preventing deterioration for a long period of time even in an environment of high temperature and strong acidity. The purpose is to do.

Aspects of the present invention include (A) a room temperature curable resin, (B) a compound that reacts with water to generate an active hydrogen-containing functional group, (C) a curing accelerator, and (D) a rocking modifier (D). However, it is a sealing material composition containing (excluding surface-treated calcium carbonate) and (E) vinyl chloride resin.

The "room temperature" of a room temperature curable resin means 25 ° C., and the room temperature curable resin means a resin having curability in an environment of at least 25 ° C.

In the aspect of the present invention, the room temperature curable resin (A) is a sealing material composition containing an isocyanate group-containing urethane prepolymer.

In the aspect of the present invention, the compound (B) that reacts with water to generate an active hydrogen-containing functional group is a sealing material composition containing an oxazolidine compound.

In the aspect of the present invention, the curing accelerator (C) is a sealing material composition containing an iron chelate compound.

In the aspect of the present invention, the iron chelate compound is a sealant composition containing iron acetylacetonate.

In the aspect of the present invention, the (D) rocking denaturing agent is a sealing material composition containing silica and / or a polyurea compound.

According to the aspect of the present invention, (A) a room temperature curable resin, (B) a compound that reacts with water to generate an active hydrogen-containing functional group, (C) a curing accelerator, and (D) imparting shake modification. By containing the agent (excluding surface-treated calcium carbonate) and (E) vinyl chloride resin, swelling, softening, and tensile strength over a long period of time even in a high temperature and highly acidic environment. , A sealing material capable of preventing deterioration of adhesiveness can be obtained. Therefore, it is possible to prevent leakage of the contents from the connection portion of the container such as the storage tank and corrosion of the material constituting the container such as the storage tank. Further, according to the aspect of the present invention, it is possible to prevent the occurrence of sagging during coating, so that the coating property is good.

According to the aspect of the present invention, (A) the room temperature curable resin contains an isocyanate group-containing urethane prepolymer, and (B) the compound that reacts with water to generate an active hydrogen-containing functional group contains an oxazolidine compound. It is possible to surely prevent foaming from occurring in the cured product of the sealant composition, and as a result, it is possible to surely prevent a decrease in adhesiveness.

According to the aspect of the present invention, since the curing accelerator (C) contains an iron chelate compound, softening can be reliably prevented for a long period of time even in an environment of high temperature and strong acidity.

According to the aspect of the present invention, since the (D) rocking denaturing agent contains silica and / or a polyurea compound, the occurrence of sagging can be reliably prevented, so that excellent coatability can be obtained.

Next, the details of the sealant composition of the present invention will be described. The sealant composition of the present invention comprises (A) a room temperature curable resin, (B) a compound that reacts with water to generate an active hydrogen-containing functional group, (C) a curing accelerator, and (D) shake modification. It contains an imparting agent (excluding surface-treated calcium carbonate) and (E) vinyl chloride resin.

(A) Room temperature curable resin (A) Room temperature curable resin is a resin that is cured by atmospheric moisture (moisture), oxygen, etc. at least at room temperature (25 ° C.), and is, for example, an isocyanate group-containing urethane prepolymer. Examples thereof include crosslinkable silyl group-containing organic polymers and polysulfide resins. (A) The sealant composition (one-component curable composition) containing a room temperature curable resin can be used as a moisture-curable type or an oxygen-curable type, but has good workability such as construction work and curability. The moisture-curable type is preferable because it is excellent in rubber elastic properties after curing and durability such as water resistance and weather resistance. (A) The room temperature curable resin is a curing component.

(A-1) Isocyanate Group-Containing Urethane Prepolymer (A-1) Isocyanate Group-Containing Urethane Prepolymer is composed of (a) an organic isocyanate compound, (b) an active hydrogen group-containing compound, and (a) an organic isocyanate compound. It is a compound obtained by blending the number of moles of isocyanate groups in a molar ratio that is excessive with respect to the total number of moles of active hydrogen groups of (b) the active hydrogen group-containing compound and reacting them.

The content of the isocyanate group of the isocyanate group-containing urethane prepolymer is not particularly limited, but for example, the lower limit thereof is preferably 1.2% by mass, more preferably 1.4% by mass, from the viewpoint of storage stability. 5.5% by mass is particularly preferable. On the other hand, the upper limit of the isocyanate group content of the isocyanate group-containing urethane prepolymer is preferably 2.2% by mass, more preferably 2.1% by mass, from the viewpoint of preventing foaming and improving adhesiveness. 0% by mass is particularly preferable.

The number of moles of the isocyanate group of the organic isocyanate compound with respect to 1.0 mol of the active hydrogen group of the active hydrogen group-containing compound is not particularly limited as long as the number of moles of the isocyanate group is excessive. From the viewpoint of storage stability, 1.9 mol is preferable, 2.0 mol is more preferable, and 2.1 mol is particularly preferable. On the other hand, the upper limit is preferably 2.6 mol, particularly preferably 2.5 mol, from the viewpoint of preventing foaming and improving adhesiveness.

(A) Organic Isocyanate Compound (a) The organic isocyanate compound is not particularly limited, and examples thereof include organic polyisocyanate, and may be used as needed for modification of an isocyanate group-containing urethane prepolymer. , Organic monoisocyanate. Examples of the organic polyisocyanate include aromatic polyisocyanates in which an isocyanate group is bonded to an aromatic hydrocarbon, and aliphatic polyisocyanates in which an isocyanate group is bonded to an aliphatic hydrocarbon.

Examples of aromatic polyisocyanis include diphenylmethane diisocyanates (MDIs) such as 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate; and toluene diisocyanates such as 2,4-toluene diisocyanate and 2,6-toluene diisocyanate. (TDIs); Examples thereof include phenylene diisocyanate, diphenyl diisocyanate, naphthalenede diisocyanate, and diphenyl ether diisocyanate.

Examples of the aliphatic polyisocyanate include aromatic aliphatic polyisocyanates such as xylylene diisocyanate; aliphatic polyisocyanates such as propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and pentamethylene diisocyanate; cyclohexane diisocyanate, methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate. Such as alicyclic polyisocyanate and the like.

In addition, carbodiimide-modified products, biuret-modified products, allophanate-modified products, dimers, trimers, and polymethylene polyphenyl polyisocyanates (crude MDI or polypeptide MDI) of the above-mentioned polyisocyanates can also be mentioned. These may be used alone or in combination of two or more. Of these, alicyclic polyisocyanates are preferable, and isophorone diisocyanates are particularly preferable, from the viewpoint of preventing yellowing after curing.

The organic monoisocyanate for modifying the isocyanate group-containing urethane prepolymer is not particularly limited, but is, for example, an aliphatic monoisocyanate such as n-butyl monoisocyanate, n-hexyl monoisocyanate, or n-octadecyl monoisocyanate. Can be mentioned. These may be used alone or in combination of two or more.

(B) Active hydrogen group-containing compound (b) The active hydrogen group-containing compound includes a high molecular weight or low molecular weight polyol, an amino alcohol, a polyamine, a compound having at least one active hydrogen group and an ethylenically unsaturated group, and the like. Can be mentioned.

Examples of the polymer polyol include polyester-based polyols, polycarbonate polyols, polyoxyalkylene-based polyols, hydrocarbon-based polyols, poly (meth) acrylate-based polyols, animal and plant-based polyols, and copolyols thereof. In the present invention, "(meth) acrylate" means "acrylate or methacrylate".

The high molecular weight polyol and high molecular weight monool mean a polyol and monool having a number average molecular weight of 1,000 or more in terms of polystyrene by gel permeation chromatography (GPC), respectively, and are a low molecular weight polyol and a low molecular weight molecule. The monool and the low molecular weight amino alcohol mean a polyol, a monool, and an amino alcohol having a number average molecular weight of less than 1,000 in terms of polystyrene by gel permeation chromatography (GPC), respectively.

When the number average molecular weight of the polymer polyol is 1,000 or more, more excellent rubber elasticity can be obtained after curing. The lower limit of the number average molecular weight of the polymer polyol is not particularly limited, but is preferably 1,500 and particularly preferably 2,000 from the viewpoint of further improving the rubber elasticity and obtaining excellent adhesiveness. On the other hand, the upper limit thereof is not particularly limited, but is preferably 100,000 from the viewpoint of preventing an increase in the viscosity of the isocyanate group-containing urethane prepolymer (A) and obtaining excellent coatability, preferably 30,000. Is more preferable, and 20,000 is particularly preferable.

Examples of the polyester-based polyol include succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid and naphthalenedicarboxylic acid. Polycarboxylic acids such as trimellitic acids; alkyl ester compounds such as methyl esters and ethyl esters of these polycarboxylic acids; one or more such as acid anhydrides of these polycarboxylic acids, ethylene glycol, 1,2-propanediol, 1,3-Propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5- Pentandiol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, ethylene oxide or propylene oxide adduct of bisphenol A, trimethylol Low molecular weight polyols such as propane, glycerin and pentaerythritol; low molecular weight polyamines such as butylenediol, hexamethylenediamine, xylylenediol and isophoronediamine (polyamines having a polystyrene-equivalent number average molecular weight of less than 1,000 by GPC); monoethanol Examples thereof include polyester polyols and polyester amide polyols obtained by dehydration condensation reaction with one or more kinds of low molecular weight amino alcohols such as amine and diethanolamine. Examples thereof include lactone-based polyester polyols obtained by ring-opening polymerization of cyclic ester (lactone) monomers such as ε-caprolactone and γ-valerolactone, using low-molecular-weight polyols and low-molecular-weight amino alcohols as initiators.

Examples of the polycarbonate polyol include a dehydrochloric acid reaction between the low molecular weight polyol used for the synthesis of the polyester polyol and phosgene, or a transesterification reaction between the low molecular weight polyol and diethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate and the like. Examples include what can be obtained.

Examples of the polyoxyalkylene-based polyol include low-molecular-weight polyols, low-molecular-weight amino alcohols, and polycarboxylic acids used in the synthesis of the above-mentioned polyester polyols, as well as low-molecular-weight sugar-based low molecules such as sorbitol, mannitol, sucrose, and glucose. (GPC-equivalent number average molecular weight of polystyrene is less than 1,000) Low-molecular-weight alcohols, bisphenol A, bisphenol F, etc. (GPC-equivalent number average molecular weight of polystyrene is less than 1,000) One or more polyvalent phenols As an initiator, one or more cyclic ether compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran are subjected to ring-opening addition polymerization or copolymerization (hereinafter, "polymerization or copolymerization" may be referred to as (co) polymerization). Polyoxyethylene-based polyols, polyoxypropylene-based polyols, polyoxybutylene-based polyols, polyoxytetramethylene-based polyols, poly- (oxyethylene)-(oxypropylene) -random or block copolymer-based polyols, etc. Be done. Further, examples of the polyoxyalkylene-based polyol include the above-mentioned polyester polyol, a polyester ether polyol using a polycarbonate polyol as an initiator, a polycarbonate ether polyol, and the like. Further, for example, a polyol obtained by reacting the above low molecular weight polyol with an organic isocyanate with an excess hydroxyl group with an isocyanate group can be mentioned.

The number of alcoholic hydroxyl groups in the polyoxyalkylene-based polyol is not particularly limited, but is preferably more than 2 on average per molecule, more preferably more than 2 to 4 on average per molecule, and more than 2 on average per molecule. Three are more preferred. Of these, polyoxyalkylene triol is particularly preferable from the viewpoint of excellent adhesiveness after curing and rubber elasticity.

Examples of the catalyst used in the preparation of the polyoxyalkylene-based polyol include cesium alkoxides such as cesium hydride, cesium methoxydo and cesium ethoxide, cesium-based compounds such as cesium hydroxide, diethyl zinc, iron chloride, and metallic porphyrin. Examples thereof include a phosphazenium compound, a complex metal cyanation complex such as a glyme complex of zinc hexacyanocobaltate and a diglyme complex.

The total degree of unsaturation of the polyoxyalkylene-based polyol is not particularly limited, but is preferably 0.1 meq / g or less, more preferably 0.07 meq / g or less, and particularly preferably 0.04 meq / g or less. The molecular weight distribution of the high molecular weight polyol [ratio of polystyrene-equivalent weight average molecular weight (Mw) to number average molecular weight (Mn) by GPC = Mw / Mn] is not particularly limited, but the viscosity of the isocyanate group-containing urethane prepolymer. 1.0 to 1.6 is preferable, and 1.0 to 1.3 is particularly preferable, from the viewpoint of reducing the amount of rubber and further improving the rubber elasticity after curing.

If necessary, for modification of the (A-1) isocyanate group-containing urethane prepolymer, a low-molecular-weight monoalcohol such as methyl alcohol, ethyl alcohol, or propyl alcohol is used as an initiator, and a cyclic ether such as the above-mentioned propylene oxide is used as an initiator. Polyoxyalkylene-based monools such as polyoxypropylene-based monools obtained by ring-opening addition (co) polymerization of the compound may be used.

The "system" such as the above-mentioned polyoxyalkylene-based polyol and polyoxyalkylene-based monool means that 50% by mass or more of the portion of the molecule excluding the hydroxyl group is composed of polyoxyalkylene. Means. Therefore, the balance may be modified with other structures such as ester, urethane, polycarbonate, polyamide, poly (meth) acrylate, and polyolefin. The portion composed of polyoxyalkylene is not particularly limited as long as it is 50% by mass or more, but 80% by mass or more is preferable, 90% by mass or more is more preferable, and 95% by mass or more is particularly preferable.

Examples of the hydrocarbon-based polyol include polyolefin polyols such as polybutadiene polyols and polyisoprene polyols; polyalkylene polyols such as hydrogenated polybutadiene polyols and hydrogenated polyisoprene polyols; and halogenated poly such as chlorinated polypropylene polyols and chlorinated polyethylene polyols. Examples thereof include alkylene polyols.

The poly (meth) acrylate-based polyol includes, for example, a hydroxyl group-containing (meth) acrylic monomer such as hydroxyethyl (meth) acrylate and, if necessary, another (meth) acrylic acid alkyl ester monomer. Examples include polymerized ones. The poly (meth) acrylic polyol contains an ethylenically unsaturated compound containing at least a hydroxyl group-containing (meth) acrylic monomer in the presence or absence of a polymerization initiator, and in the presence or absence of a solvent. A product obtained by a high-temperature continuous polymerization reaction at a temperature of 150 to 350 ° C., more preferably 210 to 250 ° C. by a known radical polymerization method such as a batch method or continuous polymerization has a narrow molecular weight distribution of the reaction product and is low. It is preferable because it has a viscosity.

The poly (meth) acrylate-based polyol may be obtained by polymerizing a hydroxyl group-containing (meth) acrylate-based monomer alone, or may be obtained by copolymerizing two or more kinds of the hydroxyl group-containing (meth) acrylate-based monomer, and may be obtained by copolymerizing two or more kinds thereof. ) An acrylate-based monomer (one or more) may be obtained by copolymerizing an ethylenically unsaturated compound other than the hydroxyl group-containing (meth) acrylate-based monomer. Of these, one or 2 of the hydroxyl group-containing (meth) acrylate-based monomers is easy to adjust the hydroxyl content of the poly (meth) acrylate-based polyol and select the physical properties of the cured resin. It is preferably obtained by copolymerizing one or more kinds of ethylenically unsaturated compounds other than the seeds and the hydroxyl group-containing (meth) acrylate-based monomer, and the hydroxyl group-containing (meth) having 9 or less carbon atoms. One or more acrylate-based monomers and one or more hydroxyl group-containing (meth) acrylate-based monomers having 10 or more carbon atoms in total of 50% by mass or more and hydroxyl group-containing (meth) ) A hydroxyl group-containing (meth) acrylate-based monomer having 9 or less carbon atoms, more preferably obtained by copolymerizing one or more ethylenically unsaturated compounds other than the acrylate-based monomer. 1 or 2 or more of the above and 1 or 2 or more of the hydroxyl group-containing (meth) acrylate-based monomers having 10 or more carbon atoms in total of 70% by mass or more, and a hydroxyl group-containing (meth) acrylate-based single amount. It is particularly preferable to obtain one obtained by copolymerizing with one or more kinds of ethylenically unsaturated compounds other than the body.

At the time of the above copolymerization, one or more hydroxyl group-containing (meth) acrylate-based monomers are used so that the average number of hydroxyl groups per molecule of the poly (meth) acrylate-based polyol is 1.0 to 10. It is preferable to use it in the case of 1.2 to 3, and it is particularly preferable to use it in an amount of 1.2 to 3. When the average number of hydroxyl groups exceeds 10, the physical properties after curing tend to be hard and the rubber-like elasticity tends to decrease. The polystyrene-equivalent number average molecular weight of the poly (meth) acrylate-based polyol by gel permeation chromatography (GPC) is preferably 1,000 to 30,000, particularly preferably 1,000 to 15,000. The Tg of the poly (meth) acrylate-based polyol is preferably 0 ° C. or lower, more preferably −70 to −20 ° C., and particularly preferably −70 to −30 ° C. The viscosity of the poly (meth) acrylate-based polyol at 25 ° C. is preferably 100,000 mPa · s or less, and particularly preferably 50,000 mPa · s or less. If the number average molecular weight is 30,000 and the viscosity at Tg at 0 ° C. and 25 ° C. exceeds 100,000 mPa · s, the workability at the time of construction deteriorates.

Examples of animal and plant-based polyols include castor oil-based diols.

Examples of the chain extender include the low-molecular-weight polyol and low-molecular-weight amino alcohol used for the synthesis of the polyester-based polyol described above, and the polyoxyalkylene-based polyol described above having a number average molecular weight of less than 1,000. Can be mentioned.

The above-mentioned polymer polyols may be used alone or in combination of two or more. Among the above-mentioned polymer polyols, polyoxyalkylene-based polyols are preferable from the viewpoint of rubber elasticity and adhesiveness, of which polyoxypropylene-based polyols are more preferable, and polyoxypropylene-based triols are particularly preferable.

Examples of the low molecular weight polyol include low molecular weight polyhydric alcohols having a number average molecular weight of less than 1,000, which are mentioned as raw materials for producing the polyester polyol.

Examples of the amino alcohol include monoethanolamine, diethanolamine, N-methyldiethanolamine, N-methyldipropanolamine, N-phenyldiethanolamine and the like.

Examples of the polyamine include high molecular weight polyamines such as polyoxyalkylene polyamines having a number average molecular weight of 1,000 or more and having an amino group at the end of the polyoxyalkylene-based polyol, such as terminal diaminoization of polypropylene glycol. Further, examples of the polyamine include low molecular weight polyamines having a number average molecular weight of less than 500, such as ethylenediamine, hexamethylenediamine, isophoronediamine, diaminophenylmethane, and diethylenetriamine.

Examples of the compound having at least one active hydrogen group and an ethylenically unsaturated group include, for example, at least one active hydrogen group that reacts with the isocyanate group of the isocyanate group-containing urethane prepolymer, and the photocurable ethylenically non-saturating group. Examples thereof include compounds having at least one saturated group.

Examples of the active hydrogen group include a hydroxyl group, a primary amino group, a secondary amino group, a carboxyl group and a mercapto group, and examples of the ethylenically unsaturated group include a vinyl group, a vinylene group and a cinnamoyl group. , Acryloyl group, methacryloyl group and the like. Of these, a hydroxyl group is preferable as the active hydrogen group because it easily reacts with the isocyanate group of the isocyanate group-containing urethane prepolymer and the increase in viscosity is relatively small, and it takes a relatively short time by being exposed to light. Acryloyl group and methacryloyl group are preferable as the photocurable ethylenically unsaturated group from the viewpoint of forming a film having excellent weather resistance by the polymerization reaction. Compounds having at least one hydroxyl group as an active hydrogen group and at least one acryloyl group and / or methacryloyl group as a photocurable ethylenically unsaturated group are, for example, "Aronix" series manufactured by Toa Synthetic Co., Ltd. Examples include the "KAYARAD" series manufactured by Nippon Kayakusha and the "epoxy ester" series manufactured by Kyoeisha Chemical Co., Ltd.

By using a compound having at least one active hydrogen group and a photocurable ethylenically unsaturated group as a part of the polyol component constituting the isocyanate group-containing urethane prepolymer, and combining it with the high molecular weight polyol, The weather resistance of the isocyanate group-containing urethane prepolymer can be improved, and the isocyanate group-containing urethane prepolymer is further mixed with (B) a compound that reacts with water to generate an active hydrogen-containing functional group, which will be described later. When a mold-curable composition is used, it can be quickly cured by preventing foaming without deteriorating workability, and the cured product can have excellent rubber properties.

The content of the compound having at least one active hydrogen group and a photocurable ethylenically unsaturated group is not particularly limited, but from the viewpoint of imparting excellent weather resistance and rubber physical characteristics to the sealant composition, (b). ) The active hydrogen group-containing compound preferably contains 1.0 to 7.0% by mass.

All of the above-mentioned active hydrogen group-containing compounds may be used alone or in combination of two or more.

(A-2) Crosslinkable Cyril Group-Containing Organic Polymer In the crosslinkable silyl group-containing organic polymer, the introduced crosslinkable silyl group hydrolyzes with moisture such as moisture at room temperature, and the silanol group generated is condensed. Then, by cross-linking and curing, it can be used as a curing component of the sealing material composition. Examples of the organic polymer include (meth) acrylic polymers having a main chain; polyoxyalkylene polymers; aliphatic hydrocarbon polymers such as polyisobutylene, polyisobutylene, and polybutadiene; polyester polymers; these. Examples include copolymers or mixtures.

The number average molecular weight of the crosslinkable silyl group-containing organic polymer is not particularly limited, but is preferably 1,000 or more, for example, the viscosity of the sealing material composition is lowered, the coatability is improved, and the stress after curing is improved. From the viewpoint of improving rubber elastic physical properties such as elongation, those having a narrow molecular weight distribution of 6,000 to 30,000 are particularly preferable. The content of the crosslinkable silyl group is not particularly limited, but for example, from the viewpoint of curability of the sealing material composition and physical properties after curing, it is preferable that 0.2 or more are contained in one molecule. It is particularly preferable that 0.4 to 5.0 pieces are contained.

（式中、Ｒは、炭化水素基であり、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基又は炭素数７〜２０のアラルキル基が好ましく、メチル基が特に好ましい。Ｒが複数の場合には、同じ基であっても異なった基であってもよい。Ｘで示される反応性基は、水素原子、水酸基、アルコキシ基、アシルオキシ基、ケトキシメート基、アミド基、酸アミド基、メルカプト基、アルケニルオキシ基及びアミノオキシ基からなる群から選択される加水分解性の基であり、Ｘが複数の場合には、Ｘは同じ基であっても異なった基であってもよい。このうち、Ｘはアルコキシ基が好ましく、メトキシ基又はエトキシ基が特に好ましい。ａは０、１又は２の整数であり、０又は１が好ましい。）で示される化学構造が好ましい。 The chemical structure of the crosslinkable silyl group has the following general formula from the viewpoint of being easy to crosslink and easy to manufacture.

(In the formula, R is a hydrocarbon group, preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and a methyl group is particularly preferable. In the case of a plurality of groups, they may be the same group or different groups. The reactive group represented by X is a hydrogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a ketoximate group, an amide group or an acid amide group. , A hydrolyzable group selected from the group consisting of a mercapto group, an alkenyloxy group and an aminooxy group, and when there are a plurality of Xs, Xs may be the same group or different groups. Of these, X is preferably an alkoxy group, particularly preferably a methoxy group or an ethoxy group. A is an integer of 0, 1 or 2, and 0 or 1 is preferable.)

As a method for introducing a crosslinkable silyl group into the main chain of an organic polymer, for example, (1) a polyoxyalkylene-based polymer having a functional group such as a hydroxyl group at the terminal or a (meth) acrylic-based polymer has this functional group. An organic compound having an active group and an unsaturated group (for example, allyl isocyanate) which is reactive with respect to the above is reacted, and then a hydrosilane having a hydrolyzable group is allowed to act on the introduced unsaturated group to hydrosilylate. Method, (2) Functional groups and cross-links that are reactive with this functional group to polymers such as polyoxyalkylene-based and (meth) acrylic-based that have functional groups such as hydroxyl groups, epoxy groups and isocyanate groups at the ends. Method of reacting a compound having a sex silyl group (Examples of the compound having a functional group showing reactivity and a crosslinkable silyl group include amino group-containing silanes, mercapto group-containing silanes, epoxy group-containing silanes, and polymerizable silanes. Examples include unsaturated group-containing silanes and isocyanate group-containing silanes), (3) Compounds having a polymerizable unsaturated bond and a crosslinkable silyl group (for example, CH ₂ = CHSi (OCH ₃ ) ₃ or CH ₂ = A method of copolymerizing CHCOO (CH ₂ ) ₂ Si (OCH ₃ ) ₃ ) with a (meth) acrylic acid alkyl ester monomer, (4) a compound having a polymerizable unsaturated bond and a functional group (for example, hydroxyethyl). (Meta) acrylate or (meth) allyl acrylate, etc.) is copolymerized with (meth) acrylate alkyl ester monomer, etc., and the copolymer produced thereafter is subjected to the above-mentioned reactive functional group and crosslinkable silyl group. compounds having a process of reacting with (e.g., or a compound having an isocyanate group and a -Si (OCH _{3) 3} group, trimethoxysilane, hydrosilane having a hydrolyzable group such as triethoxysilane), by a known method such as It can be carried out.

The main chain of the crosslinkable silyl group-containing organic polymer is a polyoxyalkylene polymer and / or a poly (meth) acrylic-modified polyoxy because it has excellent workability, rubber elastic characteristics after curing, and weather resistance. An alkylene polymer is preferable. The "poly (meth) acrylic-modified polyoxyalkylene-based polymer" is a polyoxyalkylene-based polymer modified with a (meth) acrylic polymer, and the polyoxyalkylene-based polymer is composed of (meth) acrylic. Modified by block copolymerization or pendant copolymerization of the system monomer, modified by mixing (meth) acrylic polymer with polyoxyalkylene polymer, in polyoxyalkylene polymer (meth) ) Examples thereof include those obtained by polymerizing and modifying an acrylic monomer.

The method for producing the crosslinkable silyl group-containing polyoxyalkylene polymer or the crosslinkable silyl group-containing poly (meth) acrylic-modified polyoxyalkylene polymer is not particularly limited, but for example, from the viewpoint of low cost, the polyoxyalkylene is used. A method obtained by sequentially or simultaneously reacting each of the system polyol or the poly (meth) acrylic polyol, the crosslinkable silyl group-containing isocyanate compound, and the organic isocyanate which is an optional component for improving water resistance and the like is preferable. In this reaction, the same catalyst as the urethanization catalyst used in the synthesis of the isocyanate group-containing urethane prepolymer can be used as the reaction catalyst, or a known organic solvent can be used. Further, as the polyoxyalkylene-based polyol or the organic isocyanate, the same ones used in the synthesis of the above-mentioned isocyanate group-containing urethane prepolymer can be used.

The poly (meth) acrylic polyol contains an ethylenically unsaturated compound containing at least a hydroxyl group-containing (meth) acrylic monomer in the presence or absence of a polymerization initiator, and in the presence or absence of a solvent. , The reaction product has a narrow molecular weight distribution, which is obtained by a high-temperature continuous polymerization reaction at preferably 150 to 350 ° C., more preferably 210 to 250 ° C. by a known radical polymerization method such as batch type or continuous polymerization. It is preferable because it has a low viscosity.

The poly (meth) acrylic polyol may be obtained by polymerizing a hydroxyl group-containing (meth) acrylic monomer alone, or may be obtained by copolymerizing two or more kinds of the hydroxyl group-containing (meth) acrylic monomer, and may be obtained by copolymerizing two or more kinds thereof. ) It may be obtained by copolymerizing an acrylic monomer (1 type or 2 or more types) and an ethylenically unsaturated compound other than a hydroxyl group-containing (meth) acrylic monomer. Of these, one or 2 of the hydroxyl group-containing (meth) acrylic monomers is easy to adjust the hydroxyl content of the poly (meth) acrylic polyol and select the physical properties of the cured resin. Those obtained by copolymerizing one or more kinds of ethylenically unsaturated compounds other than the seeds and the hydroxyl group-containing (meth) acrylic monomer are preferable.

At the time of the above copolymerization, one or more hydroxyl group-containing (meth) acrylic monomers are mixed so that the average number of hydroxyl groups per molecule of the poly (meth) acrylic polyol is 1.0 to 10. It is preferable to use it, and it is particularly preferable to use it so that the number is 1.2 to 3. When the average number of hydroxyl groups exceeds 10, the physical properties after curing tend to be hard and the rubber-like elasticity tends to decrease. The polystyrene-equivalent number average molecular weight of the poly (meth) acrylic polyol by gel permeation chromatography (GPC) is preferably 500 to 30,000, particularly preferably 1,000 to 15,000. The Tg of the poly (meth) acrylic polyol is preferably 0 ° C. or lower, more preferably −70 to −20 ° C., and particularly preferably −70 to −30 ° C. The viscosity of the poly (meth) acrylic polyol at 25 ° C. is preferably 100,000 mPa · s or less, and particularly preferably 50,000 mPa · s or less. If the number average molecular weight exceeds 30,000 and the viscosities at Tg 0 ° C. and 25 ° C. exceed 100,000 mPa · s, the workability during construction deteriorates.

As the hydroxyl group-containing (meth) acrylic monomer, the crosslinkable silyl group-containing isocyanate compound and the organic isocyanate have good reactivity with the isocyanate group, and the obtained crosslinkable silyl group-containing organic polymer has a viscosity. Alcoholic hydroxyl group-containing (meth) acrylic monomers are preferable, and for example, hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate; pentaerythritol tri. (Meta) acrylate, glycerin mono (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropantri (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. Examples thereof include monoacrylates of polyhydric alcohols and polyacrylates having residual hydroxyl groups.

Other ethylenically unsaturated compounds include ethylene, propylene, isobutylene, butadiene, chloroprene, vinyl chloride, vinylidene chloride, (meth) acrylic acid, vinyl acetate, styrene, 2-methylstyrene, divinylbenzene, and (meth) acrylic acid. Methyl, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic Tridecyl acid acid, cetyl (meth) acrylate, behenyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Acrylic Acid Dimer, Polyester Poly (Meta) Acrylate, 1,6-Hexanediol Di (Meta) Acrylate, Stearyl (Meta) Acrylate, Cyclohexyl (Meta) Acrylate, Lauryl (Meta) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, tridecyl (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol Examples thereof include di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, acrylamide, methacrylicamide and acrylonitrile. Of these, (meth) acrylic acid ester-based compounds such as monomers, acrylamide, methacrylicamide, and acrylonitrile are preferable, and methyl (meth) acrylate-based compounds are preferable in terms of weather resistance and properties after curing. , Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate are particularly preferred.

These may be used alone or in combination of two or more. Further, one or more (meth) acrylic monomers having 9 or less carbon atoms and one or more (meth) acrylic monomers having 10 or more carbon atoms may be used in combination. May be good.

The chemical structure of the crosslinkable silyl group-containing isocyanate compound is not particularly limited as long as it contains one or more isocyanate groups and one or more crosslinkable silyl groups in the molecule, but the reaction can be easily controlled and cured. A compound containing one isocyanate group and one crosslinkable silyl group in the molecule is preferable from the viewpoint of good rubber elasticity. Examples of the crosslinkable silyl group-containing isocyanate compound include 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropylmethyldiethoxysilane, 3-isocyanatepropylmethyldimethoxysilane, and 3-isocyanatepropyliso. Examples thereof include propoxysilane, isocyanate trimethoxysilane, and diisocyanate dimethoxysilane, which can be used alone or in admixture of two or more. Of these, 3-isocyanatepropyltrimethoxysilane is preferable.

In the present invention, as the crosslinkable silyl group-containing organic polymer, a commercially available polymer under the name of modified silicone polymer can also be used, which contains a crosslinkable silyl group in the molecule and has a main chain of polyoxyalkylene. Examples of the system polymer include ES-S2410, ES-S3610, and ES-S3630 of the MS polymer series manufactured by Kaneka Co., Ltd., S203 and S303; and the Exester series manufactured by Asahi Glass Co., Ltd. Further, examples of the crosslinkable silyl group-containing polyoxyalkylene polymer obtained by poly (meth) acrylic modification include S903 and S943 of the MS polymer series manufactured by Kaneka Corporation. These commercially available products may be used alone or in combination of two or more. Further, these commercially available products can be combined with each of the crosslinkable silyl group-containing polyoxyalkylene polymer and the crosslinkable silyl group-containing poly (meth) acrylic polymer produced by the above-mentioned reaction.

(A-3) Polysulfide-based resin Examples of the polysulfide-based resin include polysulfide resin and modified polysulfide resin. The mercapto group contained in the molecule reacts with water and oxygen in the atmosphere at room temperature to form a disulfide bond. It can be used as a curing component by curing.

As the polysulfide resin, for example, the following general formula HS- (R _4- S _m ) _n- R _5- SH (2) having two or more mercapto groups at the end.
(In the formula, the average value of m is 1.2 to 2.8, and n is an integer of 2 to 50. R ₄ and R ₅ are independently alkyl groups or ethers having 2 to 16 carbon atoms. A compound represented by a bond-containing alkyl group) can be mentioned. The number average molecular weight of the compound represented by the above general formula is not particularly limited, but is preferably 500 to 100,000, and particularly preferably 1,000 to 20,000.

R ₄ and R ₅ include -CH (CH ₃ ) CH _2- , -CH ₂ CH _2- O-CH ₂ CH _2- , -CH ₂ CH _2- , -CH ₂ CH _2- O-CH _2- O-CH ₂ CH _2- , -CH (CH ₃ ) CH _2- O- (CH ₃ ) CH _2- O-CH (CH ₃ ) CH _2- , -CH ₂ CH _2- O- (CH ₂ CH ₂₎ −O) _p −CH ₂ CH ₂ − (p = 1 to 30) is preferable, and −CH ₂ CH ₂ −O−CH ₂ −O−CH _{2 is excellent in terms of low viscosity and good workability and curability.} CH _2- (ethylformal group) is particularly preferable.

Examples of the modified polysulfide resin include a resin having a mercapto group at the terminal but not having a sulfide bond in the main chain and having a polyoxyalkylene group and a urethane bond.

(B) A compound that reacts with water to generate an active hydrogen-containing functional group (B) When a compound that reacts with water to generate an active hydrogen-containing functional group is blended, a functional group of a room-temperature curable resin (for example, an isocyanate group) Before the (isocyanate group of the urethane prepolymer contained) reacts with moisture such as moisture to release carbon dioxide, the compound that reacts with moisture to generate an active hydrogen-containing functional group reacts with moisture such as moisture and hydrolyzes. By doing so, an active hydrogen-containing functional group such as an alcoholic hydroxyl group, a primary amino group, or a secondary amino group is generated (regenerated). Further, the active hydrogen-containing functional group generated (regenerated) before the functional group of the room-temperature curable resin (for example, the isocyanate group of the isocyanate group-containing urethane prepolymer) reacts with moisture such as moisture to release carbon dioxide gas. The active hydrogen reacts with the functional group of the room temperature curable resin (for example, the isocyanate group of the isocyanate group-containing urethane prepolymer) and is crosslinked and cured. Further, when an isocyanate group-containing urethane prepolymer using isophorone diisocyanate as a raw material is used as the room temperature curable resin, the curing rate is extremely delayed when it reacts only with water, but it reacts with water and is active. By using a compound that produces a hydrogen-containing functional group, the reaction between the secondary amino group generated by the reaction with water and the isocyanate group derived from isophorone diisocyanate is cured because the reaction rate is higher than the reaction with water. You can increase the speed. Therefore, the compound that reacts with water to generate an active hydrogen-containing functional group functions as a latent curing agent for a room temperature curable resin.

Examples of the compound that reacts with water to generate an active hydrogen-containing functional group include an oxazolidine compound (a compound having an oxazolidine ring). The compound having an oxazolidine ring is a compound having one or more, preferably 2 to 6 oxazolidine rings, which are heterocycles of saturated 5-membered rings containing an oxygen atom and a nitrogen atom. A compound having an oxazolidine ring reacts with moisture (moisture) in the atmosphere and hydrolyzes, and the oxazolidine ring produces (regenerates) a secondary amino group and an alcoholic hydroxyl group to form a room-temperature curable resin (for example, isocyanate). It functions as a latent curing agent for group-containing urethane prepolymers).

Examples of the compound having an oxazolidine ring include a urethane bond-containing oxazolidine compound which is a reaction product of a hydroxyl group of a compound having a hydroxyl group and an oxazolidine ring and an isocyanate group of an organic isocyanate compound, and a hydroxyl group and a carboxylic compound having a hydroxyl group and an oxazolidine ring. Examples thereof include an ester bond-containing oxazolidine compound, an oxazolidinesilyl ether, and a carbonate group-containing oxazolidine, which are reaction products of an acid compound with a carboxyl group. Of these, a urethane bond-containing oxazolidine compound is preferable because of its ease of production and low viscosity.

As the urethane bond-containing oxazolidine compound, for example, a hydroxyl group of a compound having a hydroxyl group and an oxazolidine ring and an isocyanate group of an organic isocyanate compound have an isocyanate group / hydroxyl group molar ratio of 0.9 to 1.2 / 1.0. A compound having a hydroxyl group and an oxazolidine ring and an organic isocyanate compound are blended so as to be in the range, preferably in the range of 0.95 to 1.05 / 1.0, and an organic solvent is added as necessary, and 50 to 100 is added. Examples thereof include those obtained by reacting at a temperature of ° C.

Organic isocyanate compounds used in the synthesis of urethane bond-containing oxazolidine compounds include aromatic polyisocyanates in which an isocyanate group is bonded to an aromatic hydrocarbon, and an isocyanate group having an aromatic ring and an isocyanate group bonded to an aliphatic hydrocarbon group. Examples thereof include aromatic aliphatic polyisocyanates and aliphatic polyisocyanates consisting only of isocyanate groups and aliphatic hydrocarbon groups.

Examples of the aromatic polyisocyanate include diphenylmethane diisocyanates (MDIs) such as 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate or a mixture thereof; 2,4-toluene diisocyanate, 2,6- Toluene diisocyanates (TDIs) such as toluene diisocyanates or mixtures thereof; other examples include phenylenediocyanates, diphenyldiisocyanates, naphthalenediocyanides, diphenylether diisocyanates and the like. Examples of the aromatic aliphatic polyisocyanate include xylylene diisocyanate. Examples of the aliphatic polyisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate, pentamethylene diisocyanate, propylene diisocyanate and butylene diisocyanate; and alicyclic polyisocyanates such as cyclohexane diisocyanate, methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate. Can be mentioned.

Further, examples thereof include a carbodiimide modified product of the polyisocyanate, a biuret modified product, an allophanate modified product, a dimer and a trimer. Other examples include polymethylene polyphenyl polyisocyanate (Crude MDI, Polymeric MDI) and the like. These can be used alone or in combination of two or more. Of these, an aliphatic polyisocyanate is preferable, and hexamethylene diisocyanate is particularly preferable, because the crystallinity of the urethane bond-containing oxazolidine compound can be lowered and the workability of the obtained sealing material composition can be improved.

Examples of the compound having a hydroxyl group and an oxazolidine ring include N-hydroxyalkyloxazolidine obtained by a dehydration condensation reaction between a secondary amino group of an alkanolamine and a carbonyl group of a ketone compound or an aldehyde compound. As a method for synthesizing a compound having a hydroxyl group and an oxazolidine ring, for example, 1.0 mol or more, preferably 1.0 to 1. mol of a carbonyl group of an aldehyde or a ketone is used with respect to 1.0 mol of a secondary amino group of an alkanolamine. Examples thereof include a method in which a 5-fold molar amount, more preferably 1.0 to 1.2-fold molar amount is used, and the dehydration condensation reaction is carried out in a solvent such as toluene or xylene by heating and refluxing to remove by-product water. ..

Examples of the alkanolamine include diethanolamine, dipropanolamine, N- (2-hydroxyethyl) -N- (2-hydroxypropyl) amine and the like. Examples of the ketone compound include acetone, diethyl ketone, isopropyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, isobutyl ketone, methyl-t-butyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone and the like. .. Examples of the aldehyde compound include acetaldehyde, propionaldehyde, n-butylaldehyde, isobutylaldehyde, barrelaldehyde, isobarrelaldehyde, 2-methylbutylaldehyde, n-hexylaldehyde, 2-methylpentylaldehyde, and n-octylaldehyde. Aliphatic aldehyde compounds such as 3,5,5-trimethylhexylaldehyde; aromatic aldehyde compounds such as benzaldehyde, methylbenzaldehyde, trimethylbenzaldehyde, ethylbenzaldehyde, isopropylbenzaldeh, isobutylbenzaldehyde, methoxybenzaldehyde, dimethoxybenzaldehyde and trimethoxybenzaldehyde. And so on.

Of these, diethanolamine is a diethanolamine as an alkanolamine because it is excellent in the ease of producing a compound having a hydroxyl group and an oxazolidine ring and in the foaming prevention property by reducing the amount of carbon dioxide gas generated when the obtained sealing material composition is cured. Of the ketone compounds and aldehyde compounds, aldehyde compounds are preferable, and among aldehyde compounds, isobutylaldehyde, 2-methylpentylaldehyde, and benzaldehyde are preferable. Specific examples of these are 2-isopropyl-3- (2-hydroxyethyl) oxazolidine, 2- (1-methylbutyl) -3- (2-hydroxyethyl) oxazolidine, 2-phenyl-3- (2-hydroxyethyl). Examples thereof include oxazolidine.

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

The oxazolidine silyl ether includes, for example, the above-mentioned compounds having a hydroxyl group and an oxazolidine ring, trimethoxysilane, tetramethoxysilane, triethoxysilane, dimethoxydimethylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, and 3-glycidoxypropyl. It is obtained by a dealcohol reaction with an alkoxysilane such as trimethoxysilane or 3-glycidoxypropyltriethoxysilane.

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

Active hydrogen-containing functional group (eg, oxazolidine) of a compound that reacts with water to generate an active hydrogen-containing functional group with respect to 1.0 mol of a functional group of a room-temperature curable resin (for example, an isocyanate group of an isocyanate group-containing urethane prepolymer). The lower limit of the lower limit of the total amount of the secondary amino group and the alcoholic hydroxyl group, which are active hydrogens produced by the hydrolysis of the ring-bearing compound, is not particularly limited, but is 0 from the viewpoint of more reliably preventing the generation of carbon dioxide gas. 6.6 mol is preferable, and 0.8 mol is particularly preferable. On the other hand, an active hydrogen-containing functional group (for example) of a compound that reacts with water to generate an active hydrogen-containing functional group with respect to 1.0 mol of a functional group of a room-temperature curable resin (for example, an isocyanate group of an isocyanate group-containing urethane prepolymer). For example, the upper limit of the upper limit of the total amount of the secondary amino group and the alcoholic hydroxyl group, which are active hydrogens produced by hydrolysis of the compound having an oxazolidine ring) is not particularly limited, but 2.4 mol is not particularly limited from the viewpoint of curability. Preferably, 2.0 mol is particularly preferred.

(C) Curing Accelerator (C) Curing Accelerator is (B) an active hydrogen-containing functional group of a compound that reacts with water to generate an active hydrogen-containing functional group (for example, a compound having an oxazolidine ring is hydrolyzed. Accelerates the reaction between the active hydrogen produced (at least one of the secondary amino group and the alcoholic hydroxyl group) and (A) the functional group of the room temperature curable resin (for example, the isocyanate group of the isocyanate group-containing urethane prepolymer). Contribute to. By adding a curing accelerator to a system containing a room temperature curable resin and a compound that reacts with water to generate an active hydrogen-containing functional group, it swells even in a curable, high-temperature, and highly acidic environment. , A sealing material capable of preventing softening can be obtained.

Curing at room temperature with an active hydrogen-containing functional group of a compound that reacts with water to generate an active hydrogen-containing functional group (for example, at least one of a secondary amino group and a hydroxyl group generated by hydrolysis of a compound having an oxazolidine ring). Examples of the curing accelerator that promotes the reaction with the functional group of the sex resin (for example, the isocyanate group of the isocyanate group-containing urethane prepolymer) include chelate compounds of various metals such as zirconium, bismuth, iron, cobalt, and nickel. Can be mentioned. Specific examples include zirconium acetylacetonate, acetylacetone bismuth, iron acetylacetonate, acetylacetone cobalt, acetylacetone nickel and the like. These may be used alone or in combination of two or more. Of these, iron chelate compounds are preferable, and iron acetylacetonate is particularly preferable, because the sealant composition is particularly excellent in curability and in preventing swelling and softening even in an environment of high temperature and strong acidity.

The amount of the curing accelerator to be blended is not particularly limited, but the active hydrogen-containing functional group of the compound that reacts with water to generate an active hydrogen-containing functional group and the room-temperature curable resin with respect to 100 parts by mass of the room-temperature curable resin. From the viewpoint of more reliably promoting the reaction with the functional group, 0.01 part by mass is preferable, and 0.02 part by mass is particularly preferable. On the other hand, the upper limit is preferably 0.05 parts by mass, particularly preferably 0.04 parts by mass, with respect to 100 parts by mass of the room temperature curable resin from the viewpoint of preventing a decrease in storage stability of the sealing material composition. .. Further, with respect to 100 parts by mass of the compound that reacts with water to generate an active hydrogen-containing functional group, the active hydrogen-containing functional group of the compound that reacts with water to generate an active hydrogen-containing functional group and the functionality of the room-temperature curable resin From the viewpoint of more reliably promoting the reaction with the group, 0.20 parts by mass is preferable, and 0.25 parts by mass is particularly preferable. On the other hand, the upper limit is 0.40 parts by mass with respect to 100 parts by mass of the compound that reacts with water to generate an active hydrogen-containing functional group from the viewpoint of preventing a decrease in storage stability of the sealant composition. Is preferable, and 0.30 parts by mass is particularly preferable.

(D) Shaking denaturing agent (excluding surface-treated calcium carbonate)
(D) The shaking denaturing agent imparts shaking denaturation to the sealing material composition of the present invention, and when the sealing material composition is filled and applied to a vertical surface such as a storage tank or a fermenter, the sauce (slump) is generated. Contributes to preventing the occurrence. Prevention of sagging (slump) is an extremely important requirement when the sealant composition is used as a sealant.

As the shaking modification imparting agent, generally, calcium carbonate surface-treated with an organic acid or the like, hydrophilic fine powder silica, and the surface of hydrophilic fine powder silica contain monomethyltrichlorosilane, dimethyldichlorosilane, and ureylene group. Inorganic rocking modifiers such as surface-treated fine powder silica treated with organic groups and hydrolyzable silyl group-containing compounds; organic rocking modifiers such as organic bentonite, fatty acid amide, and polyurea compounds are used. In the sealing material composition of the present invention, calcium carbonate that has not been surface-treated can be blended, but calcium carbonate that has been surface-treated with an organic acid or the like cannot be blended. That is, the surface-treated calcium carbonate is not contained in the sealant composition of the present invention. Further, depending on the conditions of use and the like, it is preferable to remove not only the surface-treated calcium carbonate but also the unsurface-treated calcium carbonate as the rock denaturing agent. That is, it is preferable that the sealant composition of the present invention does not contain not only surface-treated calcium carbonate but also unsurface-treated calcium carbonate depending on the conditions of use and the like.

Examples of the fine powder silica include natural silica obtained by crushing quartz, silica sand, diatomaceous earth and the like into fine powder, wet silica such as sedimentation silica, and synthetic silica such as dry silica such as fumed silica. Be done. As described above, these fine powder silicas include hydrophilic fine powder silica whose surface is not treated, and monomethyltrichlorosilane, dimethyldichlorosilane, ureylene group-containing organic group and hydrolyzable silyl on the surface of the hydrophilic fine powder silica. Examples thereof include surface-treated fine powdery silica treated with a group-containing compound or the like.

The amount of finely divided silica blended with respect to 100 parts by mass of the room temperature curable resin is not particularly limited, but the lower limit thereof is preferably 5 parts by mass and 10 parts by mass from the viewpoint of surely preventing the occurrence of sagging (slump). Especially preferable. On the other hand, the upper limit is preferably 30 parts by mass, preferably 25 parts by mass, from the viewpoint of surely preventing the coatability from being lowered due to the increase in viscosity with respect to 100 parts by mass of the room temperature curable resin. Especially preferable.

Examples of fatty acid amides include amides of higher fatty acids such as oleic acid amide and stearic acid amide, and bisamides of higher fatty acids such as N, N'-ethylenebis (stearoamide) and N, N'-methylenebis (stearoamide). Be done. Examples of commercially available products of fatty acid amide include Kusumoto Kasei Co., Ltd., trade name "Disparon # 6500".

The amount of the fatty acid amide blended with respect to 100 parts by mass of the room temperature curable resin is not particularly limited, but the lower limit thereof is preferably 5 parts by mass and 10 parts by mass from the viewpoint of surely preventing the occurrence of sagging (slump) during use. Is particularly preferable. On the other hand, the upper limit is preferably 50 parts by mass, preferably 30 parts by mass, from the viewpoint of surely preventing the coatability from being lowered due to the increase in viscosity with respect to 100 parts by mass of the room temperature curable resin. More preferred.

（式中、Ｒ_１は、ポリイソシアネート残基であり、Ｒ_２、Ｒ_３は、それぞれ独立に、水素原子、置換されていてもよい脂肪族炭化水素基、脂環族炭化水素基又は芳香族炭化水素基であるが、Ｒ_２とＲ_３との両者が同時に水素原子であることはなく、ｑは、２〜４の整数を示す。）で表される、１分子中に複数の尿素結合を有する化合物を挙げることができる。 The polyurea compound has the following general formula.

(In the formula, R ₁ is a polyisocyanate residue, and R ₂ and R ₃ are independent hydrogen atoms, optionally substituted aliphatic hydrocarbon groups, alicyclic hydrocarbon groups or aromatics, respectively. Although it is a hydrocarbon group, _{both R 2} and R ₃ are not hydrogen atoms at the same time, and q represents an integer of 2 to 4), and a plurality of urea bonds in one molecule. Can be mentioned.

Polyurea compounds are, for example, polyisocyanate R ₁ [NCO] _q (in the formula, R ₁ is a polyisocyanate residue and q represents an integer of 2 to 4) and monoamine R ₂ R ₃ NH (formula). Among them, R ₂ and R ₃ are monoamine residues, which are independently hydrogen atoms, optionally substituted aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, or aromatic hydrocarbon groups, respectively. However, _{both R 2} and R ₃ are not hydrogen atoms at the same time.)), And this is obtained. That is, the monoamine may be either a first amine or a second amine.

R ₂ and _{R 3} each independently represent a hydrogen _atom; substituted by alkyl groups of C 1 ~C _4; C 1 ~C aliphatic linear or branched saturated or unsaturated ₈ hydrocarbon group C _{3 to} C ₆ aliphatic ring groups may be; benzene or naphthalene rings optionally substituted with halogen atoms or C _{1 to} C _{4 alkyl groups; aryl substituted C 1 to} C ₄ alkyl groups are preferred (provided that they are). , R ₂ and R ₃ are not both hydrogen atoms at the same time). More specifically, aliphatic primary amines (eg, methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, etc.), aliphatic secondary amines (eg, dimethylamine, diethylamine, dipropylamine, etc.) , Diisopropylamine, dibutylamine, etc.), aliphatic unsaturated amines (eg, allylamine, diallylamine, etc.), alicyclic amines (eg, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, etc.), aromatic amines (eg, cyclopropylamine, cyclopentylamine, etc.), aromatic amines (eg, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, etc.) : Aniline, diphenylamine, methylaniline, ethylaniline, toluidine, xylidine, benzylamine, naphthylamine, etc.) and the like. Of these, as the monoamine, a monoalkylamine is preferable, and a linear monoalkylamine is particularly preferable.

As a form of use of the polyurea compound, it is possible to dehydrate the polyurea compound in the form of particles or powder and then add it to a mixture containing (A) a room temperature curable resin or the like to disperse it. However, the polyurea compound is generally used. It may be difficult to obtain a dispersion of a polyurea compound having a strong cohesive force and a good appearance. Therefore, (A) a solvent dispersion in which the polyurea compound is dispersed is prepared in a liquid medium such as a solvent or a plasticizer in which the room temperature curable resin does not cure, and the appearance is obtained by blending in the form of the solvent dispersion. It is possible to obtain the sealing material composition of the present invention which is well subjected to shaking modification. Further, a solvent dispersion of a polyurea compound is prepared by reacting the polyisocyanate with the monoamine in a liquid medium such as a solvent or a plasticizer that is inactive to the polyisocyanate and does not cure the (A) room temperature curable resin. Then, by blending the solvent dispersion, it is possible to obtain the sealing material composition of the present invention having a good appearance and imparted shaking modification. When the polyisocyanate is reacted with the monoamine in a liquid medium that is inert to the isocyanate group and does not cure the (A) room temperature curable resin, the reaction ratio of the isocyanate group / amino group or imino group is 1.0 to 1. A solvent dispersion of a polyurea compound can be obtained by setting the ratio to 1 molar and reacting by a conventional method. The proportion of the polyurea compound in the solvent dispersion is not particularly limited, but if the proportion of the liquid medium is too high, the cured coating film tends to soften after the heat treatment, and if the proportion of the liquid medium is too low, the polyurea compound tends to be softened. In some cases, the dispersibility in the sealant composition of the present invention is lowered, and lumps and the like are generated to deteriorate the appearance, or the rocking denaturation is lowered and sagging (slump) is generated.

The amount of the polyurea compound to be blended with respect to 100 parts by mass of the room temperature curable resin is not particularly limited, but the lower limit thereof is preferably 5 parts by mass and 10 parts by mass from the viewpoint of surely preventing the occurrence of sagging (slump) during use. Is particularly preferable. On the other hand, the upper limit is from the viewpoint that the coatability is lowered due to the increase in viscosity and the liquid medium of the polyurea compound is surely prevented from separating with respect to 100 parts by mass of the room temperature curable resin. 110 parts by mass is preferable, and 80 parts by mass is particularly preferable.

Of these rocking denaturing agents, fine powder silica is preferable from the viewpoint of imparting rocking denaturation with a small amount, and surface-treated fine powder can maintain stable rocking denaturation even in the presence of a curing catalyst of the sealing material composition. Silica is particularly preferred.

(E) Vinyl Chloride Resin (E) Vinyl Chloride Resin contributes to imparting elongation (ductility) to the sealing material composition of the present invention. If the displacement such as expansion and contraction due to heat of the storage tank or fermenter filled or coated with the sealant composition is large, the sealant (cured product) that cannot follow the movement will break, and liquid leakage or steel plate will occur from the broken part. Corrosion will occur. The vinyl chloride resin is not particularly limited, and examples thereof include a homopolymer of vinyl chloride, a copolymer of a vinyl chloride monomer and another monomer having an unsaturated bond copolymerizable with the vinyl chloride monomer, and the like. The other monomer is not particularly limited, and is, for example, α-olefins such as ethylene, propylene and butylene; (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate. ; Examples include aromatic vinyls such as styrene. These may be used alone or in combination of two or more.

In the sealing material composition of the present invention, in addition to the above-mentioned components (A) to (E), various additives can be further added as needed. Examples of various additives include fillers (referred to as rocking denaturing agents in the present specification, calcium carbonate is excluded), adhesiveness improvers, storage stability improvers (dehydrating agents), colorants, and antioxidants. And so on.

Examples of the filler (excluding calcium carbonate, which is used as a rocking modifier in the present specification) include mica, kaolin, zeolite, graphite, diatomaceous earth, white clay, clay, talc, slate powder, silicic anhydride, and quartz fine. Inorganic powder fillers such as powder, aluminum powder, zinc powder, magnesium carbonate, alumina, magnesium oxide; fibrous fillers such as glass fibers and carbon fibers; inorganic materials such as glass balloons, silas balloons, silica balloons and ceramic balloons. Inorganic fillers such as balloon fillers; fillers whose surfaces are treated with organic substances such as fatty acids; wood flour, walnut grain flour, rice husk powder, pulp powder, cotton chips, rubber powder, thermoplastic resin, thermocuring Organic powder fillers such as fine powder of sex resin and polyethylene powder; organic fillers such as polyethylene hollow bodies and organic balloon fillers such as Saran microballoons, as well as magnesium hydroxide and aluminum hydroxide. Also mentioned is a flame-retardant filler. The particle size of the filler is not particularly limited, but is preferably 0.01 to 1,000 μm from the viewpoint of coatability.

Examples of the adhesiveness improving agent include coupling agents, and examples of the coupling agent include various coupling agents such as silane-based, aluminum-based, and zircoaluminate-based, or partially hydrolyzed condensates thereof. .. Of these, a silane coupling agent or a partially hydrolyzed condensate thereof is preferable because of its excellent adhesiveness.

Specific examples of the silane coupling agent include vinyl trimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and the like. Vinylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-Aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, etc. A molecular weight of 500 or less, preferably 400, containing an alkoxysilyl group. Examples of the following low molecular weight compounds or one or more partial hydrolysis condensates of these silane coupling agents having a molecular weight of 200 to 3,000 can be mentioned. These can be used alone or in combination of two or more.

Examples of the storage stability improving agent include vinyltrimethoxysilane, calcium oxide, p-toluenesulfonyl isocyanate, etc. that react with water present in the sealant composition of the present invention.

Examples of the colorant include inorganic pigments such as titanium oxide, iron oxide and carbon black, and organic pigments such as copper phthalocyanine. These can be used alone or in admixture of two or more. Examples of the antioxidant include hindered phenols and the like.

The total amount of the filler (excluding calcium carbonate, which is referred to as a rocking modifier in the present specification), the adhesiveness improver, the storage stability improver and the colorant is not particularly limited, but for example, (A). ) 0 to 500 parts by mass with respect to 100 parts by mass of the room temperature curable resin, preferably 5 to 300 parts by mass. In the sealant composition of the present invention, the various additives can be used alone or in combination of two or more.

Next, examples of the present invention will be described, but the present invention is not limited to these examples as long as the gist of the present invention is not exceeded.

Synthesis of Urethane Bond-Containing Oxazolidine Compound O-1 ((B) A compound that reacts with water to generate an active hydrogen-containing functional group) Synthesis Example 1
While flowing nitrogen gas through a reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube, ester tube and heating / cooling device, 420 g of diethanolamine (molecular weight 105), 177 g of toluene and isobutyraldehyde (molecular weight 72.1) were added. 317 g was charged, heated with stirring, and a reflux dehydration reaction was carried out at 110 to 150 ° C. while removing by-produced water (71.9 g) from the system. After no distillate of water was observed, the mixture was further heated under reduced pressure (50 to 70 hPa) to remove isobutyraldehyde unreacted with toluene, and N-hydroxyethyl-2-isopropyloxazolidine, which is an intermediate reaction product, was removed. Got Next, 336 g of hexamethylene diisocyanate (molecular weight 168) was further added to 636 g of the obtained N-hydroxyethyl-2-isopropyloxazolidine, and the mixture was heated at 80 ° C. for 8 hours to bring the measured NCO content by titration to 0.0% by mass. When the reaction was completed, the reaction was terminated to obtain a urethane bond-containing oxazolidine compound O-1 (molecular weight 487) having two oxazolidine rings in the molecule. The obtained urethane bond-containing oxazolidine compound O-1 was a liquid at room temperature.

Synthesis of Isocyanate Group-Containing Urethane Prepolymer PU-1 ((A) Room Temperature Curable Resin) Synthesis Example 2
10.0 g of polyoxypropylene diol (number average molecular weight 3,200, Asahi Glass Co., Ltd. Excelol-3021) and polyoxypropylene triol (number average) are placed in a heating reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube and cooler. Epoxy acrylate (Epoxyester 70PA, manufactured by Kyoeisha Chemical Co., Ltd.) 1.1 g, which is a compound having a molecular weight of 5,040, 176.5 g of Exenol-5030 manufactured by Asahi Glass Co., Ltd., and at least one active hydrogen group and ethylenically unsaturated group. 18.0 g of naphthenic solvent (Exol D40 manufactured by Exxon Mobile) and 130.0 g of diisononyl phthalate were charged, and 30.0 g (R value (NCO)) of isophorone diisocyanate (molecular weight 222, manufactured by Ebonic Japan) was added while stirring. Equivalent / OH equivalent) = 2.3) and 0.1 g of bismastris (2-ethylhexanoate) (Nitto Kasei Co., Ltd., Neostan U-600) are added, and then heated to 2 at 70-80 ° C. Stirring was carried out for a period of time, and when the isocyanate group concentration became equal to or less than the theoretical value (1.74% by mass), the reaction was terminated by cooling to room temperature (measured isocyanate group concentration 1.72% by mass). The obtained isocyanate group-containing urethane prepolymer PU-1 was a transparent liquid at room temperature with a viscosity of 2000 mPa · s / 25 ° C.

Synthesis of DOP dispersion paste UP-1 ((D) shaking denaturing agent) of polyurea compound Synthesis Example 3
A solution prepared by dissolving 100.0 g of diphenylmethane diisocyanate (molecular weight 250.2) in 300.0 g of dioctylphthalate (DOP) and 55.0 g of n-butylamine (molecular weight 73.1) in 320.0 g of dioctylphthalate (DOP). The dissolved solution was reacted at room temperature to obtain a DOP-dispersed paste of a polyurea compound. This dispersed paste comprises 20% by mass of the polyurea compound and 80% by mass of dioctyl phthalate (DOP).

Preparation of sealant composition (Examples 1 and 2, Comparative Examples 1 to 5)
Example 1
3. In a kneading container with a nitrogen seal tube, 365.7 g of the isocyanate group-containing urethane prepolymer PU-1 obtained in Synthesis Example 2 under a nitrogen gas stream, carbon black (Asahi Thermal Co., Ltd., Furnace Black) 10. 0 g, polyvinyl chloride resin ((E) component) (Shin Daiichi PVC Co., Ltd., ZEST P21) 140.0 g, hydrophobic fumed silica ((D) component) (Tokuyama Co., Ltd., Leoloseal MT-10) 50. Add 0 g and stir, then 5.0 g of hindered phenolic antioxidant (BASF Japan, IRGANOX245), 3-glycidoxypropyltrimethoxysilane (Shinetsu Chemical, KBM-403, molecular weight 236.3). 1.0 g, iron (III) acetylacetonate (component (C)) (manufactured by Wako Pure Chemical Industries, Ltd.) 0.05 g, p-toluenesulfonyl isocyanate 1.0 g and urethane bond-containing oxazolidin compound O obtained in Synthesis Example 1. 18.5 g of -1 was charged, and the mixture was stirred and mixed until the contents became uniform to prepare a sealing material composition.

Example 2
In Example 1, 140.0 g of DOP dispersion paste UP-1 of the polyurea compound obtained in Synthesis Example 3 was charged in place of hydrophobic fumed silica, and the same operation was carried out to prepare a sealant composition.

Comparative Example 1
In Example 1, 200.0 g of surface-treated calcium carbonate (Shiroishi CCR, manufactured by Shiraishi Kogyo Co., Ltd.) was charged instead of hydrophobic fumed silica, and the same operation was carried out to prepare a sealing material composition.

Comparative Example 2
In Example 1, the same operation was carried out except that the urethane bond-containing oxazolidine compound O-1 was not charged, and the sealant composition was prepared.

Comparative Example 3
In Example 1, the same operation was carried out except that iron (III) acetylacetonate was not charged, and the sealant composition was prepared.

Comparative Example 4
In Example 1, the same operation was carried out except that hydrophobic fumed silica was not charged, and the sealant composition was prepared.

Comparative Example 5
In Example 1, the same operation was carried out except that the polyvinyl chloride resin was not charged, to prepare the sealant composition.

Evaluation (1) Slump The slump (vertical) at 23 ° C. was measured by the "5.1 slump test" of JIS A1439: 2016 "Test method for building sealant".

(2) Anti-foaming property A quadrangular frame was created on a paper pattern using a square backer having a thickness of 10 mm, and a sealing material composition was placed in the frame. The excess sealant composition was then removed with a spatula, its surface flattened and cured in a 35 ° C., 70% RH atmosphere for 7 days. After curing, the sealant composition was cut in half and the inside was visually confirmed. Those in which bubbles could be confirmed inside were evaluated as "x", and those in which bubbles could not be confirmed or those in which only a small number could be confirmed were evaluated as "○".

(3) Preparation of tensile property test piece A quadrangular frame was prepared on a paper pattern using a square backer having a thickness of 3 mm, and a sealing material composition was placed in the frame. The excess sealant composition was then removed with a spatula, the surface of which was flattened, and a sheet cured at 35 ° C. and 70% RH for 7 days was obtained. Based on JIS K6251: 2010, a dumbbell-shaped No. 3 test piece was prepared from the obtained sheet of the sealing material.

Test method Using the test piece obtained as described above, a tensile test (tensile speed 500 mm / min) was performed using a tensile tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., trade name STROGRAPH VG10-E) in an atmosphere of 23 ° C. ) Was carried out and the elongation Eb (%) at the time of cutting was measured.

(4) Preparation of Acid-Resistant Solution Resistant Specimen A quadrangular frame of 130 mm in length × 50 mm in width was prepared on a paper pattern using a square backer having a thickness of 5 mm, and a sealing material composition was placed in the frame. Next, the excess sealant composition was removed with a spatula, the surface was flattened, and the test piece was cured in a 70% RH atmosphere at 35 ° C. for 7 days, and then the square backer and the release paper were removed. did.

Test method After measuring the volume and Shore A hardness of each test piece, the test solution was immersed in a test solution having the composition shown in Table 2 below at 80 ° C. for 14 days, then taken out and dried in a 50% RH atmosphere at 23 ° C. for 1 day. After drying, the volume and Shore A hardness were measured. The value after immersion of 90% to 110% with respect to the volume before immersion and the hardness of Shore A is "○", and the value of 70 to 89% or 111% to 130% is "Δ", 69% or less or 131. Those with% or more were evaluated as "x".

Table 1 below shows the blending amounts and evaluation results of each component of Examples 1 and 2 and Comparative Examples 1 and 5.

From Table 1, in Examples 1 and 2 in which the components (A) to (E) are blended, a cured product having a slump of 0 mm, which can prevent the occurrence of sagging, and has excellent foaming prevention and elongation characteristics can be obtained. Was made. Further, in Examples 1 and 2, swelling and softening could be prevented even when exposed to an acidic solution for a long period of time in a high temperature (80 ° C.) environment, and excellent acid resistance solution resistance was obtained.

On the other hand, in Comparative Example 1 in which surface-treated calcium carbonate was used as the (D) rocking denaturing agent, elongation characteristics could not be obtained, and when exposed to an acidic solution for a long period of time in a high temperature (80 ° C.) environment, Swelling and softening occurred, and acid-resistant solution resistance could not be obtained. (B) In Comparative Example 2 in which a compound that reacts with water to generate an active hydrogen-containing functional group was not blended, neither foaming prevention property nor elongation property was obtained. (C) In Comparative Example 3 in which the curing accelerator was not blended, when exposed to an acidic solution for a long period of time in a high temperature (80 ° C.) environment, softening occurred and acid-resistant solution resistance could not be obtained. (D) In Comparative Example 4 in which the shaking denaturing agent was not blended, sagging occurred and coatability could not be obtained. In Comparative Example 5 in which the vinyl chloride resin (E) was not blended, elongation characteristics could not be obtained.

The sealing material obtained from the sealing material composition of the present invention can prevent deterioration for a long period of time even in an environment of high temperature and strong acidity. Therefore, for example, a sealing material for a biogas recovery device or a sealing material for a sabo dam. High utility value in the field of.

Claims (7)

(A) Room temperature curable resin, (B) Compound that reacts with moisture to generate active hydrogen-containing functional group, (C) Curing accelerator, (D) Shaking modification imparting agent (However, surface treatment is performed. A sealant composition containing (excluding calcium carbonate) and (E) vinyl chloride resin .
The sealant composition does not contain calcium carbonate . The sealant composition according to claim 1, wherein the room temperature curable resin (A) contains an isocyanate group-containing urethane prepolymer. The sealant composition according to claim 1 or 2, wherein the compound (B) that reacts with water to generate an active hydrogen-containing functional group contains an oxazolidine compound. The sealant composition according to any one of claims 1 to 3, wherein the curing accelerator (C) contains an iron chelate compound. The sealant composition according to claim 4, wherein the iron chelate compound contains iron acetylacetonate. The sealant composition according to any one of claims 1 to 5, wherein the rocking denaturing agent (D) contains silica and / or a polyurea compound. Any one of claims 1 to 6 in which the (D) rocking modifier contains silica and contains 10 parts by mass or more and 30 parts by mass or less of the silica with respect to 100 parts by mass of the room temperature curable resin (A). The sealant composition according to the section.