JP5394545B2 - Polyurethane sealant and polyol composition used therefor - Google Patents

Description

  The present invention relates to a polyurethane sealant and a polyol composition used therefor.

  A polyurethane resin is a resin having a urethane bond that uses a polyol component and a polyisocyanate component as raw materials, and is generally an elastic resin rich in stretchability, and is used for a sealant for construction or waterproofing. The physical property items indicating the properties of polyurethane-based sealants include break elongation, which represents the degree of elongation at break when the resin is stretched until it breaks, and break strength, which represents the stress at break, and the greater these values, the greater the elongation. It can be said to be a tough sealant that is easy to break. The elongation at break and the strength at break are adjusted by changing the molecular weight and the number of functional groups of the polyol, which is a raw material of the polyurethane resin. However, the elongation at break and the strength at break are generally conflicting items (for example, see Non-Patent Document 1). ). Specifically, an increase in the urethane bond concentration due to a decrease in the molecular weight of the polyol, which is a measure for improving the breaking strength, or an increase in the crosslinking density due to an increase in the number of functional groups of the polyol, the resulting resin becomes rigid and the elongation at break decreases. If the elongation at break can be improved while improving the breaking strength of the polyurethane-based sealant, a sealant having excellent durability is obtained and the application range is expanded. Therefore, a polyurethane-based sealant capable of achieving both high breaking strength and high breaking elongation is desired.

"The latest polyurethane design / modification and advanced technology collection", 1st edition, Technical Information Association, March 2007, p84-85

  An object of the present invention is to provide a polyurethane-based sealant having excellent mechanical properties such as elongation at break and strength at break and a polyol composition capable of producing the same.

As a result of intensive studies to achieve the above object, the present inventors have obtained a polyurethane sealant having high mechanical properties (breaking elongation and breaking strength) by using a polyol for producing a polyurethane sealant having a specific structure. The present invention has been found. That is, the present invention relates to a compound (S) represented by the general formula (1) and a polyol (a1) other than (S) having a hydroxyl value of 20 to 2000 mgKOH / g and a molar average functional group number of 2 to 8. A polyol composition (A) for a polyurethane sealant characterized by containing a main component containing a polyisocyanate component (I) and a curing agent containing an active hydrogen component (H). And / or (2), a two-component curable urethane sealant;
(1) The polyisocyanate component (I) contains a urethane prepolymer or urethane prepolymer composition having an isocyanate group at the terminal obtained by reacting the polyol composition (A) with the organic polyisocyanate (B). To do.
(2) The active hydrogen component (H) contains the polyol composition (A).
A one-component curable urethane containing a urethane prepolymer or urethane prepolymer composition having an isocyanate group at the terminal obtained by reacting the polyol composition (A) with the organic polyisocyanate (B). System sealant;

[In the general formula (1), X ¹ represents a residue obtained by removing c active hydrogens from an m-valent active hydrogen-containing compound; c represents an integer satisfying 1 ≦ c ≦ m; X ² represents a residue obtained by removing one active hydrogen from an active hydrogen-containing compound, a plurality of X ² may be the same or different, and X ² and X ¹ may be the same or different Y represents a residue obtained by removing all carboxyl groups from a trivalent or higher valent aromatic polycarboxylic acid, and the aromatic ring of Y is composed of carbon atoms, and the carbon atoms are substituted with other than carboxyl groups. A group and / or a halogen atom may be bonded, but at least one carbon atom is not bonded to a substituent; a represents an integer of 1 or more, b represents an integer of 0 or more, and 2 ≦ a + b ≦ d−2 is satisfied; d is the carbo of the aromatic polycarboxylic acid. This represents the number of hydrogen atoms bonded to the carbon atom constituting the aromatic ring when all the substituents including the xyl group are substituted with hydrogen atoms, that is, the number of sites that can be substituted on the aromatic ring. ]

  By using the polyol composition of the present invention, a polyurethane sealant having excellent mechanical properties such as elongation at break and strength at break can be obtained.

  The polyol composition (A) used for the polyurethane-based sealant of the present invention contains a polyol (a1) other than the compounds (S) and (S) represented by the general formula (1).

  The compound (S) represented by the general formula (1) is composed of a compound (S1) having at least one active hydrogen and (S2) having no active hydrogen.

When the compound (S1) is used in the polyol composition (A), the compound (S1) is incorporated into the molecular skeleton of the polyurethane resin after curing of the polyurethane sealant using (A), thereby obtaining the predetermined effect. Play. When compound (S2) is used in (A), (S2) is not incorporated into the molecular skeleton of the polyurethane resin after curing of the polyurethane sealant using (A), and the polyurethane resin and compound (S2) are combined. The resulting polyurethane resin composition contains the same effects as when (S1) is incorporated into the polyurethane resin.
Compound (S1) and (S2) may be used individually by 1 type, and may use 2 or more types together.

  Hereinafter, although the compound (S) represented by the general formula (1) will be described, the composition and numerical values described as a preferred range as the compound (S) have at least one active hydrogen incorporated into the polyurethane resin. The case of the compound (S1) and the case of the compound (S) used in the polyurethane resin composition are the same unless otherwise specified.

X ¹ in the general formula (1) represents a residue obtained by removing c active hydrogens from an m-valent active hydrogen-containing compound.

  Examples of the active hydrogen-containing compound include a hydroxyl group-containing compound, ammonia, an amino group-containing compound, and a thiol group-containing compound. An active hydrogen containing compound may be used individually by 1 type, or may use 2 or more types together.

  Examples of the hydroxyl group-containing compound include monovalent alcohols having 1 to 20 carbon atoms, polyhydric alcohols having 2 to 20 carbon atoms, phenols, and alkylene oxide (hereinafter abbreviated as AO) adducts.

  Examples of monohydric alcohols having 1 to 20 carbon atoms include alkanols having 1 to 20 carbon atoms (methanol, ethanol, butanol, octanol, decanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, etc.), and those having 2 to 20 carbon atoms. Alkenol (oleyl alcohol, linoleyl alcohol, etc.), aromatic aliphatic alcohol having 7 to 20 carbon atoms (benzyl alcohol, naphthyl ethanol, etc.) and the like can be mentioned.

  The polyhydric alcohol having 2 to 20 carbon atoms includes a dihydric alcohol having 2 to 20 carbon atoms [aliphatic diol (ethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol). , Neopentyl glycol and 1,10-decanediol, etc.), alicyclic diols (cyclohexanediol and cyclohexanedimethanol etc.) and araliphatic diols [1,4-bis (hydroxyethyl) benzene etc.] etc.], carbon 3 to 20 trihydric alcohols [aliphatic triols (such as glycerin and trimethylolpropane)] and 4 to 8 carbon atoms having 5 to 20 carbons [aliphatic polyols (pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin) And dipentaerythritol, etc.) and sugars (sho , Glucose, mannose, fructose, methyl glucoside and derivatives thereof)], and the like.

  Examples of the phenols include monovalent phenols (phenol, 1-hydroxynaphthalene, anthrol, 1-hydroxypyrene, etc.) and polyhydric phenols (phloroglucin, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1 , 3,6,8-tetrahydroxynaphthalene, 1,4,5,8-tetrahydroxyanthracene, a condensate of phenol and formaldehyde (novolak) and polyphenols described in US Pat. No. 3,265,641].

  Examples of amino group-containing compounds include monohydrocarbylamines having 1 to 20 carbon atoms [alkylamines (such as butylamine), benzylamine and aniline], aliphatic polyamines having 2 to 20 carbon atoms (ethylenediamine, hexamethylenediamine, diethylenetriamine, etc.) ), Alicyclic polyamines having 6 to 20 carbon atoms (such as diaminocyclohexane, dicyclohexylmethanediamine and isophoronediamine), aromatic polyamines having 2 to 20 carbon atoms (such as phenylenediamine, tolylenediamine and diphenylmethanediamine), and 2 carbon atoms. ~ 20 heterocyclic polyamines (such as piperazine and N-aminoethylpiperazine), alkanolamines (such as monoethanolamine, diethanolamine and triethanolamine), dicarboxylic acids and excess polyamines Polyamide polyamine, polyether polyamine obtained by condensation, hydrazine (such as hydrazine and monoalkylhydrazine), dihydrazide (such as succinic acid dihydrazide and terephthalic acid dihydrazide), guanidine (such as butylguanidine and 1-cyanoguanidine) and dicyandiamide .

  Examples of the thiol group-containing compound include monovalent thiol compounds having 1 to 20 carbon atoms (alkanethiol such as ethanethiol, benzenethiol and phenylmethanethiol) and polyvalent thiol compounds (1,2-ethanedithiol and 1,6 -Hexanedithiol etc.).

  In addition, as an active hydrogen containing compound, the compound which has 2 or more types of active hydrogen containing functional groups (a hydroxyl group, an amino group, a thiol group, etc.) in a molecule | numerator can also be used.

  Moreover, as the active hydrogen-containing compound, an alkylene oxide AO adduct of the active hydrogen-containing compound can also be used.

  As AO added to the active hydrogen-containing compound, AO having 2 to 4 carbon atoms such as ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO), 1,3-propylene. Examples thereof include oxide, 1,2-, 1,3- or 2,3-butylene oxide and tetrahydrofuran (hereinafter abbreviated as THF). Of these, EO, PO and THF are preferred from the viewpoint of breaking strength. AO may be used alone or in combination of two or more. As an addition method when two or more of AO are used in combination, block addition or random addition may be used. It may be used in combination.

The number of added moles of AO is preferably 8 to 100, more preferably 10 to 80, from the viewpoint of breaking strength. The hydroxyl value of the AO adduct is preferably 18 to 360 mgKOH / g.
In the present invention, the hydroxyl value is measured according to JIS K1557-1.

As the active hydrogen-containing compound for introducing X ¹ into the compound (S), preferred from the viewpoint of the breaking elongation and breaking strength of the sealant are a hydroxyl group-containing compound, an amino group-containing compound, and an AO adduct thereof. Preferred is a polyether polyol obtained by adding AO to a polyhydric alcohol having 2 to 20 carbon atoms and a polyhydric alcohol having 2 to 20 carbon atoms, an aliphatic polyamine having 2 to 20 carbon atoms and a polyvalent thiol compound, particularly preferred. Is a polyhydric alcohol having 2 to 20 carbon atoms and a polyether polyol obtained by adding AO to a polyhydric alcohol having 2 to 20 carbon atoms, and most preferably a polyether having AO added to a polyhydric alcohol having 2 to 20 carbon atoms. It is a polyol.

  The valence m of the active hydrogen-containing compound is usually 1 to 20, preferably 1 to 8, more preferably 1 to 4, particularly preferably 2 from the viewpoint of the elongation at break and the breaking strength of the sealant.

  C in the general formula (1) represents an integer satisfying 1 to 20 and 1 ≦ c ≦ m, and preferably 1 to 8, more preferably 1 to 4, particularly from the viewpoint of the breaking elongation and breaking strength of the sealant. Preferably it is 2.

X ² in the general formula (1) represents a residue obtained by removing one active hydrogen from a 1-20 valent active hydrogen-containing compound, and the plurality of X ² may be the same or different.
Examples of the active hydrogen-containing compound used to constitute X ² include the same compounds as the active hydrogen-containing compound represented by X ¹ above, and X ² and X ¹ may be the same or different, From the viewpoint of breaking elongation and breaking strength of the sealant, X ¹ and at least one X ² are preferably different groups.
The valence of X ² is usually 1 to 20, preferably 1 to 8, more preferably 1 to 4, particularly preferably 1 to 2, and most preferably 2 from the viewpoint of the breaking elongation and breaking strength of the sealant. It is.

Although it is possible to introduce the X ¹ and X ² in the compound (S) by reacting the active hydrogen-containing compound to the trivalent or higher polycarboxylic acids used to construct the Y described below, X ¹ and In the case where X ² is a diol having 2 to 4 carbon atoms or a polyether polyol having 2 to 4 carbon atoms in the repeating unit, it is equivalent by adding the AO having 2 to 4 carbon atoms to the carboxyl group of the polycarboxylic acid. Can be obtained.

  Y in General formula (1) represents the residue remove | excluding all the carboxyl groups from trivalent or more aromatic polycarboxylic acid. The aromatic ring of Y is composed of carbon atoms, and a substituent other than a carboxyl group and / or a halogen atom may be bonded to the carbon atom, but at least one carbon atom is not bonded to a substituent. Must be bonded to a hydrogen atom.

  Examples of the substituent other than the carboxyl group include an alkyl group, vinyl group, allyl group, cycloalkyl group, amino group, hydroxyl group, hydroxyamino group, nitro group, thiol group, aryl group, and cyano group.

Examples of the trivalent or higher valent aromatic polycarboxylic acid used for constituting Y include aromatic polycarboxylic acids having 9 to 30 carbon atoms such as trimellitic acid, 1,2,3-benzenetricarboxylic acid, trimesic acid, Hemicitic acid, 1,2,4-, 1,3,6- or 2,3,6-naphthalenetricarboxylic acid and tricarboxylic acids such as 2,3,6-anthracentricarboxylic acid; pyromellitic acid, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid, 2,2 ′, 3,3′-benzophenone tetracarboxylic acid, 2,3,3 ′, 4′-benzophenone tetracarboxylic acid, 3,3 ′, 4,4′- Biphenyltetracarboxylic acid, 2,2 ′, 3,3′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 4,4′-oxybisphthalic acid, diphenylmethane Tracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid and 4,4 ′-(hexa) And tetracarboxylic acids such as fluoroisopropylidene) bisphthalic acid. Aromatic polycarboxylic acid may be used individually by 1 type, and may use 2 or more types together.
In producing the compound (S), these ester-forming derivatives [acid anhydrides, lower alkyl (carbon number 1 to 4) esters (methyl esters, ethyl esters, isopropyl esters, etc.) and acid halides (acid chlorides) Etc.)] can also be used.

  Of these aromatic polycarboxylic acids, from the viewpoint of the breaking elongation and breaking strength of the sealant, two that form the aromatic ring adjacent to the carbon atom to which the substituent is not bonded and that form the aromatic ring are preferable. Are preferably those having a structure in which a carboxyl group is bonded to each of the carbon atoms, more preferably a structure in which one carboxyl group is further bonded to at least one of the carbon atoms adjacent to the carbon atom to which the carboxyl group is bonded. It is what you have.

  For example, when the aromatic ring of the aromatic polycarboxylic acid is a benzene ring, the aromatic polycarboxylic acid preferably has a structure in which a carboxyl group is bonded to the 1-position and the 3-position, and more preferably, the 4-position of the benzene ring to which the carboxyl group is bonded and It has a structure in which a carboxyl group is further bonded to the 6-position.

  From the viewpoint of breaking elongation and breaking strength of the sealant, monocyclic compounds are particularly preferred as the aromatic polycarboxylic acid used for constituting Y, and trimellitic acid and pyromellitic acid are most preferred.

  In the general formula (1), a represents an integer of 1 or more, b represents an integer of 0 or more, and 2 ≦ a + b ≦ d−2 is satisfied, and d includes all carboxyl groups of the aromatic polycarboxylic acid. Represents the number of hydrogen atoms bonded to the carbon atom constituting the aromatic ring, that is, the number of sites that can be substituted on the aromatic ring. For example, when the aromatic ring is a benzene ring composed of 6 carbon atoms, d is 6, a + b can take a value of 2 to 4, and when the aromatic ring is a naphthalene ring composed of 10 carbon atoms, d is 8, and a + b can take a value of 2-6. When the aromatic ring is a monocyclic aromatic ring, a + b is preferably 2 or 3 from the viewpoint of the breaking elongation and breaking strength of the sealant. Further, from the viewpoint of the breaking elongation and breaking strength of the sealant, b is preferably 1/2 or less of a, particularly preferably 0.

The hydroxyl value of the compound (S) in the present invention is preferably 0 or 70 to 500 mg KOH / g from the viewpoint of the breaking elongation and breaking strength of the sealant, and more preferably 75 to 350 mg KOH / g when (S) has a hydroxyl group. It is. When (S) has a hydroxyl group, when the hydroxyl value is less than 70 mgKOH / g, the breaking strength of the sealant tends to decrease, and when it exceeds 500 mgKOH / g, the breaking elongation of the sealant tends to decrease.
In addition, the hydroxyl value of compound (S) being 0 means that all of X ¹ , X ² and Y in the general formula (1) do not have a hydroxyl group.

  The concentration of Y in the compound (S) means the number of millimoles of the residue Y in 1 g of the compound (S), and preferably 1.0 to 3.5 mmol / g from the viewpoint of the breaking elongation and breaking strength of the sealant. More preferably, it is 1.1-3.4 mmol / g, Most preferably, it is 1.2-3.3 mmol / g. When the concentration of Y is less than 1.0 mmol / g, the breaking strength of the sealant tends to decrease, and when it exceeds 3.5 mmol / g, the elongation at break of the sealant tends to decrease.

  The carbonyl group concentration of the compound (S) is preferably 3.0 to 10.0 mmol / g, more preferably 3.0 to 9.7 mmol / g, and particularly preferably 3 from the viewpoint of the breaking elongation and breaking strength of the sealant. 0.0 to 9.5 mmol / g. When the carbonyl group concentration is less than 2.0 mmol / g, the breaking strength of the sealant tends to decrease, and when the carbonyl group concentration exceeds 10.0 mmol / g, the elongation at break tends to deteriorate. The carbonyl group at the carbonyl group concentration in the present invention is a carbonyl group bonded to Y in the general formula (1), that is, a carboxyl group of a trivalent or higher valent aromatic polycarboxylic acid used for introducing Y, and derived therefrom. A carbonyl group in a functional group such as an ester group, a thioester group and an amide group.

From the viewpoint of the mechanical strength of the sealant, the number of mole average functional groups of the compound (S) is preferably 2 to 8, more preferably 2 to 6, and particularly preferably 2 to 4.
The number of mole average functional groups in the present invention is a value obtained by dividing the sum of values obtained by multiplying the number of functional groups having active hydrogen of each component in the composition by the number of moles of each component by the sum of the number of moles of each component. The number of moles of each component is a value obtained by dividing the weight of each component by the molecular weight of each component. As the molecular weight used in the calculation, the chemical formula weight is used when the molecular weight is not distributed as in the case of a low molecular weight compound, and the number average molecular weight (hereinafter abbreviated as Mn) is used when the molecular weight is distributed. Mn of the compound (S) and polyol in the present invention is measured by gel permeation chromatography using THF as a solvent and polyoxypropylene glycol as a standard substance. The sample concentration is 0.25 wt%, the column stationary phase is styrene divinylbenzene [TSKgel Super H2000, 3000, 4000 (manufactured by Tosoh Corporation)], and the column temperature is 40 ° C.

The compound (S1) having at least one active hydrogen is a compound in which at least one of X ¹ , X ² and Y in the general formula (1) has an active hydrogen. More specifically, at least the valences x and c of X ¹ satisfy m> c, or Y is substituted with a substituent having an active hydrogen such as an amino group, a hydroxyl group, a hydroxyamino group and a thiol group, When the active hydrogen-containing compound constituting X ² is divalent or higher, or b is 1 or higher, the compound (S1) has at least one active hydrogen.

  The polyol (a1) contained in the polyol composition (A) of the present invention has a hydroxyl value of 20 to 2000 mgKOH / g, a molar average functional group number of 2 to 8, and a polyvalent number of 2 to 20 carbon atoms. Examples include alcohols, polyether polyols obtained by adding AO having 2 to 4 carbon atoms to the polyhydric alcohols having 2 to 20 carbon atoms, polyester polyols other than (S), and other polyols. A polyol (a1) may be used individually by 1 type, or may use 2 or more types together.

  Among the polyether polyols as the polyol (a1), AO is preferably EO, PO, 1,2-butylene oxide and / or THF from the viewpoint of breaking strength.

  As the polyester polyol, the polyhydric alcohol having 2 to 20 carbon atoms and / or the polyether polyol, the divalent to tetravalent aromatic polycarboxylic acid and / or the aliphatic polycarboxylic acid, and their anhydrides or lower alkyls ( An alkyl group having 1 to 4 carbon atoms and a condensation reaction product with an ester-forming derivative such as an ester other than the compound (S); an AO adduct thereof; a polylactone polyol [for example, the carbon number 2 Obtained by ring-opening polymerization of a lactone (ε-caprolactone or the like) using a polyhydric alcohol of ˜20]; and a polycarbonate polyol (for example, reaction of the polyhydric alcohol having 2 to 20 carbon atoms with an alkylene carbonate) Thing); etc. are mentioned.

  Examples of the divalent to tetravalent aromatic polycarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8- Naphthalenedicarboxylic acid, anthracene dicarboxylic acid, 4,4′-benzophenone dicarboxylic acid, 3,3′-biphenyl dicarboxylic acid, 4,4′-biphenyl dicarboxylic acid, 3,3′-biphenyl ether dicarboxylic acid, 4,4′- Examples thereof include aromatic dicarboxylic acids having 8 to 30 carbon atoms such as biphenyl ether dicarboxylic acid and 4,4′-binaphthyl dicarboxylic acid, and the above trivalent or tetravalent aromatic polycarboxylic acids.

  Examples of the divalent to tetravalent aliphatic polycarboxylic acid include oxalic acid, succinic acid, malonic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, itaconic acid, tricarbaryl. Examples thereof include aliphatic polycarboxylic acids having 2 to 30 carbon atoms such as acid and hexanetricarboxylic acid.

  Examples of other polyols include monocyclic polyhydric phenols (pyrogallol, hydroquinone, phloroglucin, etc.) or bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) having 1 mol of AO added per hydroxyl group, silicone polyols, Examples thereof include polymer polyols, polydiene polyols (such as polybutadiene polyols), hydrogenated products of polydiene polyols, acrylic polyols, natural oil-based polyols (such as castor oil), and modified products of natural oil-based polyols.

  The hydroxyl value of the polyol (a1) is usually 20 to 2000 mgKOH / g, preferably 25 to 1900 mgKOH / g, from the viewpoint of the elongation at break and the breaking strength of the sealant. When the hydroxyl value is less than 20 mgKOH / g, the breaking strength of the sealant decreases, and when it exceeds 2000 mgKOH / g, the breaking elongation of the sealant deteriorates.

  The number of mole average functional groups of the polyol (a1) is preferably 2 to 8, more preferably 2 to 6, particularly preferably 2 to 4, and most preferably 2 from the viewpoint of elongation at break of the sealant.

  The content of the compound (S) is preferably 0.01 to 10% by weight, more preferably 0.015 to 8%, from the viewpoint of the breaking elongation and breaking strength of the sealant, based on the weight of the polyol composition (A). % By weight, particularly preferably 0.02 to 6% by weight.

  The content of the polyol (a1) is preferably 90 to 99.99% by weight, more preferably 92 to 99.985% by weight, particularly from the viewpoint of the elongation at break of the sealant based on the weight of the polyol composition (A). Preferably it is 94-99.98 weight%.

  The polyurethane sealant of the present invention has two forms, a two-component curable polyurethane sealant and a one-component curable polyurethane sealant.

The two-component curable polyurethane sealant of the present invention comprises a main agent containing a polyisocyanate component (I) and a curing agent containing an active hydrogen component (H), and satisfies the following (1) and / or (2). A sealant characterized by:
(1) Urethane prepolymer or urethane prepolymer composition having an isocyanate group at the terminal obtained by reacting the polyisocyanate component (I) with the polyol composition (A) of the present invention and the organic polyisocyanate (B). Containing;
(2) The active hydrogen component (H) contains the polyol composition (A) of the present invention.

  In the above (1), when the compound (S) contained in the polyol composition (A) is a compound (S1) having at least one active hydrogen, the terminal formed by the reaction of (A) and (B) The compound (S1) is incorporated into the molecular skeleton of the urethane prepolymer having an isocyanate group, and the compound (S1) is incorporated into the molecular skeleton of the polyurethane resin formed by two-component curing. When the compound (S) contained in the polyol composition (A) is a compound (S2) having no active hydrogen, the compound (S2) is not incorporated into the molecular skeleton of the urethane prepolymer having an isocyanate group at the terminal, The urethane prepolymer composition is composed of a prepolymer and (S2), and the compound (S2) is not incorporated into the molecular skeleton of the polyurethane resin formed by two-component curing, resulting in a polyurethane resin composition. However, in any of these cases, the predetermined effect of the present invention can be achieved.

  In the above (2), when the compound (S) contained in the polyol composition (A) is a compound (S1) having at least one active hydrogen, the compound ( S1) will be incorporated. When the compound (S) contained in the polyol composition (A) is a compound (S2) having no active hydrogen, the compound (S2) is not incorporated into the molecular skeleton of the polyurethane resin formed by two-component curing, and the polyurethane It becomes a resin composition. However, in any of these cases, the predetermined effect of the present invention can be achieved.

  The one-component curable polyurethane sealant of the present invention contains a urethane prepolymer having an isocyanate group at the terminal obtained by reacting the polyol composition (A) of the present invention with an organic polyisocyanate (B). And

  By using the polyol composition (A) as a constituent of the urethane prepolymer, when the compound (S) contained in (A) is a compound (S1) having at least one active hydrogen, a one-component curable polyurethane sealant In the case where the skeleton of the compound (S1) is incorporated in the polyurethane urea resin in the sealant after the moisture curing, and the compound (S) is a compound (S2) having no active hydrogen, the one-component curable polyurethane sealant is moisture. The compound (S2) is added to the cured sealant, and in any case, the effects of the present invention can be achieved.

  The ratio of the weight of the compound (S) to the total weight of the polyisocyanate component (I) in the main agent and the active hydrogen component (H) in the curing agent in the two-component curable polyurethane sealant is from the viewpoint of elongation at break and strength at break. The amount is preferably 1 to 10% by weight, more preferably 1 to 5% by weight.

  Compound (S) with respect to the total weight of the polyol composition (A) and the organic polyisocyanate (B), which is a raw material of the urethane prepolymer when producing a urethane prepolymer having an isocyanate group at the terminal in a one-component curable polyurethane sealant From the viewpoint of elongation at break and strength at break, the weight ratio is preferably 1 to 10% by weight, more preferably 1 to 5% by weight.

  The organic polyisocyanate (B) used for the main component of the two-component curable polyurethane-based sealant or the urethane prepolymer having an isocyanate group at the terminal in the one-component curable polyurethane-based sealant is generally an organic material used for the production of polyurethane resins. All polyisocyanates can be used, such as aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates and their modified products (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, etc. , Isocyanurate group and oxazolidone group-containing modified products).

These organic polyisocyanates (B) can also be used as a component of the polyisocyanate component (I), which is the main component of the two-component curable polyurethane sealant.
An organic polyisocyanate (B) may be used individually by 1 type, or may use 2 or more types together.

  Examples of the aromatic polyisocyanate include aromatic diisocyanates having 6 to 16 carbon atoms (excluding carbon in the NCO group; the following polyisocyanates are the same), aromatic triisocyanates having 6 to 20 carbon atoms, and those isocyanates. Examples include crude products. Specific examples include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4′- or 4,4′-diphenylmethane diisocyanate ( MDI), polymethylene polyphenylene polyisocyanate (crude MDI), naphthylene-1,5-diisocyanate, triphenylmethane-4,4 ′, 4 ″ -triisocyanate and the like.

  Examples of the aliphatic polyisocyanate include aliphatic diisocyanates having 6 to 10 carbon atoms (such as 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate).

  Examples of the alicyclic polyisocyanate include alicyclic diisocyanates having 6 to 16 carbon atoms (such as isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, and norbornane diisocyanate).

Examples of the araliphatic isocyanate include araliphatic diisocyanates having 8 to 12 carbon atoms (such as xylylene diisocyanate and α, α, α ′, α′-tetramethylxylylene diisocyanate).
Specific examples of the modified polyisocyanate include carbodiimide-modified MDI.

  Among these, aromatic polyisocyanates are preferable from the viewpoint of breaking strength, and TDI and MDI are more preferable.

  The urethane prepolymer having an isocyanate group at the terminal in the main component of the two-component curable polyurethane sealant or the one-component curable polyurethane sealant is usually an excess amount of an organic polyisocyanate (S) or the polyol composition (A) ( It is obtained by reacting with B). The R value (NCO / OH), which is the equivalent ratio of the isocyanate group of the organic polyisocyanate (B) and the hydroxyl group of the compound (S) or polyol composition (A), is preferably 1.1 to 3.0, more preferably It is 1.2 to 2.5, particularly preferably 1.8 to 2.2.

  The reaction method of the urethane prepolymer is not particularly limited. For example, (S) or (A), (B) and, if necessary, the curing accelerating catalyst (C1) are charged in a reaction tank having a temperature control function, A method of reacting by maintaining the temperature at 50 to 200 ° C. for 1,000 minutes, (S) or (A), and (B) and, if necessary, (C1) are supplied to the twin screw extruder, and the temperature is from 100 to The method of making it react continuously at 220 degreeC etc. are mentioned.

  As the curing accelerating catalyst (C1) used in the reaction of the urethane prepolymer, a metal catalyst [for example, tin-based catalyst (trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, stannous octet Ate and dibutyltin maleate), lead-based catalysts (lead oleate, lead 2-ethylhexanoate, lead naphthenate and lead octenoate, etc.), metal naphthenates such as cobalt naphthenate and phenylmercury propionate] Amine-based catalysts [e.g., triethylenediamine, tetramethylethylenediamine, tetramethylhexylenediamine, diazabicycloalkenes [1,8-diazabicyclo [5,4,0] -7-undecene {"DBU" manufactured by San Apro, Inc. (registered) Trademark)}] etc .; Killaminoalkylamines (dimethylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminoethylamine, dimethylaminooctylamine, dipropylaminopropylamine, etc.) or heterocyclic aminoalkylamines {2- (1-aziridinyl ) Ethylamine and 4- (1-piperidinyl) -2-hexylamine etc.} carbonate or organic acid salt (eg formate) etc .; N-methylmorpholine, N-ethylmorpholine, triethylamine, diethylethanolamine and dimethylethanolamine Etc.], and a mixture of two or more of these, etc. Among these catalysts, amine-based catalysts containing no heavy metal compounds are preferred.

  The NCO content% of the urethane prepolymer having an isocyanate group at the terminal in the main component of the two-component curable polyurethane sealant or the one-component curable polyurethane sealant is 0.3 to 10% by weight, preferably 1.0 to 3.0% by weight. %. If it is 0.3% by weight or more, the curing reaction tends to proceed quickly, and if it is 10% by weight or less, the curing reaction tends to be mild and foaming tends to be less.

  The curing agent of the two-component curable polyurethane sealant and the one-component curable polyurethane sealant can further contain a filler and a curing accelerating catalyst (C2).

  Examples of fillers include clay, heavy calcium carbonate, fatty acid-treated calcium carbonate, barium sulfate, alumina, silica, carbon black, calcium oxide, titanium oxide, diatomaceous earth, glass fiber and crushed materials thereof (cut Glass, milled glass, glass flake, etc.), talc, mica, shirasu balloon, and other inorganic fillers. The content of the filler is preferably 5 to 50% by weight, more preferably 10 to 30% by weight.

  As the curing accelerating catalyst (C2), those similar to the curing accelerating catalyst (C1) can be used, and preferred ones are also the same. The total amount of the curing accelerating catalysts (C1) and (C2) is preferably 1% by weight or less, more preferably 0, based on the weight of the whole sealant (in the case of a two-component curing type, the total amount of the main agent and the curing agent). 0.05% by weight or less, particularly preferably 0.01% by weight or less.

  In the polyurethane-based sealant of the present invention, the main component of a two-component curable polyurethane-based sealant for the purpose of improving the mixing property and workability by reducing the viscosity before curing, and imparting elasticity and flexibility to the cured sealant. And / or a curing agent and a one-component curable polyurethane-based sealant further containing at least one selected from the group consisting of a plasticizer, a diluent (thickening agent), an antioxidant, an ultraviolet absorber, and a thixotropic agent. You may let them.

  Examples of the plasticizer include ester plasticizers [dibutyl phthalate, dioctyl phthalate, dioctyl adipate and polyethylene glycol (weight average molecular weight: 200) diadipate, etc.], tar plasticizers (tar and asphalt, etc.) and petroleum resin plasticizers. It is done. The content of the plasticizer is preferably 5 to 5 on the basis of the total weight of the main agent and the curing agent in the case of the two-component curable type, and on the basis of the weight of the urethane prepolymer having an isocyanate group at the terminal in the case of the one-component curable type. 70% by weight is more preferably 15 to 50% by weight.

  Diluents (and thickeners) include aliphatic hydrocarbons such as n-hexane and n-heptane, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate, butyl acetate and cellosolve, acetone And solvents such as ketones such as methyl ethyl ketone and ethers such as diethylene glycol dimethyl ether and ethylene glycol dibutyl ether. The content is preferably 0 to 20% by weight based on the total weight of the main agent and the curing agent in the case of the two-component curable type, and based on the weight of the urethane prepolymer having an isocyanate group at the terminal in the case of the one-component curable type. More preferably, it is 0 to 5% by weight.

Antioxidants include hindered phenolic antioxidants [Irganox 1010 and Irganox 1076 (both manufactured by BASF Japan), etc.] and hindered amine antioxidants [Sanol LS770 and Sanol LS-744 (both manufactured by Sankyo). )].
The content of the antioxidant is preferably 0 based on the total weight of the main agent and the curing agent in the case of the two-component curable type, and based on the weight of the urethane prepolymer having an isocyanate group at the terminal in the case of the one-component curable type. 0.001 to 10% by weight, more preferably 0.01 to 5% by weight.

Examples of the ultraviolet absorber include triazole-based ultraviolet absorbers [Tinuvin 320 (manufactured by BASF Japan), etc.] and benzophenone-based ultraviolet absorbers [Siasorb UV9 (manufactured by Cyanamid), etc.].
The content of the ultraviolet absorber is preferably 0 on the basis of the total weight of the main agent and the curing agent in the case of the two-component curable type, and on the basis of the weight of the urethane prepolymer having an isocyanate group at the terminal in the case of the one-component curable type. 0.001 to 10% by weight, preferably 0.01 to 5% by weight.

  Examples of the thixotropic agent include colloidal silica, finely divided carbon black, fatty acid amide, and fatty acid metal soap. The content of the thixotropic agent is preferably based on the total weight of the main agent and the curing agent in the case of the two-component curable type, and based on the weight of the urethane prepolymer having an isocyanate group at the terminal in the case of the one-component curable type. It is 0 to 50% by weight, preferably 0 to 20% by weight.

  The method for producing the sealant of the present invention is not particularly limited. In the case of the one-component curable type, for example, a urethane prepolymer having an isocyanate group at the terminal obtained by reacting the polyol composition (A) and the organic polyisocyanate (B). In addition to fillers, plasticizers, diluents (thickening agents), antioxidants, UV absorbers and thixotropic agents as necessary, mixing equipment such as a planetary mixer with a vacuum device and three rolls is sufficient. After kneading, it is preferable to add the curing accelerating catalyst (C2) (in this case, the curing catalyst may be dissolved in a solvent such as toluene) and further kneaded sufficiently. In this case, it is preferable to carry out the process while removing moisture under reduced pressure. The pressure during decompression is preferably 1 to 70 kPa, more preferably 4 to 40 kPa. The mixing temperature is preferably 0 to 40 ° C, more preferably 10 to 30 ° C. The mixing time is preferably 30 minutes to 10 hours, more preferably 1 to 5 hours.

In the case of the two-component curing type, the main agent is a urethane prepolymer having an isocyanate group at the terminal obtained by reacting the compound (S) or polyol composition (A) with the organic polyisocyanate (B), and the organic polyisocyanate (B). ) If necessary. The mixing method is not particularly limited, but it is preferably performed in an inert gas atmosphere such as nitrogen.
The curing agent is, for example, an active hydrogen component (H) containing the polyol composition (A) and, if necessary, a filler, a curing accelerating catalyst (C2), a plasticizer, a diluent (thickening agent), an antioxidant, and an ultraviolet absorber. It can be obtained by adding the agent and the thixotropic agent and mixing well as in the case of the one-component curable type.

  The viscosity (25 ° C., B-type viscometer) of the one-component curable polyurethane sealant of the present invention is preferably 1 to 500 Pa · s, more preferably 20 to 200 Pa · s. In the case of the two-component curable type, the viscosity of the main agent is preferably 1 to 300 Pa · s, more preferably 10 to 200 Pa · s, and the viscosity of the curing agent is preferably 0.5 to 500 Pa · s, more preferably. Is 1 to 200 Pa · s.

  In the case of the two-component curable type, the mixing method of the main agent and the curing agent is not particularly limited, and they can be mixed and used by an ordinary method. The ratio (weight ratio) between the main agent and the curing agent is preferably 10:90 to 90:10, more preferably 30:70 to 70:30. The R value (NCO / OH), which is the equivalent ratio of the isocyanate group of the polyisocyanate component (I) in the main agent and the hydroxyl group of the active hydrogen component (H) in the curing agent, is preferably 0.8. It is -1.6, More preferably, it is 1.0-1.3.

  The method of using the polyurethane-based sealant of the present invention is not particularly limited. For example, the sealant is injected and cured in a liquid state in the gap between the target materials and the joint, and the material is sprayed and cured at the seam of the material. Examples thereof include a spray method, a brush coating method in which a material is brushed and cured, or an attachment method in which a precured sealant is attached to fill a gap.

  The use of the sealant of the present invention is not particularly limited. For example, each joint part of various buildings or structures such as corrugated sheets, slate, plastic sheets, aluminum sheets and tin, joints of concrete, ceramic pipes, glass, roads and floors It can be used as joints for joints and joints of vehicles such as covering seams, automobiles, ships and aircraft, joints of pipes and prefabricated buildings, adhesives and caulking materials.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these. In the following, parts represent parts by weight.

Production Example 1 [Production of Compound (S1-1)]
In a stainless steel autoclave equipped with a stirrer and a temperature controller, propylene glycol PO / EO block adduct (“Sanix PL-910” manufactured by Sanyo Chemical Industries, Ltd .; Mn900, hydroxyl value 124.7) 900.0 parts, Half esterification of acid anhydride group part by charging 384.0 parts of trimellitic anhydride and 2.0 parts of alkali catalyst (N-ethylmorpholine) and reacting at 0.20 MPa at 130 ± 10 ° C. for 5 hours under nitrogen atmosphere The ester compound obtained by reacting 2 moles of trimellitic anhydride with 1 mole of the propylene glycol PO / EO block adduct was obtained. Subsequently, 198.0 parts of EO was added dropwise over 5 hours while controlling the pressure at 100 ± 10 ° C. so that the pressure was 0.50 MPa or less, and then aged at 100 ± 10 ° C. for 1 hour to obtain the carboxyl of the ester compound. The compound (S1-1) which added EO to the group was obtained.

Production Example 2 [Production of Compound (S1-2)]
Same as Production Example 1 except that 900.0 parts of propylene glycol PO / EO block adduct is changed to 1000.0 parts of polytetramethylene ether glycol ("PTMG1000" manufactured by Mitsubishi Chemical Corporation; Mn1000, hydroxyl value 112.2). Thus, a compound (S1-2) was obtained.

Production Example 3 [Production of Compound (S1-3)]
900.0 parts of PO / EO block adduct of propylene glycol is added to 1500.0 parts of polyoxypropylene triol (“Sanix GP-1500” manufactured by Sanyo Chemical Industries, Ltd .; Mn 1500, hydroxyl value 112.2), and trimellitic anhydride Compound (S1-3) was obtained in the same manner as in Production Example 1, except that the amount of acid charged was 576.0 parts and the amount of EO charged was 297.0 parts.

Production Example 4 [Production of Compound (S1-4)]
Add 900.0 parts of PO / EO block adduct of propylene glycol to 1000.0 parts of polypropylene glycol (“Sanix PP-1000” manufactured by Sanyo Chemical Industries, Ltd .; Mn1000, hydroxyl value 112.2), and charge EO Compound (S1-4) was obtained in the same manner as in Production Example 1 except that the amount was changed to 101.2 parts.

Production Example 5 [Production of Compound (S1-5)]
In a stainless steel autoclave equipped with a stirrer and a temperature controller, 324.0 parts of diethylene glycol monobutyl ether, 218.0 parts of pyromellitic anhydride, 542.0 parts of dimethylformamide as a solvent, and an alkali catalyst (N-ethylmorpholine) 2 0.02 parts, reacted in a nitrogen atmosphere at 0.20 MPa at 25 ± 10 ° C. for 5 hours to half-esterify the acid anhydride group part, and ester obtained by reacting 1 mol of pyromellitic anhydride with 2 mol of diethylene glycol monobutyl ether A compound was obtained. Subsequently, 198.0 parts of EO was added dropwise over 5 hours while controlling the pressure at 50 ± 10 ° C. so that the pressure was 0.50 MPa or less, and then aged for 1 hour at 50 ± 10 ° C., and dimethylformamide was added at 100 ° C. It was removed over 5 hours while controlling the pressure to be −0.1 MPa at ± 10 ° C. to obtain a compound (S1-5) in which EO was added to the carboxyl group of the ester compound.

Production Example 6 [Production of Compound (S1-6)]
A stainless steel autoclave equipped with a stirrer and a temperature controller was charged with 60.0 parts of ethylenediamine, 384.0 parts of trimellitic anhydride, 1.0 part of alkali catalyst (N-ethylmorpholine) and 219 parts of THF as a solvent. Under an atmosphere, the reaction was carried out at 80 ± 10 ° C. for 2 hours to half-amidize the acid anhydride group portion, and an amide compound in which 2 mol of trimellitic anhydride was reacted with 1 mol of ethylenediamine was obtained. Subsequently, 198.0 parts of EO was added dropwise over 5 hours while controlling the pressure at 80 ± 10 ° C. so that the pressure was 0.50 MPa or less, and then aged at 80 ± 10 ° C. for 1 hour, 80 ± 10 ° C., 10 kPa The compound (S1-6) which added EO to the carboxyl group of the said amide compound was obtained by distilling a solvent off.

Production Example 7 [Production of Compound (S2-1)]
In a stainless steel autoclave equipped with a stirrer and a temperature controller, propylene glycol PO / EO block adduct (“Sanix PL-910” manufactured by Sanyo Chemical Industries, Ltd .; Mn900, hydroxyl value 124.7) 900.0 parts, Trimellitic anhydride (384.0 parts), alkali catalyst (N-ethylmorpholine) (1.0 part) and toluene (460 parts) were charged and reacted in a nitrogen atmosphere at 0.20 MPa and 130 ± 10 ° C. for 5 hours to obtain an acid anhydride group part. The ester compound obtained by reacting 2 moles of trimellitic anhydride with 1 mole of the PO / EO block adduct of propylene glycol was obtained. Subsequently, 432.0 parts of benzyl alcohol was added and controlled to be 95 ± 5 ° C. and 0.06 MPa or less. Volatilized toluene and water were condensed in a cooler, and the toluene separated by the trap was continuously added to the reaction vessel. The reaction was allowed to proceed for 6 hours. After the reaction, the solvent was distilled off at 80 ± 10 ° C. and 10 kPa to obtain a compound (S2-1) in which the carboxyl group of the ester compound was a benzyloxycarbonyl group.

Production Example 8 [Production of Compound (S2-2)]
Compound (S2-2) was obtained in the same manner as in Production Example 7, except that 432.0 parts of benzyl alcohol was changed to 428.0 parts of benzylamine.

Production Example 9 [Production of Compound (S2-3)]
Compound (S2-3) was obtained in the same manner as in Production Example 7, except that 432.0 parts of benzyl alcohol was changed to 496.0 parts of benzylthiol.

Production Example 10 [Production of Compound (S2-4)]
A stainless steel autoclave with a stirrer and temperature controller was charged with 60.0 parts of ethylenediamine, 384 parts of trimellitic anhydride, 1.0 part of alkali catalyst (N-ethylmorpholine) and 460 parts of toluene as a solvent, and a nitrogen atmosphere Then, the reaction was carried out at 80 ± 10 ° C. for 2 hours to half-amidize the acid anhydride group, and an amide compound in which 2 mol of trimellitic anhydride was reacted with 1 mol of ethylenediamine was obtained. Subsequently, 432.0 parts of benzyl alcohol was added and controlled to be 95 ± 5 ° C. and 0.06 MPa or less. Volatilized toluene and water were condensed in a cooler, and the toluene separated by the trap was continuously added to the reaction vessel. The reaction was allowed to proceed for 6 hours. After the reaction, the solvent was distilled off at 80 ± 10 ° C. and 10 kPa to obtain a compound (S2-4) having the carboxyl group of the amide compound as a benzyloxycarbonyl group.

Comparative Production Example 1 [Production of Compound (S1′-1)]
900.0 parts of PO / EO block adduct of propylene glycol is added to 3200.0 parts of polyoxypropylene triol (“Sanix GP-3000” manufactured by Sanyo Chemical Industries, Ltd .; Mn 3200, hydroxyl value 52.6), and trimellitic anhydride Compound (S1′-1) was obtained in the same manner as in Production Example 1, except that 384.0 parts of acid was changed to 444 parts of phthalic anhydride and the amount of EO charged was changed to 149.0 parts.

Comparative Production Example 2 [Production of Compound (S1′-2)]
Compound (S1′-2) was obtained in the same manner as in Production Example 1, except that 384.0 parts of trimellitic anhydride was changed to 296 parts of phthalic anhydride and the amount of EO charged was changed to 99.0 parts.

  Table 1 shows the analysis results of the compounds obtained in Production Examples 1 to 10 and Comparative Production Examples 1 and 2.

<Examples 1-16 and Comparative Examples 1-3>
According to the formulation shown in Table 2, the compound (S) and the polyol (a1) were charged into a container and stirred at 60 ° C. for 15 minutes, and the polyol compositions (A-1) to (A-16) of the present invention and comparison were made. Polyol compositions (A′-1) to (A′-3) were obtained. Table 2 shows analytical values of the compound (S) and the polyol (a1).
The compositions of PP-2000, GH-5000, and GP-3000 in Table 2 are as follows.
PP-2000: polyoxypropylene polyol having a molar average functional group number of 2.0 and a hydroxyl value of 56.1 obtained by adding PO to propylene glycol (“SANNICS PP-2000” manufactured by Sanyo Chemical Industries, Ltd.)
GH-5000: Polyoxypropylene polyol having a molar average functional group number of 3.0 and a hydroxyl value of 33.7 obtained by adding PO to glycerin (“Sanix GH-5000” manufactured by Sanyo Chemical Industries, Ltd.)
GP-3000: Polyoxypropylene polyol having a molar average functional group number of 3.0 and a hydroxyl value of 56.1 obtained by adding PO to glycerin (“SANNICS GP-3000” manufactured by Sanyo Chemical Industries, Ltd.)

<Examples 17 to 30 and Comparative Examples 4 to 6>
In a reaction vessel equipped with a stirrer and a thermometer, the polyol composition (A) and the organic polyisocyanate (B) in the number of parts shown in Table 3 were charged and reacted at 70 ° C. for 12 hours in a dry nitrogen atmosphere. Urethane prepolymers having a group or urethane prepolymer compositions (P-1) to (P-14) and urethane prepolymers (P′-1) to (P′-3) having an isocyanate group at a terminal for comparison. Obtained.

  Urethane prepolymer having an isocyanate group at the terminal or urethane prepolymer compositions (P-1) to (P-14) and urethane prepolymer having an isocyanate group at the terminal for comparison (P′-1) to (P′−). 3) As a one-component curable polyurethane-based sealant, cast on a polypropylene tray so that the film thickness is 1000 μm, and dry under reduced pressure at 50 ° C. for 1 hour, and a constant temperature and humidity chamber at 23 ° C. and a humidity of 50%. It was allowed to stand for 5 days, and then cured at 50 ° C. for 2 days to cure the moisture. The breaking elongation and breaking strength of the obtained resin were measured according to JIS K 7311. The measurement result is the sum of the content of the compound (S) in the polyol composition (A) used and the polyol composition (A), which is a raw material of the urethane prepolymer having an isocyanate group at the terminal, and the organic polyisocyanate (B). It shows in Table 3 with the ratio (weight%) of the weight of compound (S) with respect to weight.

<Examples 31 to 60 and Comparative Examples 7 to 12>
Urethane prepolymer or urethane prepolymer composition (P-1) to (P-14) having an isocyanate group at the terminal obtained in Examples 17 to 30 and Comparative Examples 4 to 6 and an isocyanate group at the terminal for comparison Using urethane prepolymers (P′-1) to (P′-3) as the main components of a two-component curable polyurethane sealant, a molar average functional group number of 3.0 and a hydroxyl value of 56 obtained by adding PO to glycerin. 1 polyoxypropylene triol (“Sanix GP-3000” manufactured by Sanyo Chemical Industries, Ltd.), polyol composition (A-15) or polyol composition (A-16) was used as a curing agent.

  The main component and the curing agent in the number of parts shown in Tables 4 and 5 were kneaded with a planetary mixer under reduced pressure (4 kPa), and cast onto a polypropylene tray so that the film thickness became 1000 μm. And allowed to cure for 5 days. The breaking elongation and breaking strength of the obtained resin were measured according to JIS K 7311. The measurement results are calculated based on the content of the compound (S) in the polyol composition (A) used for the prepolymer and the total weight of the polyisocyanate component (I) in the main agent and the active hydrogen component (H) in the curing agent. It shows in Table 4 and Table 5 with the ratio (weight%) of the weight of (S).

  The sealant using the polyol composition (A) for polyurethane-based sealant of the present invention is excellent in elongation at break and strength at break as compared with the conventional one. Therefore, it is particularly useful as a sealant used for architectural applications and waterproof applications.

Claims (10)

The compound (S) represented by the general formula (1) and a polyol (a1) other than the above (S) having a hydroxyl value of 20 to 2000 mgKOH / g and a molar average functional group number of 2 to 8 are contained. A polyol composition (A) for a polyurethane sealant characterized by the above.

[In the general formula (1), X ¹ represents a residue obtained by removing c active hydrogens from an m-valent active hydrogen-containing compound; c represents an integer satisfying 1 ≦ c ≦ m; X ² represents a residue obtained by removing one active hydrogen from an active hydrogen-containing compound, a plurality of X ² may be the same or different, and X ² and X ¹ may be the same or different Y represents a residue obtained by removing all carboxyl groups from a trivalent or higher valent aromatic polycarboxylic acid, and the aromatic ring of Y is composed of carbon atoms, and the carbon atoms are substituted with other than carboxyl groups. A group and / or a halogen atom may be bonded, but at least one carbon atom is not bonded to a substituent; a represents an integer of 1 or more, b represents an integer of 0 or more, and 2 ≦ a + b ≦ d−2 is satisfied; d is the carbo of the aromatic polycarboxylic acid. This represents the number of hydrogen atoms bonded to the carbon atom constituting the aromatic ring when all the substituents including the xyl group are substituted with hydrogen atoms, that is, the number of sites that can be substituted on the aromatic ring. ]   The polyol composition according to claim 1, wherein the compound (S) has a hydroxyl value of 0 or 70 to 500 mg KOH / g.   The polyol composition according to claim 1 or 2, wherein the concentration of Y in the compound (S) is 1.0 to 3.5 mmol / g.   The polyol composition according to any one of claims 1 to 3, wherein the compound (S) has a carbonyl group concentration of 2.0 to 10.0 mmol / g.   The trivalent or higher valent aromatic polycarboxylic acid has a structure in which a carboxyl group is bonded to two carbon atoms adjacent to a carbon atom constituting the aromatic ring and not having a substituent bonded thereto. Any polyol composition.   The polyol composition according to claim 5, which has a structure in which a carboxyl group is further bonded to at least one of carbon atoms adjacent to the carbon atom to which the carboxyl group is bonded.   The polyol composition according to any one of claims 1 to 6, wherein the content of the compound (S) is 0.01 to 10% by weight based on the weight of the polyol composition (A). The polyol (a1) is a monocyclic polyhydric phenol or a polyol obtained by adding 1 to 2 moles of an alkylene oxide per 1 hydroxyl group to a hydroxyl group of a bisphenol, a polyhydric alcohol having 2 to 20 carbon atoms, a polyether polyol, Polyester polyol, silicone polyol, polymer polyol, polydiene polyol, hydrogenated polydiene polyol, at least one polyol selected from the group consisting of acrylic polyols, natural oil-based polyols, and modified natural oil-based polyols. The polyol composition according to any one of claims 1 to 7.
Composition. A two-component curable urethane sealant comprising a main component containing a polyisocyanate component (I) and a curing agent containing an active hydrogen component (H) and satisfying the following (1) and / or (2) ;
(1) The urethane prepolymer or urethane having an isocyanate group at the terminal obtained by reacting the polyisocyanate component (I) with the polyol composition according to any one of claims 1 to 8 and the organic polyisocyanate (B). Containing a prepolymer composition;
(2) The said active hydrogen component (H) contains the polyol composition in any one of Claims 1-8.   It contains the urethane prepolymer or urethane prepolymer composition which has an isocyanate group at the terminal obtained by making the polyol composition and organic polyisocyanate (B) in any one of Claims 1-8 react. One-component curable urethane sealant.