JP2011173978A - Lightweight infill repair material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an infill repair material that is lightweight and easy to apply, is excellent in workability because curing is performed at proper speed, and is also excellent in toughness, water resistance, warm water resistance, and weatherability. <P>SOLUTION: The lightweight infill repair material includes a component (A), a component (B), and a component (C) and has specific gravity of less than 1 as follows: (A) an anionic group-containing alkoxysilyl group-terminated polymer obtained by reaction of a compound (A1) containing no anionic group and a plurality of isocyanate reactive groups, a compound (A2) containing an anionic group and a plurality of isocyanate reactive groups, a polyisocyanate compound (A3), and isocyanate reactive group-containing alkoxysilane compound (A4); (B) water; and (C) inorganic hollow powders. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a lightweight filling repair material, and more specifically, a lightweight filling repair material used to obtain a smooth surface by applying a spatula or the like to joints or defective portions of gypsum board, lightweight cellular concrete, mortar, plywood, etc. About.

  Conventionally, as a lightweight filling repair material, an acrylic resin emulsion as a binder and a hollow balloon (for example, an organic microballoon, an inorganic microballoon, etc.) and an inorganic fine powder (for example, calcium carbonate) as a filler are mixed with water. The putty obtained is known (Patent Documents 1 and 2). However, these putties tend to get rid of meat as the water evaporates, and also have problems with weather resistance, such as being unable to follow shrinkage due to drying and often causing cracks, and have a completely smooth coated surface. In order to form, it was necessary to repeat construction several times. In addition, since a large amount of inorganic fine powder such as calcium carbonate is contained, the specific gravity often exceeds 1 even though it is light, and the problem is that spatula elongation is poor and coating is difficult.

  As an example that does not contain inorganic fine powder (for example, calcium carbonate) as a filler, the invention described in Patent Document 3 is known, but because the fluidity is too high, it takes too much time for drying, and the work It was a problem that the property was low. Furthermore, water resistance and hot water resistance are low, and it is difficult to use for repairing water around cracks and gaps in bathrooms and toilets.

JP 2000-212481 A JP-A-48-32127 Japanese Patent Publication No. 61-29388

  Accordingly, an object of the present invention is to provide a filling repair material that is lightweight, easy to apply, and hardened at an appropriate speed, so that it has excellent workability and is excellent in toughness, water resistance, warm water resistance and weather resistance.

  As a result of intensive studies to solve the above problems, the present inventor obtained an anionic group-containing alkoxysilyl group-terminated polymer as a binder and mixed the inorganic hollow powder as a filler and water with water. The light weight filling repair material is made by reacting water with the silyl group of the anionic group-containing alkoxysilyl group-terminated polymer, and when it is applied to the surface to be repaired, the silanol groups dehydrate and condense as the water evaporates. The three-dimensional cross-linked structure is cured and cured, and at the same time, the silanol group is firmly bonded to the hydroxyl group present on the surface of the inorganic hollow powder, or has excellent hardness, water resistance, and warm water resistance. It is possible to form a product and to maintain the space between the inorganic hollow powders even if the contained water evaporates and drys. There has been found that it is possible to prevent the meat lean. The present invention has been completed based on these findings.

That is, this invention provides the lightweight filling repair material characterized by containing the following (A) component, (B) component, and (C) component, and specific gravity being less than one.
(A) Anionic group-free and plural isocyanate-reactive group-containing compound (A1), anionic group and plural isocyanate-reactive group-containing compound (A2), polyisocyanate compound (A3), and isocyanate reactivity Anionic group-containing alkoxysilyl group-terminated polymer obtained by reacting group-containing alkoxysilane compound (A4) (B) Water (C) Inorganic hollow powder

  The anionic group-containing alkoxysilyl group-terminated polymer is preferably an anionic group-containing alkoxysilyl group-terminated urethane prepolymer, and the anionic group is preferably a carboxyl group.

  Moreover, it is preferable that the true specific gravity of (C) inorganic hollow powder is 0.10-0.60, and it is preferable that a non volatile matter is 20-60 mass%.

  The lightweight filling repair material according to the present invention comprises an anionic group-containing alkoxysilyl group-terminated polymer as a binder, an inorganic hollow powder and water as a filler. And when the silyl group of the anionic group-containing alkoxysilyl group-terminated polymer reacts with water to form a silanol group and is applied to the surface to be repaired, at the same time the silanol groups are dehydrated and condensed with each other as the moisture evaporates. In order to form a three-dimensional cross-linking structure by bonding the silanol group firmly with the hydroxyl group present on the surface of the inorganic hollow powder, or to form a cured product having excellent hardness, water resistance, and warm water resistance. Can do. Therefore, it can be suitably used for repairing around the water in a bathroom or a bathroom. Moreover, since it is not necessary to use an organic solvent, problems such as sick house syndrome are not caused, and the safety to the human body and the environment is high. Furthermore, since the curing proceeds as the water evaporates, the curing proceeds at an appropriate speed and can be carried out without rushing the coating operation. And even if the water evaporates, it is difficult to squeeze the meat and the generation of cracks can be suppressed, so that it is not necessary to repeat the construction over and over. Furthermore, since the inorganic hollow powder is used as the filler, the specific gravity of the lightweight filling repair material can be made less than 1, it can be easily transported, the spatula is light, and the workability is excellent.

[Anionic group-containing alkoxysilyl group-terminated polymer (A)]
The anionic group-containing alkoxysilyl group-terminated polymer (A) according to the present invention contains an anionic group-free compound, a plurality of isocyanate-reactive group-containing compounds (A1), an anionic group, and a plurality of isocyanate-reactive group-containing compounds. It is obtained by reacting (A2), a polyisocyanate compound (A3), and an isocyanate-reactive group-containing alkoxysilane compound (A4). The anionic group may have a salt form.

[Anionic group-free compound and a plurality of isocyanate-reactive group-containing compounds (A1)]
The compound (A1) not containing an anionic group and containing a plurality of isocyanate-reactive groups (hereinafter sometimes referred to as “isocyanate-reactive compound (A1)”) has an anionic group in the molecule. The compound is not particularly limited as long as it is a compound having at least two isocyanate-reactive groups in the molecule. The isocyanate-reactive group (A1) is not particularly limited as long as it is a group reactive to an isocyanate group, and examples thereof include a hydroxyl group, a primary amino group (unsubstituted amino group), and a secondary amino group. Examples include a group (mono-substituted amino group) and a mercapto group. Accordingly, examples of the isocyanate-reactive compound (A1) include an anionic group-free polyol compound, an anionic group-free polyamine compound, and an anionic group-free polythiol compound.

  As the isocyanate-reactive group in the present invention, a hydroxyl group, a primary amino group or a secondary amino group (particularly a hydroxyl group) is preferable. As the isocyanate-reactive compound (A1), an anionic group-free polyol compound or An anionic group-free polyamine compound (particularly an anionic group-free polyol compound) is preferred. These can be used alone or in admixture of two or more.

  Examples of the anionic group-free polyol compound (A1) (hereinafter sometimes referred to as “polyol (A1)”) in the isocyanate-reactive compound (A1) include polyhydric alcohols, polyether polyols, polyester polyols, and polycarbonates. A polyol, polyolefin polyol, polyacryl polyol, castor oil, etc. can be mentioned. In the present invention, polyether polyols, polyester polyols, and polycarbonate polyols (particularly, polyether polyols) are preferred because they are relatively easy to handle during production.

  Examples of the polyether polyol include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polyoxytetramethylene glycol (PTMG), as well as a plurality of alkylene oxides as monomer components such as an ethylene oxide-propylene oxide copolymer ( An alkylene oxide-other alkylene oxide) copolymer etc. can be mentioned. These can be used alone or in admixture of two or more.

  Examples of the polyester polyol include a condensation polymer of a polyhydric alcohol and a polycarboxylic acid; a ring-opening polymer of a cyclic ester (lactone); a polyhydric alcohol, a polycarboxylic acid, and a cyclic ester. A reactant or the like can be used. These can be used alone or in admixture of two or more. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, and 2-methyl-1,3-trimethylene. Diol, 1,5-pentamethylenediol, neopentyl glycol, 1,6-hexamethylenediol, 3-methyl-1,5-pentamethylenediol, 2,4-diethyl-1,5-pentamethylenediol, glycerin, Examples include trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A), and sugar alcohols (such as xylitol and sorbitol). . On the other hand, examples of polycarboxylic acids include aliphatic dicarboxylic acids such as malonic acid, maleic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; 1,4-cyclohexane Examples thereof include alicyclic dicarboxylic acids such as dicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylene dicarboxylic acid, and trimellitic acid. Examples of the cyclic ester include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone.

  Examples of the polycarbonate polyol include a reaction product of a polyhydric alcohol and phosgene; a ring-opening polymerization product of a cyclic carbonate. These can be used alone or in admixture of two or more. Examples of the polyhydric alcohol used for the reaction between the polyhydric alcohol and phosgene include the same examples as those of the polyhydric alcohol. Examples of the cyclic carbonate include alkylene carbonates such as ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, and hexamethylene carbonate. In the present invention, the polycarbonate polyol may be any compound having a carbonate bond in the molecule and having a terminal hydroxyl group, and may have an ester bond together with the carbonate bond.

  Examples of the polyamine compound containing no anionic group in the isocyanate-reactive compound (A1) (hereinafter sometimes referred to as “polyamine (A1)”) include compounds corresponding to the polyol (A1). it can.

  The number average molecular weight of the isocyanate-reactive compound (A1) in the present invention is, for example, preferably about 500 to 5000, and more preferably about 1000 to 3000. When the number average molecular weight is less than 500, the adhesion to the coated body tends to decrease. On the other hand, when the number average molecular weight exceeds 5000, it tends to be difficult to disperse in water. Moreover, there exists a tendency for the heat resistance of a hardened | cured material, water resistance, warm water resistance, and solvent resistance to fall.

  Furthermore, as the isocyanate-reactive compound (A1) in the present invention, the above-mentioned isocyanate-reactive compound having a number average molecular weight of 500 or more and an isocyanate-reactive compound having a number average molecular weight of less than 500 may be used in combination. Thus, the toughness can be further enhanced by using a combination of a high molecular weight isocyanate-reactive compound and a low molecular weight isocyanate-reactive compound.

  Further, the number average molecular weight of the isocyanate-reactive compound having a number average molecular weight of less than 500 is not particularly limited as long as it is less than 500, but is, for example, in the range of 48 or more and less than 500 (in particular, in the range of 62 to 300). It is preferable.

  Examples of the isocyanate-reactive compound having a number average molecular weight of less than 500 include N, N-bis (2-hydroxyethyl) -N-methylamine (N-methyldiethanolamine) (molecular weight: 119.16), N-ethyldiethanolamine. Etc.

  The mixing ratio of the isocyanate-reactive compound having a number average molecular weight of 500 or more and the isocyanate-reactive compound having a number average molecular weight of less than 500 is, for example, [isocyanate-reactive group of an isocyanate-reactive compound having a number-average molecular weight of 500 or more ( Hydroxyl group and the like]] / [isocyanate-reactive group of the isocyanate-reactive compound having a number average molecular weight of less than 500 (hydroxyl group and the like)] (molar ratio) = a range of about 0.05 to 4 can be appropriately selected.

[Anionic group and plural isocyanate-reactive group-containing compound (A2)]
The compound (A2) containing an anionic group and a plurality of isocyanate-reactive groups (hereinafter sometimes referred to as “isocyanate-reactive compound (A2)”) has at least one anionic group in the molecule. And a compound having at least two isocyanate-reactive groups in the molecule is not particularly limited.

  Examples of the anionic group in the isocyanate-reactive compound (A2) include a carboxyl group and a sulfo group. Among them, a carboxyl group is preferable because it is relatively easy to handle during production.

  In addition, the isocyanate-reactive group in the isocyanate-reactive compound (A2) is not particularly limited as long as it is a group having reactivity with an isocyanate group, and examples thereof include a hydroxyl group, a primary amino group, or a secondary amino group, A mercapto group etc. can be mentioned. In the present invention, among them, a hydroxyl group, a primary amino group or a secondary amino group is preferable, and a hydroxyl group is particularly preferable.

  Therefore, as the isocyanate-reactive compound (A2) in the present invention, for example, carboxyl group-containing polyol compound, carboxyl group-containing polyamine compound, carboxyl group-containing polythiol compound, sulfo group-containing polyol compound, sulfo group-containing polyamine compound, sulfo group-containing A polythiol compound can be mentioned, and among them, a carboxyl group-containing polyol compound and a carboxyl group-containing polyamine compound are preferable, and a carboxyl group-containing polyol compound is particularly preferable. These isocyanate-reactive compounds (A2) can be used alone or in combination of two or more.

As the carboxyl group-containing polyol compound in the present invention, it is preferable to use a polyhydroxycarboxylic acid represented by the following formula (1).
(HO) _X L (COOH) _Y (1)
(In the formula, L represents a hydrocarbon moiety having 1 to 12 carbon atoms. X is an integer of 2 or more, and Y is an integer of 1 or more.)

  In the formula (1), examples of the hydrocarbon moiety represented by L include a linear or branched aliphatic hydrocarbon moiety. X is an integer of 2 or more, and Y is an integer of 1 or more. X and Y may be the same or different. Further, two or more hydroxyl groups may be bonded to the same carbon atom or may be bonded to different carbon atoms. Furthermore, when Y is 2 or more, two or more carboxyl groups may be bonded to the same carbon atom or may be bonded to different carbon atoms. In the present invention, X is preferably 2, and Y is preferably 1.

  Examples of such polyhydroxycarboxylic acid include dimethylol alkanoic acid, among which 2,2-dimethylol alkanoic acid is preferable. Examples of 2,2-dimethylolalkanoic acid include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolpentanoic acid, 2,2-dimethylolhexanoic acid, 2 2, 2-dimethylol heptanoic acid, 2,2-dimethylol octanoic acid, 2,2-dimethylol nonanoic acid, 2,2-dimethylol decanoic acid and the like. These can be used alone or in admixture of two or more.

[Polyisocyanate compound (A3)]
The polyisocyanate compound (A3) is not particularly limited as long as it is a compound having at least two isocyanate groups in the molecule. Examples of the polyisocyanate compound (A3) include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates.

  Examples of the aliphatic polyisocyanate include 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,3-pentamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexa Methylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 3-methyl -1,5-pentamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,6-diisocyanate methyl caproate Lysine diiso Ane - and aliphatic diisocyanates such as bets can be mentioned. These can be used alone or in admixture of two or more.

  Examples of the alicyclic polyisocyanate include 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4. '-Methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane, 1,4-bis (isocyanate methyl) cyclohexane, isophorone diisocyanate And alicyclic diisocyanates such as norbornane diisocyanate. These can be used alone or in admixture of two or more.

  Examples of aromatic polyisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and naphthylene. 1,4-diisocyanate, naphthylene-1,5-diisocyanate, 4,4'-diphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane di Isocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3, 3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, 3,3'-dimethoxydiphenyl 4,4' diisocyanate - such as aromatic diisocyanates such as bets can be mentioned. These can be used alone or in admixture of two or more.

  Examples of the araliphatic polyisocyanate include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, ω, ω′-diisocyanate-1,4-diethylbenzene, 1,3-bis. Aroaliphatic diisocyanates such as (1-isocyanate-1-methylethyl) benzene, 1,4-bis (1-isocyanate-1-methylethyl) benzene, 1,3-bis (α, α-dimethylisocyanatomethyl) benzene And so on. These can be used alone or in admixture of two or more.

  As the polyisocyanate compound (A3) in the present invention, among others, 1,6-hexamethylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, , 4-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,3 -Xylylene diisocyanate, 1,4-xylylene diisocyanate, norbornane diisocyanate, 1,3-bis (α, α-dimethylisocyanatomethyl) benzene can be suitably used. These can be used alone or in admixture of two or more. Further, when an aliphatic polyisocyanate or an araliphatic polyisocyanate is used as the polyisocyanate compound (A3), a resin with little discoloration can be obtained.

  In the present invention, the polyisocyanate compound (A3) is a dimer or trimer based on the above-mentioned aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, or araliphatic polyisocyanate. Reaction products or polymers (eg diphenylmethane diisocyanate dimers and trimers, reaction products of trimethylolpropane and tolylene diisocyanate, reaction products of trimethylolpropane and hexamethylene diisocyanate, polymethylene poly Phenyl isocyanate, polyether polyisocyanate, polyester polyisocyanate, etc.) can also be used.

[Isocyanate-reactive group-containing alkoxysilane compound (A4)]
The isocyanate-reactive group-containing alkoxysilane compound (A4) is not particularly limited as long as it is a silane compound having at least one isocyanate-reactive group in the molecule and having at least one alkoxy group in the molecule.

  The isocyanate-reactive group is not particularly limited as long as it is reactive to an isocyanate group. For example, a primary amino group (unsubstituted amino group), a secondary amino group (mono-substituted) Amino group), mercapto group, hydroxyl group and the like. In the present invention, primary or secondary amino group and mercapto group are particularly reactive, and the target compound is obtained in high yield. It is preferable at the point which can do. Accordingly, the isocyanate-reactive group-containing alkoxysilane compound (A4) in the present invention includes primary or secondary amino group-containing alkoxysilane compounds (A4-1) and mercapto group-containing alkoxysilane compounds (A4-2). preferable.

  The primary or secondary amino group-containing alkoxysilane compound (A4-1) has at least one primary or secondary amino group in the molecule, and at least one in the molecule. If it is a silane compound which has an alkoxy group, it will not restrict | limit in particular. The primary or secondary amino group-containing alkoxysilane (A4-1) may contain a tertiary amino group.

  Further, the primary or secondary amino group may be directly bonded to the silicon atom, but is preferably bonded via a divalent group. Examples of such a divalent group include a divalent hydrocarbon group composed only of a hydrocarbon group such as an alkylene group, an arylene group, an alkylene-arylene group, and an alkylene-arylene-alkylene group; Hydrocarbon groups such as alkylene groups, alkylene-carbonyl-oxy-alkylene groups, alkylene-oxy-carbonyl-alkylene groups, alkylene-poly (oxyalkylene) groups and other groups (oxy groups, carbonyl-oxy groups, etc.) Various divalent groups constituted by various combinations can be exemplified.

（式中、Ｒ¹、Ｒ²は、同一又は異なって、置換基を有していてもよいアルキル基を示し、Ｒ³、Ｒ⁴は、同一又は異なって、置換基を有していてもよいアルキレン基を示し、Ｒ⁵は置換基を有していてもよいアリール基、置換基を有していてもよいアルキル基又は置換基を有していてもよいシクロアルキル基を示す。また、ｍは１〜３の整数である。ｍが１である場合、２個のＲ²は同一であってもよく、異なっていてもよい。ｍが２以上の整数である場合、２個以上のＲ¹Ｏ−基は同一であってもよく、異なっていてもよい） As the primary or secondary amino group-containing alkoxysilane compound (A4-1) in the present invention, it is preferable to use compounds represented by the following formulas (2a), (2b) and (2c).

(In the formula, R ¹ and R ² are the same or different and each represents an optionally substituted alkyl group, and R ³ and R ⁴ may be the same or different and have a substituent. R ⁵ represents an aryl group that may have a substituent, an alkyl group that may have a substituent, or a cycloalkyl group that may have a substituent. m is an integer of 1 to 3. When m is 1, two R ² may be the same or different, and when m is an integer of 2 or more, 2 or more. R ¹ O— groups may be the same or different)

Examples of the alkyl group in R ¹ , R ² and R ⁵ in the above formulas (2a), (2b) and (2c) include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t -Alkyl groups having about 1 to 4 carbon atoms such as a butyl group can be mentioned. The alkylene group for R ^3, R ^4, for example, a methylene group, an ethylene group, and an alkylene group of about 1 to 3 carbon atoms such as trimethylene group. Examples of the aryl group for R ⁵ include a phenyl group, and examples of the cycloalkyl group include a cyclohexyl group.

Examples of the substituent that R ^{1 to} R ⁵ may have include, for example, an aryl group such as a phenyl group; an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group; and a cycloalkyl such as a cyclohexyl group. Examples include groups. The hydrocarbon group may be further substituted with other substituents (eg, alkoxy group, aryloxy group, cycloalkyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, cycloalkyloxycarbonyl group, acyl group, amino group, etc.) You may have.

  Examples of the amino group-containing alkoxysilane having only a primary amino group as the isocyanate-reactive group represented by the formula (2a) include aminomethyltrimethoxysilane, aminomethyltriethoxysilane, and β-aminoethyl. Trimethoxysilane, β-aminoethyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltripropoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltri Aminoalkyltrialkoxysilanes such as butoxysilane; β-aminoethylmethyldimethoxysilane, β-aminoethylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropy And the like (aminoalkyl) alkyl dialkoxy silane or aminoalkyl dialkyl (mono) alkoxysilanes corresponding to these, such as methyl dipropoxy silane.

  Examples of the amino group-containing alkoxysilane having a primary amino group and a secondary amino group as the isocyanate-reactive group represented by the formula (2b) include N-β (aminoethyl) -γ-amino. N- (aminoalkyl) aminoalkyltrialkoxysilane such as propyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane; N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, Examples thereof include N- (aminoalkyl) aminoalkylalkyldialkoxysilanes such as N-β (aminoethyl) -γ-aminopropylmethyldiethoxysilane.

  Examples of the amino group-containing alkoxysilane having only a secondary amino group as the isocyanate-reactive group represented by the formula (2c) include N-phenyl-β-aminoethyltrimethoxysilane, N-phenyl- N-phenyl-β-aminoethyltrialkoxysilane such as β-aminoethyltriethoxysilane; N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ -N-phenyl-γ-aminopropyltrialkoxysilane such as aminopropyltripropoxysilane, N-phenyl-γ-aminopropyltributoxysilane, and the corresponding N-phenylaminoalkyl (mono or di) alkyl (di Or mono) alkoxysilane; N-methyl-3-aminopropylto Methoxysilane, N-ethyl-3-aminopropyltrimethoxysilane, Nn-propyl-3-aminopropyltrimethoxysilane, Nn-butyl-aminomethyltrimethoxysilane, Nn-butyl-2-amino Ethyltrimethoxysilane, Nn-butyl-3-aminopropyltrimethoxysilane, Nn-butyl-3-aminopropyltriethoxysilane, Nn-butyl-3-aminopropyltripropoxysilane, etc.), Mention may be made of N-alkylaminoalkyltrialkoxysilanes such as N-alkylaminoalkyl (mono or di) alkyl (di or mono) alkoxysilanes.

  The mercapto group-containing alkoxysilane compound (A4-2) is not particularly limited as long as it is a silane compound having at least one mercapto group in the molecule and having at least one alkoxy group in the molecule.

  Further, the mercapto group may be directly bonded to the silicon atom, but is preferably bonded via a divalent group. Examples of such a divalent group include a divalent hydrocarbon group composed only of a hydrocarbon group such as an alkylene group, an arylene group, an alkylene-arylene group, and an alkylene-arylene-alkylene group; Hydrocarbon groups such as alkylene groups, alkylene-carbonyl-oxy-alkylene groups, alkylene-oxy-carbonyl-alkylene groups, alkylene-poly (oxyalkylene) groups and other groups (oxy groups, carbonyl-oxy groups, etc.) Various divalent groups constituted by various combinations can be exemplified.

  As the mercapto group-containing alkoxysilane compound (A4-2) in the present invention, a compound represented by the following formula (2d) can be particularly preferably used.

（式中、Ｒ¹、Ｒ²は、同一又は異なって、置換基を有していてもよいアルキル基を示し、Ｒ³は置換基を有していてもよいアルキレン基を示す。また、ｍは１〜３の整数である。ｍが１である場合、２個のＲ²は同一であってもよく、異なっていてもよい。ｍが２以上の整数である場合、２個以上のＲ¹Ｏ−基は同一であってもよく、異なっていてもよい）

(Wherein R ¹ and R ² are the same or different and each represents an alkyl group which may have a substituent, and R ³ represents an alkylene group which may have a substituent. M Is an integer of 1 to 3. When m is 1, two R ² may be the same or different, and when m is an integer of 2 or more, 2 or more of R 2 ¹ O-groups may be the same or different)

The R ^1, R ^2, R ³ in the above formula (2d), the formula (2a), (2b), can be the same examples as R ^1, R ^2, R ³ in (2c) . In addition, R ¹ , R ² , and R ^{3 in} the above formulas (2a), (2b), and (2c) may have substituents that R ¹ , R ² , and R ³ may have. Examples similar to the above substituents may be given.

  Examples of the mercapto group-containing alkoxysilane represented by the formula (2d) include mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, β-mercaptoethyltrimethoxysilane, and β-mercaptoethyltriethoxysilane. , Γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltripropoxysilane, γ-mercaptopropyltriisopropoxysilane, mercaptoalkyltrialkoxysilane such as γ-mercaptopropyltributoxysilane; β -Mercaptoethylmethyldimethoxysilane, β-mercaptoethylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldie Kishishiran and γ- mercaptopropyl methyl dipropoxy silane of (mercaptoalkyl) alkyl dialkoxy silane or those in the corresponding mercaptoalkyl dialkyl (mono) alkoxysilanes can be mentioned.

  The isocyanate-reactive group-containing alkoxysilane compound (A4) in the present invention is a primary or secondary amino group-containing alkoxysilane compound (A4) from the viewpoints of easy reaction, wide commercial availability and easy availability. -1) is preferred.

  As the primary or secondary amino group-containing alkoxysilane compound (A4-1), trade names “KBM602”, “KBM6063”, “X-12-896”, “KBM576”, “X-12” -565 "," X-12-580 "," X-12-5263 "," X-12-666 "," KBM6123 "," X-12-575 "," X-12 " -577 "," X-12-563B "," X-12-730 "," X-12-562 "," X-12-5202 "," X-12-5204 ", Commercial products such as “KBE9703” (manufactured by Shin-Etsu Chemical Co., Ltd.) can be preferably used.

  Furthermore, in the present invention, an unsaturated carboxylic acid ester (A5) is added to the primary or secondary amino group-containing alkoxysilane compound (A4-1) as the isocyanate-reactive group-containing alkoxysilane compound (A4). An ester-modified amino group-containing alkoxysilane (A4-5) containing at least a secondary amino group as an isocyanate-reactive group obtained by reaction may be used.

  The unsaturated carboxylic acid ester (A5) is particularly limited as long as it is a compound in which at least one (preferably all) carboxylic acid groups (carboxyl groups) of the unsaturated carboxylic acid are in the form of an ester. The unsaturated monovalent carboxylic acid ester or the unsaturated polyvalent carboxylic acid ester (for example, unsaturated divalent carboxylic acid ester) may be used.

  As the unsaturated carboxylic acid ester (A5), a carboxyl group or an ester thereof (for example, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, etc.) directly on a carbon atom forming a carbon-carbon double bond. Can be mentioned. Examples of such a compound include acrylic acid ester, methacrylic acid ester, crotonic acid ester, isocrotonic acid ester, 2-butenoic acid ester, 3-methyl-2-butenoic acid ester, 2-pentenoic acid ester, and 2-octene ester. In addition to acid esters, etc., unsaturated monovalent carboxylic acid esters such as cinnamic acid ester; unsaturated 2 such as maleic acid ester (mono or diester), fumarate ester (mono or diester), itaconic acid ester (mono or diester) And esters of polyvalent carboxylic acids. In the present invention, acrylic acid esters, methacrylic acid esters (hereinafter, these may be collectively referred to as “(meth) acrylic acid esters”), and maleic acid diesters are particularly preferable.

  Examples of the ester moiety in the unsaturated carboxylic acid ester (A5) include methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, s-butyl ester, t-butyl ester, pentyl ester, isopentyl ester, Aliphatic carbonization such as hexyl ester, heptyl ester, octyl ester, 2-ethylhexyl ester, nonyl ester, decyl ester, isodecyl ester, undecyl ester, dodecyl ester, tridecyl ester, tetradecyl ester, hexadecyl ester, octadecyl ester Esters with hydrogen (alkyl esters, etc.); cyclohexyl ester, isobornyl ester, bornyl ester, dicyclopentadienyl ester, dicyclope Examples include esters with alicyclic hydrocarbons such as tanyl esters, dicyclopentenyl esters, and tricyclodecanyl esters (cycloalkyl esters, etc.); esters with aromatic hydrocarbons such as phenyl esters, benzyl esters, etc. (aryl esters, etc.) be able to. In addition, when it has multiple ester site | parts, each ester site | part may be the same and may differ.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, and (meth) acrylic. Examples include (meth) acrylic acid alkyl esters such as 2-ethylhexyl acid, dodecyl (meth) acrylate, and octadecyl (meth) acrylate. Examples of maleic acid diesters include maleic compounds such as dimethyl maleate, diethyl maleate, dibutyl maleate, dihexyl maleate, dioctyl maleate, di (2-ethylhexyl) maleate, didodecyl maleate and dioctadecyl maleate. And acid dialkyl esters.

  As the ester-modified amino group-containing alkoxysilane (A4-5), for example, the β-position carbon atom in the carbon-carbon double bond of the unsaturated carboxylic acid ester (A5) is an amino group in the primary amino group-containing alkoxysilane. Examples thereof include compounds bonded to the nitrogen atom of the group. That is, in the ester-modified amino group-containing alkoxysilane (A4-5), the nitrogen atom of the amino group in the primary amino group-containing alkoxysilane is an unsaturated bond (carbon-carbon double) of the unsaturated carboxylic acid ester (A5). A compound obtained by performing a Michael addition reaction to (bonding) is preferable. The reaction can be carried out in the presence or absence of a solvent. In the reaction, heating or pressurization may be performed.

  Specifically, the ester-modified amino group-containing alkoxysilane (A4-5) is a compound in which the primary amino group-containing alkoxysilane is represented by the formula (2a), and the unsaturated carboxylic acid ester (A5) is When it is an unsaturated carboxylic acid ester represented by the following formula (3), it can be represented by the following formula (4).

（式中、Ｒ⁶、Ｒ⁸は、同一又は異なって、水素原子又はアルキル基を示す。Ｒ⁷はアルキル基、アリール基又はシクロアルキル基を示す。Ｒ⁹は水素原子、アルキル基、アリール基、アルコキシカルボニル基、アリールオキシカルボニル基、シクロアルキルオキシカルボニル基から選択された基を示す）

(In the formula, R ⁶ and R ⁸ are the same or different and each represents a hydrogen atom or an alkyl group. R ⁷ represents an alkyl group, an aryl group or a cycloalkyl group. R ⁹ represents a hydrogen atom, an alkyl group or an aryl group. A group selected from an alkoxycarbonyl group, an aryloxycarbonyl group, and a cycloalkyloxycarbonyl group)

（式中、Ｒ¹〜Ｒ³、Ｒ⁶〜Ｒ⁹及びｍは前記に同じ）

(Wherein R ^{1 to} R ³ , R ^{6 to} R ⁹ and m are the same as above)

  When the primary amino group-containing alkoxysilane is a compound represented by the above formula (2b) and the unsaturated carboxylic acid ester (A5) is an unsaturated carboxylic acid ester represented by the above formula (3) The ester-modified amino group-containing alkoxysilane (A4-5) can be represented by the following formula (5a) or the following formula (5b).

（式（5a）及び（5b）中、Ｒ¹〜Ｒ⁴、Ｒ⁶〜Ｒ⁹及びｍは前記に同じ）

(In the formulas (5a) and (5b), R ^{1 to} R ⁴ , R ^{6 to} R ⁹ and m are the same as above)

Moreover, as an alkyl group in R < ⁶ >, C1-C2 alkyl groups, such as a methyl and an ethyl group, etc. can be mentioned, for example. Examples of the alkyl group for R ⁷ include alkyl groups having about 1 to 20 carbon atoms such as methyl, ethyl, propyl, butyl, isobutyl, t-butyl, hexyl, octyl, and 2-ethylhexyl groups. In addition, examples of the aryl group in R ⁷ include a phenyl group, and examples of the cycloalkyl group in R ⁷ include a cyclohexyl group. Examples of the alkyl group for R ⁸ include alkyl groups having about 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, isobutyl, t-butyl, and hexyl groups. Examples of the alkyl group for R ⁹ include alkyl groups having about 1 to 2 carbon atoms such as methyl and ethyl groups. Examples of the aryl group include phenyl groups, and alkoxy groups. Examples of the alkyl group portion, aryl group portion, and cycloalkyl group portion of the carbonyl group, aryloxycarbonyl group, and cycloalkyloxycarbonyl group include the same examples as the alkyl group, aryl group, and cycloalkyl group exemplified in the above R ^7. be able to.

[Anionic group-containing alkoxysilyl group-terminated polymer (A)]
The anionic group-containing alkoxysilyl group-terminated polymer (A) in the present invention includes the isocyanate-reactive compound (A1), the isocyanate-reactive compound (A2), the polyisocyanate compound (A3), and the isocyanate-reactive group-containing alkoxysilane compound. It is a reaction product obtained by reacting (A4) with an anionic group derived from the isocyanate-reactive compound (A2) in the molecule and an isocyanate-reactive group-containing alkoxysilane compound (A4) at the end of the main chain. It is a polymer having an alkoxysilyl group derived therefrom.

  Examples of the anionic group-containing alkoxysilyl group-terminated polymer (A) in the present invention include an isocyanate-reactive compound (A1) (particularly polyol (A1)), an isocyanate-reactive compound (A2) (particularly polyol (A2)), and Terminal alkoxysilyl obtained by reaction of an anionic group-containing polymer (particularly an anionic group-containing urethane prepolymer) which is a reaction product of a polyisocyanate compound (A3) with an isocyanate-reactive group-containing alkoxysilane compound (A4) An anionic group-containing urethane prepolymer is preferred.

  The terminal isocyanate group content of the anionic group-containing polymer is preferably, for example, about 0.3 to 7.0% by weight. When the content of the terminal isocyanate group exceeds 7.0% by weight, water dispersion tends to be difficult. On the other hand, if the content of the terminal isocyanate group is less than 0.3% by weight, the viscosity at the time of synthesis tends to be too high and the synthesis tends to be difficult.

  When mixing the isocyanate-reactive compound (A1), the isocyanate-reactive compound (A2), the polyisocyanate compound (A3), and the isocyanate-reactive group-containing alkoxysilane compound (A4), the mixing order of each component is not limited. The order of mixing can be selected as appropriate according to the type of component. In the present invention, after the polyisocyanate compound (A3) is added to the mixture of the isocyanate-reactive compound (A1) and the isocyanate-reactive compound (A2) and reacted to prepare an anionic group-containing polymer, the reaction mixture It is preferable in terms of yield to prepare an anionic group-containing alkoxysilyl group-terminated polymer (A) by adding an isocyanate-reactive group-containing alkoxysilane compound (A4) to the reaction.

  When the polyol (A1) is used as the isocyanate-reactive compound (A1) and the polyol (A2) is used as the isocyanate-reactive compound (A2), the anionic group-containing polymer is obtained by reacting the polyol compound with the polyisocyanate compound. It can be obtained by reacting according to a known or conventional method for preparing a polymer. As the anionic group-containing polymer in the present invention, a polymer having a terminal isocyanate group is preferable.

  When reacting the polyol (A1), polyol (A2), and polyisocyanate compound (A3), a polymerization catalyst may be used to accelerate the reaction. The reaction can be performed in a solvent.

  As the polymerization catalyst, a known or commonly used polymerization catalyst (curing catalyst) used in the reaction between the polyol compound and the polyisocyanate compound can be used. For example, a base such as an organic tin compound, a metal complex, or an amine compound. And organic phosphoric acid compounds. Examples of the organic tin compound include dibutyltin dilaurate, dibutyltin malate, dibutyltin phthalate, stannous octylate, dibutyltin methoxide, dibutyltin diacetylacetate, dibutyltin diversate, and the like. Examples of the metal complex include titanate compounds such as tetrabutyl titanate, tetraisopropyl titanate and triethanolamine titanate; carboxylic acid metal salts such as lead octylate, lead naphthenate, nickel naphthenate and cobalt naphthenate; aluminum Examples thereof include metal acetylacetonate complexes such as acetylacetonate complexes and vanadium acetylacetonate complexes. Furthermore, examples of basic compounds such as amine compounds include aminosilanes such as γ-aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane; quaternary ammonium salts such as tetramethylammonium chloride and benzalkonium chloride. Linear or cyclic containing a plurality of nitrogen atoms, such as Sankyo Air Products' trade name “DABCO” series and “DABCO BL” series, 1,8-diazabicyclo [5.4.0] undec-7-ene; There may be mentioned tertiary amines or quaternary ammonium salts. Furthermore, examples of the organic phosphoric acid compound include monomethyl phosphoric acid, di-n-butyl phosphoric acid, and triphenyl phosphate.

  The subsequent reaction between the anionic group-containing polymer and the isocyanate-reactive group-containing alkoxysilane compound (A4) can be carried out by mixing both and heating as necessary. By this reaction, the isocyanate group at the terminal of the anionic group-containing polymer is alkoxysilylated to obtain the anionic group-containing alkoxysilyl group-terminated polymer (A). In the reaction, a polymerization catalyst may be used as necessary. The reaction can be performed in a solvent.

  The method for preparing an anionic group-containing alkoxysilyl group-terminated polymer (A) when the polyol (A1) is used as the isocyanate-reactive compound (A1) and the polyol (A2) is used as the isocyanate-reactive compound (A2) In the case of using a polyamine compound or a polythiol compound as the isocyanate-reactive compound (A1) or the isocyanate-reactive compound (A2), an anionic group-containing alkoxysilyl group-terminated polymer (A) is obtained by the same method. Can be prepared.

  The isocyanate-reactive compound (A1) is a combination of an isocyanate-reactive compound having a number average molecular weight of 500 or more and an isocyanate-reactive compound having a number average molecular weight of less than 500, the number average molecular weight being less than 500. When the polyamine (A1) is used, the isocyanate-reactive compound (A1), the isocyanate-reactive compound (A2), and the polyisocyanate compound (A3) other than the polyamine (A1) having a number average molecular weight of less than 500 are mixed. And an anionic group-containing polymer, and then reacting with an isocyanate-reactive group-containing alkoxysilane compound (A4) to obtain an anionic group-containing polymer partially terminally alkoxysilylated, Add polyamine (A1) with number average molecular weight less than 500 to add anionic group-containing alcohol A xylyl group-terminated polymer (A) may be prepared.

  In the present invention, the ratio of each component of the isocyanate-reactive compound (A1), the isocyanate-reactive compound (A2), the polyisocyanate compound (A3), and the isocyanate-reactive group-containing alkoxysilane compound (A4) is particularly limited. The ratio of the polyisocyanate compound (A3) to the isocyanate-reactive compound (A1) and the isocyanate-reactive compound (A2) is, for example, the isocyanate group / isocyanate in the polyisocyanate compound (A3). Isocyanate-reactive group (NCO / NCO-reactive group) (equivalent ratio) in reactive compound (A1) and isocyanate-reactive compound (A2) is greater than 1 and less than or equal to 1.5 (preferably greater than 1 and less than or equal to 1.3 And more preferably in the range of more than 1 and 1.2 or less) That. When the ratio of the NCO / NCO reactive group is too large (for example, exceeding 1.5 (equivalent ratio)), the storage stability of the lightweight filling repair material tends to be lowered. On the other hand, if the ratio of the NCO / NCO reactive group is too small (for example, 1 or less (equivalent ratio)), it becomes difficult to introduce a silyl group, and the toughness, warm water resistance, and water resistance decrease. Tend to.

  The polyisocyanate compound (A3) has an isocyanate group content in the anionic group-containing polymer of 0.3 to 7.0% by mass (preferably 0.3 to 5.0% by mass, more preferably 1). (0.0-3.0 mass%). By adjusting the content of the isocyanate group to be within the above range, toughness, warm water resistance, and water resistance can be improved.

  Furthermore, the isocyanate-reactive compound (A2) has an anionic group content in the anionic group-containing alkoxysilyl group-terminated polymer (A) of 0.2 to 5.0% by mass (preferably 0.5 to 4). (0.0 mass%, more preferably 0.8-3.5 mass%). When there is too much content of this anionic group (for example, it exceeds 5.0 mass%), while the viscosity of a lightweight filling repair material will become high and workability | operativity will fall, warm water resistance and water resistance after hardening are also good. There is a tendency to decrease. On the other hand, when there is too little content of this anionic group (for example, it is less than 0.2 mass%), there exists a tendency for the dispersion stability of the binder component in a lightweight filling repair material to fall.

  Furthermore, in the isocyanate-reactive group-containing alkoxysilane compound (A4), the silicon atom content in the anionic group-containing alkoxysilyl group-terminated polymer (A) is 0.05 to 1.0% by mass (preferably 0). 0.1 to 0.8% by mass, and more preferably 0.2 to 0.6% by mass). When the silicon content is too large (for example, exceeding 1.0% by mass), the storage stability of the lightweight filling repair material is lowered, while when it is too small (for example, less than 0.05% by mass). ), The toughness, warm water resistance, and water resistance of the lightweight filling repair material tend to decrease.

  When the unsaturated carboxylic acid ester (A5) is used, it is desirable that the amount used of the ester-modified amino group-containing alkoxysilane (A4-5) is an amount that leaves at least one secondary amino group. For example, it can be selected from a range of about 0.8 to 2 moles with respect to 1 mole of the primary amino group and the secondary amino group in the primary amino group-containing alkoxysilane. The unsaturated carboxylic acid ester can be used after being reacted under the condition that at least the secondary amino group remains.

[Water (B)]
In the present invention, as water (B), for example, tap water, ion-exchanged water, pure water or the like can be used. And the hardening rate of a lightweight filling repair material can be adjusted by adjusting the usage-amount of water. In the present invention, it is preferable to use water so that the nonvolatile content in the lightweight filling repair material is, for example, 20 to 60% by mass (preferably 30 to 55% by mass). As a result, it is possible to achieve an appropriate fluidity and an appropriate curing speed, so that a light filling repair material that is light in spatula and can be applied without hurrying and has excellent workability can be obtained. .

[Inorganic hollow powder (C)]
In this invention, an inorganic hollow powder is contained as a filler. The hydroxyl group on the surface of the inorganic hollow powder can react with the silyl group of the anionic group-containing alkoxysilyl group-terminated polymer (A) to be firmly bonded. Therefore, a strong three-dimensional crosslinked structure can be formed, and a cured product having excellent toughness, weather resistance, warm water resistance, and water resistance can be obtained. As the inorganic hollow powder, it is preferable to use one having a true specific gravity of, for example, 0.10 to 0.60, preferably 0.15 to 0.40, particularly preferably 0.20 to 0.40. Thereby, the specific gravity of a lightweight filling repair material can be reduced, and workability | operativity can be improved.

  In addition, the average particle size (by observation with an electron microscope) of the inorganic hollow powder can be appropriately selected and used depending on the application, and is, for example, about 10 to 150 μm, preferably about 20 to 70 μm. If the average particle size of the inorganic hollow powder exceeds the above range, the fluidity of the light weight filling repair material tends to decrease, and it becomes difficult to use the spatula to squeeze into the repaired part. On the other hand, if the average particle size of the inorganic hollow powder is less than the above range, it becomes difficult to maintain a three-dimensional cross-linked structure as the water evaporates, which tends to cause meat fraying.

  Examples of the inorganic hollow powder in the present invention include silica balloon, shirasu balloon, glass balloon, pearlite foam and the like. In the present invention, it is preferable to use a glass balloon having excellent heat resistance and strength, low dielectric constant, and low thermal conductivity.

  In the present invention, for example, commercially available products such as trade name “Glass Bubbles” (manufactured by Sumitomo 3M Co., Ltd.) and trade name “Fuji Balloon” (manufactured by Fuji Silysia Chemical Ltd.) can be suitably used. .

[Lightweight filling repair material]
The lightweight filling repair material according to the present invention contains the component (A), the component (B), and the component (C), and the specific gravity is less than 1 (for example, 0.3 or more and less than 1, preferably 0.3 to 0.7, particularly preferably 0.3 to 0.5).

  As a method for preparing a lightweight filling repair material according to the present invention, it can be prepared by mixing the components (A), (B), and (C), and the order of mixing is particularly limited. However, it is preferable to promote the reaction such as the hydrolysis reaction by blending the component (B) and the component (C) with the component (A) and vigorously stirring.

  As content of (A) component in a lightweight filling repair material, it is about 1.0-20.0 mass%, for example, Preferably it is 3.0-15.0 mass%, Especially 4.0-15.0 mass. % Is preferred. When the content of the component (A) is below the above range, curing takes too much time, workability tends to be reduced, and it is difficult to prevent the occurrence of meat fraying and cracking, and the weather resistance is lowered. Tend to. On the other hand, when content of (A) component exceeds the said range, there exists a tendency for fluidity | liquidity to fall and workability | operativity to fall, and there exists a tendency for the water resistance of a hardened | cured material, and warm water resistance to fall.

  As content of (B) component in a lightweight filling repair material, it is about 30.0-70.0 mass%, for example, Preferably it is 40.0-70.0 mass%, Especially 45.0-65.0 mass. % Is preferred. When content of (B) component is less than the said range, fluidity | liquidity will become low too much and it will become difficult to apply | coat using a spatula. In addition, since curing proceeds too quickly, there is a tendency that the workable time becomes too short. On the other hand, when the content of the component (B) exceeds the above range, the fluidity becomes too high, and it becomes difficult to apply using a spatula. In addition, since the curing rate is slow and it takes too much time to cure, workability tends to be reduced.

  As content of (C) component in a lightweight filling repair material, about 20.0-50.0 mass% is preferable, for example, Preferably 25.0-50.0 mass% is preferable. When content of (C) component is less than the said range, there exists a tendency for fluidity | liquidity to fall and workability | operativity to fall, and there exists a tendency for the water resistance of a hardened | cured material and warm water resistance to fall. On the other hand, if the content of the component (C) exceeds the above range, curing takes too much time, workability tends to be reduced, and it becomes difficult to prevent the occurrence of meat fraying and cracking, and weather resistance. Tends to decrease.

  In addition to the component (A), the component (B), and the component (C), other additives may be used as necessary for the lightweight filling repair material according to the present invention. Examples of other additives include fillers other than the above inorganic hollow powder, thickeners, antifoaming agents, plasticizers, anti-aging agents, ultraviolet absorbers, antioxidants, thermal stabilizers, colorants (pigments) And fungicides, wetting accelerators, viscosity improvers, fragrances, various tackifiers (emulsion tackifiers, etc.), coupling agents (titanate coupling agents, aluminum coupling agents, etc.), photocuring catalysts , Emulsifiers, surfactants, emulsions, latexes, various additives or components such as crosslinking agents, organic solvents, and the like.

  Examples of fillers other than the inorganic hollow powder include calcium carbonate and calcium carbonate that has been subjected to various treatments, fumed silica, clay, talc, various balloons, noble silica, kaolin, aluminum silicate, etc. Preferred). These can be used within a range where the specific gravity of the lightweight filling repair material is less than 1, for example, 20% by mass or less, particularly 15% by mass or less, preferably 5 to 15% in the lightweight filling repair material. Mass% is preferred. Within the above range, when calcium carbonate or the like is used in combination with the inorganic hollow powder, the specific gravity of the lightweight filling repair material can be maintained at less than 1, so that toughness can be enhanced while maintaining excellent workability. It is possible to improve hardness and hot water resistance.

  Examples of the thickener include hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like. By adding a thickener, the lightweight filling repair material can be wetted, the ironing into the repaired portion can be facilitated, the spatula can be lightened, and workability can be improved.

  Examples of the plasticizer include phthalic acid esters such as dioctyl phthalate and dibutyl phthalate; and aliphatic carboxylic acid esters such as dioctyl adipate and dibutyl sebacate.

  Examples of the tackifier include emulsion tackifiers such as stabilized rosin ester, polymerized rosin ester, terpene phenol, and petroleum resin.

  Examples of the crosslinking agent that can be used include an isocyanate crosslinking agent, an epoxy crosslinking agent, a carbodiimide crosslinking agent, an aziridine crosslinking agent, a polyethyleneimine crosslinking agent, a melamine crosslinking agent, and colloidal silica.

  The lightweight filling repair material according to the present invention may be completely aqueous without any organic solvent, but for viscosity adjustment and the like, (A) component, (B) component, (C) component and the like A compatible hydrophilic organic solvent (water-soluble organic solvent) may be contained.

  The lightweight filling repair material according to the present invention contains an anionic group-containing alkoxysilyl group-terminated polymer (A) as a binder, water (B), and an inorganic hollow powder (C) as a filler. Until the coating is applied to the part, the silyl group in the anionic group-containing alkoxysilyl group-terminated polymer (A) reacts with water to form a highly reactive silanol group, but remains stable. The reason is not clear, but silanol groups are protected by water molecules present in a large amount in the system, so that condensation reaction between silanol groups is suppressed or prevented, and / or silanol groups are isocyanates. Bonded to the primary or secondary amino group nitrogen atom derived from the primary or secondary amino group-containing alkoxysilane (A4-1) as the reactive group-containing alkoxysilane compound (A4) This is considered to be because the condensation reaction between the silanol groups is suppressed or prevented by being protected by a substituent (for example, a long-chain substituent derived from the unsaturated carboxylic acid ester (A5) or its ester moiety). It is.

  And by applying to the part to be repaired, moisture evaporates, silanol groups undergo dehydration condensation reaction, and at the same time, the hydroxyl groups present on the surface of the inorganic hollow powder are strongly bonded, so A three-dimensional network crosslinked structure can be formed and cured. For this reason, the obtained cured product is excellent in toughness without occurrence of meat fraying and cracking even when moisture is evaporated and dried. Moreover, the outstanding water resistance and warm water resistance can be exhibited. Therefore, the lightweight filling repair material according to the present invention can be suitably used as a repair material around water such as a bathroom. In addition, since the inorganic hollow powder is used as the filler, the specific gravity can be less than 1. Therefore, since the spatula is light and can be easily applied, workability is excellent. Furthermore, since it is a water-based type (in particular, it may be completely water-free without any organic solvent), it is excellent in handling and workability, and is highly safe for the human body and the environment.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples.

Production Example 1 (Preparation of terminal alkoxysilylated anionic group-containing urethane prepolymer)
In a four-necked separable flask equipped with a stirrer, nitrogen inlet tube, thermometer and condenser, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane (trade name “KBM602”, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 mol of 2-ethylhexyl acrylate was mixed with respect to 1 mol and reacted at 50 ° C. for 7 days to obtain an ester-modified amino group-containing alkoxysilane compound.
In a similar four-necked separable flask different from the above, polyoxytetramethylene glycol (trade name “PTMG2000”, manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 2000, hydroxyl value: 56.1 mg-KOH / g) 150 Parts by mass, N, N-bis (2-hydroxyethyl) -N-methylamine (N-methyldiethanolamine) (trade name “aminoalcohol MDA”, manufactured by Nippon Emulsifier Co., Ltd., molecular weight: 119.16, hydroxyl value: 941. 6 mg-KOH / g) 12 parts by mass, 2,2-dimethylolbutanoic acid (hydroxyl value: 758.1 mg-KOH / g) 25 parts by mass, isophorone diisocyanate [isocyanate content (NCO content): 37.8% ] 91 parts by mass, 17 parts by mass of triethylamine, and 100 parts by mass of methyl ethyl ketone, 80 to 85 ° C. Performed under a nitrogen stream for 5 hours at a temperature, a carboxyl group-containing isocyanate-terminated urethane prepolymer was obtained a reaction mixture containing (residual isocyanate group content of 2.0 wt%) of (1).
After blending and mixing 15 parts by mass of the previously obtained ester-modified amino group-containing alkoxysilane compound with the total amount of the reaction mixture (1), the reaction is performed at a temperature of 75 to 80 ° C. for 1 hour under a nitrogen stream. Further, 540 parts by mass of deionized water was added and dispersed. Thereafter, methyl ethyl ketone was distilled off at 45 to 50 ° C. under reduced pressure, and a binder containing terminal alkoxysilylated carboxyl group-containing urethane prepolymer (carboxyl group content: 2.41% by mass, silicon atom content) : 0.27% by mass, sometimes referred to as “SU”).

Production Example 2 (Preparation of anionic group-containing acrylic emulsion)
31 parts by weight of butyl acrylate, 26 parts by weight of methyl methacrylate, 1 part by weight of acrylic acid, 2 parts by weight of an anionic emulsifier (trade name “Perex SSH”, manufactured by Kao Corporation), a nonionic emulsifier (trade name “Emulgen 930”) 2 parts by weight of Kao Co., Ltd.), 0.1 part by weight of ammonium persulfate, and 38 parts by weight of water, and emulsion polymerization by a conventional method to obtain an acrylic polymer emulsion (solid content: 60%, pH) : 4, sometimes referred to as “acrylic Em”).

The materials used in the examples and comparative examples are as follows.
[filler]
Inorganic hollow powder Product name “Glass Bubbles S22” (glass balloon, average particle size: 30 μm, true specific gravity: 0.22), product name “Fuji Balloon S35” (glass balloon, average particle size, manufactured by Sumitomo 3M Limited) : 40 μm, true specific gravity: 0.35), manufactured by Fuji Silysia Chemical Co., Ltd. Calcium carbonate Product name “Shiraka Hana CCR-B”, manufactured by Shiraishi Calcium Co., Ltd.

[binder]
Product name "Cirrus PC-751" (terminal alkoxysilylated anionic group-containing acrylic emulsion), manufactured by Toagosei Co., Ltd.

[Commercially available filling repair materials used in comparative examples]
Product name "ONE TIME" (acrylic emulsion), Red Devil product name "Super Putty" (acrylic emulsion), Asahi Pen Co., Ltd. Product name "Flat One" (acrylic emulsion), Kansai Putty Chemicals Co., Ltd. Name "Seal Putty" (acrylic emulsion), manufactured by Yayoi Chemical Industry Co., Ltd.

Examples 1-3, Comparative Examples 1-6
It mixed by the composition (mass%) shown in following Table 1, and the filling repair material was obtained. About the obtained filling repair agent, it evaluated by the following method.

Evaluation method [State immediately after production]
The filling repair materials obtained in the examples and comparative examples were visually observed and evaluated according to the following criteria.
Evaluation criteria ○: Uniform and smooth state ×: Crunchy state or moisture floating state

[Workability of filling]
The workability when the filling repair materials obtained in Examples and Comparative Examples were filled in a hole (diameter: 1 cm) formed in a gypsum board was evaluated according to the following criteria.
Evaluation criteria ○: Can be easily taken out from the container, smoothly applied to the hole, and does not collapse after filling. ×: It is difficult to remove from the container, difficult to enter the hole, or collapse after filling due to stickiness or crunchiness.

[Hera judgment]
About the filling repair material obtained by the Example and the comparative example, the spatula judgment at the time of carrying out filling construction to the hole (diameter: 1 cm) drilled in the gypsum board was evaluated according to the following reference | standard.
Evaluation criteria ○: Light and non-uniformity ×: Heavy or uneven with a spatula

[Meat Yase]
The filled repair materials obtained in the examples and comparative examples were filled in a polyethylene container having a diameter of 3 cm and a depth of 6 mm, left standing at 23 ° C. and 50% RH for 24 hours, then visually observed, and evaluated according to the following criteria: did.
Evaluation criteria ○: No meat fraying or cracking ×: Meat fraying or cracking seen

[hardness]
The filled repair materials obtained in the examples and comparative examples were filled in a polyethylene container having a diameter of 3 cm and a depth of 6 mm, and left at 23 ° C. and 50% RH for 24 hours, and then a type A durometer in accordance with JIS K 6253 was used. Used to measure hardness.

[Water and warm water resistance]
The filling repair materials obtained in the examples and comparative examples were applied on a slate plate so that the width was about 20 mm × length 30 mm × thickness 3 mm, and allowed to cure at 23 ° C. and 50% RH for 24 hours. After that, the whole slate plate is immersed in 23 ° C. water or 50 ° C. warm water for 24 hours, and the state of the cured product taken out of the water is observed visually and by finger biting, and the heat resistance and water resistance are evaluated according to the following criteria. did.
Evaluation criteria ◎: Does not contain water, no change at all ○: Almost no change △: Slightly contains water, or partly collapses ×: Contains much water, or collapses more than half Have

Claims (5)

A lightweight filling repair material comprising the following component (A), component (B), and component (C) and having a specific gravity of less than 1.
(A) Anionic group-free and plural isocyanate-reactive group-containing compound (A1), anionic group and plural isocyanate-reactive group-containing compound (A2), polyisocyanate compound (A3), and isocyanate reactivity Anionic group-containing alkoxysilyl group-terminated polymer obtained by reacting group-containing alkoxysilane compound (A4) (B) Water (C) Inorganic hollow powder   The lightweight filling repair material according to claim 1, wherein the anionic group-containing alkoxysilyl group-terminated polymer is an anionic group-containing alkoxysilyl group-terminated urethane prepolymer.   The lightweight filling repair material according to claim 1 or 2, wherein the anionic group is a carboxyl group.   (C) The true specific gravity of inorganic hollow powder is 0.10-0.60, The lightweight filling repair material in any one of Claims 1-3.   The lightweight filling repair material according to any one of claims 1 to 4, wherein the nonvolatile content is 20 to 60% by mass.