JP2000104037A - One-can moisture-curing urethane resin composition and preparation thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide one-pack moisture-curing urethane resin compositions having long-term storage stability, quick curability and reduced foaming at the time of curing. SOLUTION: A one-pack moisture-cure urethane resin composition comprises a urethane prepolymer, a hydrophilic ketimine and zeolite powder. The prepolymer has a polyoxyalkylene structural unit such as a polyoxypropylene structural unit in its main chain structure and isocyanate groups at its terminals. The hydrophilic ketimine has an oxyalkylene structural unit such as a polyoxypropylene structural unit. As the compounding ratio it is preferred that, based on 100 pts.wt. urethane prepolymer, the ketimine is 1-8 pts.wt. and the zeolite powder is 10-15 pts.wt. This urethane resin composition is difficult to foam at the time of curing and accordingly, most suitable in use as the adhesive for stone 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a one-pack moisture-curable urethane resin composition which is fast-curing, has excellent long-term storage stability, and prevents foaming during curing, and a method for producing the same. Further, the present invention relates to a one-component moisture-curable urethane resin composition which can be suitably used as an adhesive used when applying a stone material to a wall or the like.

[0002]

2. Description of the Related Art Hitherto, urethane resin compositions containing a urethane prepolymer having an isocyanate group at a molecular terminal have been widely used in the industrial world as adhesives, sealants, paints, coatings and the like. In this urethane resin composition, the moisture in the air reacts with the isocyanate group, and the resin is crosslinked and cured. Therefore, it can be used as a one-part moisture-curing type, and is excellent in workability as compared with a two-part urethane resin composition of a type in which a curing agent is mixed before use.

[0003] However, the one-part moisture-curable urethane resin composition has a disadvantage that it is difficult to obtain quick-curing properties as compared with the two-part urethane resin composition. In order to solve this difficulty, conventionally, a means of blending ketimines such as oxazoline, ketimine, and aldimine as a curing accelerator has been often used. These ketimines are dehydration-condensation products of an amine compound having a skeleton of a residue of an aliphatic compound, an aromatic compound or a heterocyclic compound with a carbonyl compound, and a common feature is that the skeleton is hydrophobic. Such ketimines are easily hydrolyzed by moisture in the air, and the generated active hydrogen reacts with the isocyanate groups of the urethane prepolymer to accelerate the crosslinking and curing reaction.

[0004] Certainly, a one-pack moisture-curable urethane resin composition containing ketimines can provide a quick-curing property,
There is a disadvantage that the composition is easily cured during storage, and the long-term storage stability is reduced. As a means for solving this drawback, it has been proposed that ketimines are adsorbed on a porous inorganic filler such as zeolite powder and blended with a urethane prepolymer (Japanese Patent Publication No. 6-835). However, in this case, since the zeolite powder itself has a property of easily adsorbing moisture, ketimines are less likely to be hydrolyzed by moisture in the air, and that the rapid curing property of the urethane resin composition is reduced. there were.

[0005]

The inventors of the present invention have conducted intensive studies to develop a one-pack moisture-curable urethane resin composition having both fast-curing properties and long-term storage stability. The invention according to Japanese Patent Application No. 10-212907 (hereinafter, referred to as “prior application invention”) has been reached. That is, the prior application invention replaces ketimines having a conventional hydrophobic skeleton,
It is based on the discovery that the use of a hydrophilic ketimine having an oxyalkylene structural unit provides a one-pack moisture-curable urethane resin composition having both fast curing properties and long-term storage stability.

[0006] The present invention relates to a use invention of the prior application, and is intended to provide a one-component moisture-curable urethane resin composition with quick-curing property, long-term storage stability, and low foaming property during curing. Is what you do.

Conventionally, it has been known to blend a zeolite powder that adsorbs carbon dioxide gas as a foaming gas into a one-component moisture-curable urethane resin composition that foams during curing. However, since the zeolite powder also adsorbs moisture well, the zeolite powder adsorbs moisture in the air as in the invention according to Japanese Patent Publication No. 6-835 described above.
It was considered that the hydrophilic ketimine was less likely to be hydrolyzed, and the rapid curability of the urethane resin composition was reduced. However,
It has been found that the use of the prior invention makes it difficult for the hydrolysis of the hydrophilic ketimine to be inhibited, and the urethane resin composition hardly deteriorates in the quick-curing property. The present invention has been made based on such findings while utilizing the prior invention.

[0008]

That is, the present invention provides a urethane prepolymer having a polyoxyalkylene structural unit in the main chain structure and an isocyanate terminal group, a hydrophilic ketimine having an oxyalkylene structural unit, The present invention relates to a one-component moisture-curable urethane resin composition containing zeolite powder and a method for producing the same. Also, the present invention relates to an adhesive for stone using the composition.

The urethane prepolymer used in the present invention is:
It has a polyoxyalkylene structural unit in the main chain structure and has a terminal group formed of an isocyanate group. In general, a polyoxyalkylene polyol is reacted with an excess of polyisocyanate with respect to the equivalent of the polyoxyalkylene polyol to obtain a polyoxyalkylene polyol residue (a group obtained by removing a terminal hydroxyl group of the polyoxyalkylene polyol). And thus contains a polyoxyalkylene structural unit)) as the main chain structure;
A urethane prepolymer having an isocyanate group bonded to its terminal can be used. Here, the polyoxyalkylene structural unit referred to herein is represented by the formula-(RO) _n- , where R is a hydrocarbon group,
Not only an alkylene group but also a group containing an aromatic ring such as a styrene group may be used. N is an integer of 2 or more.

As the polyoxyalkylene polyol, polyoxyalkylene diol, polyoxyalkylene triol and the like are generally used, and in addition, polyoxyalkylene tetraol having four or more hydroxyl groups in one molecule is also used. Can be As the polyoxyalkylene diol, for example, polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol and the like and a copolymer thereof are used. As the polyoxyalkylene triol, for example, a product obtained by addition-polymerizing triol such as glycerin or trimethylolpropane with ethylene oxide, propylene oxide, butylene oxide, styrene oxide or the like is used. In particular, in the present invention, it is preferable to use triol obtained by addition polymerization of polyoxypropylene glycol or propylene oxide.

In the present invention, a urethane prepolymer may be obtained by reacting a polyoxyalkylene polyol with another polyether-type polyol or polyester-type polyol in combination with a polyisocyanate. In that case, 10 to 10 parts by weight of the other polyol per 100 parts by weight of the polyoxyalkylene polyol.
00 parts by weight can be blended. In particular, it is preferable to use a polyoxypropylene polyol as the polyoxyalkylene polyol and a polyol obtained by blending another polyol. In this case, it is more preferable that the polyoxypropylene polyol is blended in an amount of 10% by weight or more in all the polyols. This is because a hydrophilic ketimine having a polyoxypropylene structural unit is often used as the hydrophilic ketimine, and the affinity between the hydrophilic ketimine and the urethane prepolymer is further improved.

In the present invention, polyoxyalkylene polyols or other polyols used as polyols are listed below. [Polyether polyol] ・ Diols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and bisphenol A; At least one selected from the group consisting of triols such as trimethylolethane, trimethylolpropane and glycerin and polyols having four or more hydroxyl groups such as sorbitol, ammonia, ethylenediamine, urea, monomethyldiethanolamine, monoethyldiethanolamine At least one selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and styrene oxide in the presence of one or more amines such as And random or block copolymers obtained by ring-opening addition polymerization of at least one kind, and mixtures thereof.

[Polyester polyol] A polymer obtained by polycondensation of a dicarboxylic acid alone or a mixture thereof such as maleic acid, fumaric acid, adipic acid, sebacic acid or phthalic acid, and the above diols alone or a mixture. Ring-opened polymers such as ε-caprolactone and valerolactone; Active hydrogen compounds having two or more active hydrogens, such as castor oil. As the above-mentioned polyester polyols, those having a molecular weight of usually 100 to 20,000 are used, and they may be properly used depending on the purpose of use and performance.

[Polythiol] General formula HS- (R-SS)_n-R-SH (wherein,
R is -C_TwoH_Four−, −C_ThreeH₆−, −C_TwoH_Four-O-
C_TwoH_Four−, −C_TwoH_Four-O-CH_Two-OC_Two H_Four−,
-C_ThreeH₆-OC_ThreeH₆-OC_ThreeH₆-Or -C
_TwoH_Four-O- (C_TwoH_Four-O)_m-C_TwoH_Four-
n and m are integers of 2 to 50. Liquid)
Polysulfide and the like.

As the polyisocyanate to be reacted with a polyol such as a polyoxyalkylene polyol, polyisocyanates such as diisocyanate compounds, triisocyanate compounds and tetraisocyanate compounds can be used. Examples of the diisocyanate compound include aliphatic, alicyclic, araliphatic, and aromatic diisocyanate compounds. Examples of polyisocyanate compounds such as triisocyanate compounds include aliphatic, alicyclic, araliphatic, and aromatic polyisocyanate compounds. Hereinafter, various commonly used isocyanate compounds will be listed.

Aliphatic diisocyanate compounds: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene Diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate and the like.

Alicyclic diisocyanate compound: 1,3-
Cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-
Trimethylcyclohexyl isocyanate, 4,4'-
Methylene bis (cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-
Bis (isocyanatomethyl) cyclohexane 1,4-
Bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and the like.

Aromatic diisocyanate compound: 1,
3- or 1,4-xylylene diisocyanate or a mixture thereof, ω, ω'-diisocyanate-1,4
-Diethylbenzene, 1,3- or 1,4-bis (1-isocyanate-1-methylethyl) benzene or a mixture thereof.

Aromatic diisocyanate compound: m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5
-Naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 24- or 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate and the like.

Aliphatic triisocyanate compounds: lysine ester triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,3 6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanatomethyloctane and the like.

Alicyclic triisocyanate compound: 1,
3,5-triisocyanatecyclohexane, 1,3
5-trimethylisocyanatecyclohexane, 2-
(3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo [2,2,1] heptane,
2- (3-isocyanatopropyl) -2,6-di (isocyanatomethyl) -bicyclo [2,2,1] heptane, 3- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo [ 2,2,1] heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo [2,2,1] heptane 6- (2-isocyanatoethyl) -2 -Isocyanatomethyl-3-
(3-isocyanatopropyl) -bicyclo [2,2
1] heptane, 5- (2-isocyanatoethyl) -2
-Isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo [2,2,1] heptane, 6- (2
-Isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo [2,2,1] heptane and the like.

The araliphatic triisocyanate compound:
1,3,5-triisocyanatomethylbenzene and the like.

Aromatic triisocyanate compound: triphenylmethane-4,4 ', 4 "-triisocyanate;
1,3,5-triisocyanatebenzene, 2,4,6
-Triisocyanate toluene and the like.

Aromatic tetraisocyanate compound: 4,
4'-diphenylmethane-2,2 ', 5,5'-tetraisocyanate and the like.

When yellowing becomes a problem when using the above-mentioned various polyisocyanate compounds, it is preferable to use an aliphatic, alicyclic or araliphatic polyisocyanate compound.

An isocyanate-terminated urethane prepolymer having a polyoxyalkylene structural unit in the main chain structure is usually synthesized by allowing an excess of a polyisocyanate compound to act on the above-described polyoxyalkylene polyol. The synthesis method is not particularly limited, and it may be produced by a conventionally known method.

The hydrophilic ketimine having an oxyalkylene structural unit used in the present invention (hereinafter simply referred to as “hydrophilic ketimine”)
Sometimes I say. ) Means a compound containing an oxyalkylene structure among ketimines formed by dehydration condensation of a primary amine or a secondary amine with a carbonyl compound. Specifically, a compound formed by the dehydration condensation of a primary amine or a secondary amine having an oxyalkylene structure and an alkyl ketone is used. Note that the oxyalkylene structure referred to herein is represented by the formula-(RO) _n- , where R is an alkylene group. N is an integer of 1 or more. Specific examples of the hydrophilic ketimine include a diamine represented by Chemical Formula 1 and a monoalkyl ketone [RHCO].
Alternatively, it is preferable to use a compound represented by Chemical Formula 2, which is obtained by dehydrating and condensing a dialkyl ketone [(R) ₂ CO].

Embedded image (In the formula, R ₅ and R ₆ represent an alkylene group having 1 to 4 carbon atoms, and n represents an arbitrary integer of 1 to 20.) The diamine represented by Chemical Formula 1 is ethylenediamine or propylene. For alkylene diamines such as diamines,
It is obtained by adding 1 to 20 mol of an alkylene oxide such as ethylene oxide or propylene oxide.

Embedded image (Wherein, R ₁ , R ₂ , R ₃ , and R ₄ represent a hydrogen atom or a carbon atom
It represents 6 alkyl group, R _5, R ₆ represents an alkylene group having 1 to 4 carbon atoms, n represents represents any integer from 1 to 20. )

As a typical example of the hydrophilic ketimine represented by the chemical formula 2, 2 mol of a dialkyl ketone such as methyl isobutyl ketone is dehydrated and condensed with 1 mol of oxypropylene diamine obtained by adding 1 to 6 mol of propylene oxide to propylene diamine. Ketimine obtained by the above method. The weight-average molecular weight of the hydrophilic ketimine represented by Chemical Formula 2 is preferably about 100 to 1,000, and particularly preferably 300 to 7
About 00 is good.

Further, a triamine represented by the following formula (3):
It is also preferable to use a hydrophilic ketimine represented by Chemical Formula 4, which is obtained by dehydrating and condensing a monoalkyl ketone [RHCO] or a dialkyl ketone [(R) ₂ CO].

Embedded image (Wherein, R ₁₀ represents a hydrocarbon residue having 1 to 6 carbon atoms;
R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , and R ₁₆ represent an alkylene group having 1 to 4 carbon atoms, x, y, and z are 0 or any integer, and x + y + z = 1 to 20. . The triamine represented by Chemical formula 3 is obtained by adding 1 to 20 mol of an alkylene oxide such as ethylene oxide or propylene oxide to a triaminoisoalkane such as triaminoisohexane.

Embedded image(Where R_TenRepresents a hydrocarbon residue having 1 to 6 carbon atoms,
R₁₁, R₁₂, R₁₃, R₁₄, R_Fifteen, R₁₆Is carbon
Represents an alkylene group of Formulas 1 to 4,₁₇, R₁₈ ,
R₁₉, R₂₀, R_{twenty one}, R_{twenty two}Is a hydrogen atom or carbon number
Represents an alkyl group of 1 to 6, wherein x, y and z are 0 or optional
Where x + y + z = 1 to 20. )

As a typical example of the hydrophilic ketimine represented by the chemical formula 4, 1 mol of oxypropylene triamine obtained by adding about 6 mol of propylene oxide to 1-amino-2- (diaminomethylene) butane is added to methyl propyl ketone or the like. Ketimines obtained by dehydrating and condensing 3 moles of a dialkyl ketone are exemplified. The weight average molecular weight of the hydrophilic ketimine represented by Chemical Formula 4 is preferably about 200 to 1500, and particularly preferably about 400 to 900. In the narrow sense, ketimine means a compound in which an oxygen atom of a carbonyl group of a ketone is substituted with an imino group.In the present invention, ketimine is used in such a narrow sense. A compound obtained by the dehydration condensation of a primary amine or a secondary amine with a carbonyl compound is widely referred to as a ketimine.

The zeolite powder used in the present invention is an inorganic powder comprising an aluminosilicate compound. This inorganic powder has many cavities inside, and these cavities are connected to pores from the surface. Since these pores have a very uniform diameter, the zeolite powder has a characteristic that only molecules (adsorbed substances) that can pass through this diameter are adsorbed in the cavities. . Compound constituting such a zeolite powder are those which have a different chemical composition, for _{example, M 2 / n O · Al} 2 O 3 · xSiO 2 · yH 2
A compound represented by O (where M is a metal cation, n is a valence, and x and y are arbitrary integers), or M _z · A
It may be a compound represented by 10 ₂ · xSiO ₂ · yH ₂ O (however, z, x and y represent arbitrary integers).

In general, the zeolite powder preferably has an average particle size of 10 μm or less. The zeolite powder includes natural products and synthetic products, and any of them may be used. As particularly preferred zeolite powder,
It is preferable to use a synthetic zeolite 4A. Zeolite 4A is composed of Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂
] 27H ₂ O. The zeolite 4A powder has a pore diameter of 4 angstroms, and adsorbs carbon dioxide gas well. In addition, as the zeolite powder, zeolite 3A, zeolite 5A, zeolite 13X, and the like can also be used.

In the present invention, the amount of the hydrophilic ketimine having an oxyalkylene structural unit is preferably 1 to 8 parts by weight based on 100 parts by weight of the urethane prepolymer. When the amount of the hydrophilic ketimine is less than 1 part by weight, the urethane resin composition tends to have a low curability. If the amount of the hydrophilic ketimine exceeds 8 parts by weight, the long-term storage stability tends to decrease.

In the present invention, the amount of the zeolite powder is 10 parts by weight based on 100 parts by weight of the urethane prepolymer.
It is preferably from 15 to 15 parts by weight. When the compounding amount of the zeolite powder is less than 10 parts by weight, a tendency that it is difficult to suppress foaming during curing of the urethane resin composition occurs,
On the other hand, if the amount of the zeolite powder exceeds 15 parts by weight, the urethane resin composition tends to have a low curability.

The one-pack moisture-curable urethane resin composition according to the present invention contains, in addition to the urethane prepolymer, hydrophilic ketimine and zeolite powder, known inorganic fillers, viscosity improvers, organic solvents, plasticizers, Various modifiers or additives such as urethane catalysts other than the hydrophilic ketimine may be blended in desired amounts. In addition, since this composition is a one-component moisture-curing type, it is preferable to minimize the mixing of water. For example, when moisture is contained in a modifier or an additive such as an inorganic filler, it is preferable to dehydrate by means such as heating or decompression.

The one-component moisture-curable urethane resin composition according to the present invention can be widely used as an adhesive, a sealant, a paint, a coating agent and the like. Further, a composition containing the above-mentioned various modifiers or additives is suitable as an adhesive, and is particularly suitable for use as an adhesive for stone. That is, when a stone is applied to a wall or the like using an adhesive, the base is not always flat. Therefore, the base is flattened with the adhesive, and final surface adjustment of the stone is performed. Therefore, if the adhesive foams during curing, the stone moves, and this surface adjustment is disturbed, and it is difficult to obtain a flat finished surface. Since the one-component moisture-curable urethane resin composition according to the present invention suppresses foaming at the time of curing, disorder in surface adjustment is less likely to occur, a flat finished surface is obtained, and the appearance is hardly impaired. . Therefore, the one-pack moisture-curable urethane resin composition according to the present invention is excellent as an adhesive for stone materials.

When the one-component moisture-curable urethane resin composition of the present invention is used as an adhesive for stone, the stones that can be bonded include marble, granite, terrazzo block, sandstone, tuff, slate, mica, andesite. Diorite, amphibolite,
Quartz, calcite, limestone, feldspar, basalt, talc, quartz, agate and the like. These can be suitably bonded and applied irrespective of natural, artificial, or finishing methods.

The one-component moisture-curable urethane resin composition according to the present invention is employed not only as an adhesive for stone materials but also as a material capable of suitably adhering and applying materials similar to stone materials or other materials. Can be. For example, materials similar to stone include unglazed ceramics, ceramics, molded products such as cement, bricks, whetstones, ceramic tiles, tiles, asbestos cement boards, rock wool boards, glass wool boards, asbestos cement calcium silicate boards, gypsum boards, It can be suitably used when bonding and constructing sizing boards, glass, shells, various metals, alloys and the like. Other materials include
Suitable for bonding and construction of interior finishing materials such as plywood, wood, styrofoam, wood brick, insulation board, particle board, flooring material, fiberboard, FRP (fiber reinforced plastic), vinyl flooring, etc. Can be used.

As a method of bonding and applying various materials such as stone materials, an adhesive containing the urethane resin composition according to the present invention is applied to a base and / or an adherend, and then bonded together.・ Can be constructed. The method of applying the adhesive is as follows: a method of applying a dango in order to have a certain thickness, a method of flattening the applied adhesive using a plastering iron or a spatula, and a streak using a comb-shaped iron Coating method, a method of applying a bead using a cartridge or a squeezing device, a method of applying with a roller, a method of automatically applying with a machine, and the like.One or more of these are combined. It can be applied suitably.

The method for producing a one-pack moisture-curable urethane resin composition according to the present invention can be consistently compounded in one reaction / processing pot, or a urethane prepolymer is synthesized in a reaction pot. Can be transferred to a processing kettle and blended. Here, the latter method will be described.

The above-mentioned polyoxyalkylene polyol and other polyols were charged into a closed reaction vessel equipped with a stirrer, a condenser, a vacuum dehydrator, and a nitrogen gas blower, and after dehydration under reduced pressure, the NCO / OH ratio was adjusted to 1 or more equivalents. Compounding the set polyisocyanate, under nitrogen stream 70-
The reaction is carried out at 100 ° C. for about 3 to 8 hours, and the polymerization is continued until the NCO content approaches the designed value.
Then, this urethane prepolymer is charged into a closed processing kettle equipped with a stirrer, a condenser, a vacuum dehydrator, and a nitrogen gas flow device, and a known modifier such as an adhesive, a sealant, a paint, a coating agent or the like according to the final use. Is blended. When a large amount of these modifiers is blended to cause a large amount of moisture to be contained in the composition, it is preferable to perform a sufficient dehydration treatment before or after the blending. Further, a monoisocyanate compound such as p-toluenesulfonyl isocyanate, which is a dehydrating agent, may be added and blended with the modifier. Thereafter, a hydrophilic ketimine having an oxyalkylene structural unit and a zeolite powder are blended, and preferably mixed homogeneously under a nitrogen stream to minimize the influence of moisture to obtain a one-part moisture-curable urethane resin composition. obtain. In addition,
The hydrophilic ketimine and the zeolite powder may be added and mixed at the same time, or may be added and mixed before and after the step of adsorbing the hydrophilic ketimine to the zeolite powder. A simple addition and mixing method may be used. If hydrophilic ketimine is adsorbed on the zeolite powder, the pores of the zeolite powder are blocked, and it is difficult to adsorb the foaming gas generated during curing, which is not preferable. Finally, when the one-part moisture-curable urethane resin composition is stored in a sealed container subjected to nitrogen substitution, the final product is obtained.

[0042]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments, but the present invention is not limited to the embodiments. The present invention is a utilization invention of the prior application invention, and even if zeolite powder is added to and blended with the composition according to the prior application invention, the rapid curability hardly decreases, and foaming during curing is well prevented. Should be interpreted as being based on the discovery that

The compounds used in the examples and comparative examples are as follows. [Urethane prepolymer (A)] In a reaction vessel, preminol 4010 (Asahi Glass Co., Ltd., average molecular weight 1000
Of polyoxypropylene polyol) and 100 parts by weight of G-1500 (polyoxypropylene polyol having an average molecular weight of 1500, manufactured by Asahi Denka Kogyo KK).
Parts by weight and 27.1 parts by weight of Sumidur 44V20 [crude MDI (4,4'-diphenylmethane diisocyanate) manufactured by Sumitomo Bayer Urethane Co., Ltd.]
The mixture was reacted at 90 ° C. for 3 hours with stirring under a nitrogen atmosphere to obtain a urethane prepolymer (A). Terminal isocyanate group (NCO) of this urethane prepolymer (A)
Was 5.0% by weight.

[Hydrophilic ketimine (1)]

Embedded image (However, n is in the range of 1 to 6.) [Hydrophilic ketimine (2)]

Embedded image (However, x + y + z is about 5.3.)

[Zeolite powder] Zeolite 4A powder (a powder having a pore diameter of 4 Å and an average particle diameter of 10 μm or less; trade name: Virit L, manufactured by Kurita Kogyo Co., Ltd.)

[Filler] Calcium carbonate (manufactured by Nitto Powder Chemical Co., Ltd., trade name: NS100) containing 200 pp of water
m. [Urethane catalyst] A tin catalyst (trade name: Stan BL, manufactured by Sankyoki Gosei Co., Ltd.). [Layer separation inhibitor] Hydrophobic silica fine powder (generally referred to as fumed silica; trade name: R972, manufactured by Nippon Aerosil Co., Ltd.) [Dehydrating agent] monoisocyanate compound (manufactured by Sumitomo Bayer Urethane Co., trade name: Additive TI)

Example 1 400 parts by weight of a urethane prepolymer, 900 parts by weight of a filler and 30 parts by weight of fumed silica were mixed and stirred under reduced pressure. Thereafter, 12 parts by weight of the hydrophilic ketimine (1),
40 parts by weight of Bilit L, 0.2 parts by weight of a tin catalyst and 10 parts by weight of a dehydrating agent were added, and the mixture was stirred under reduced pressure to obtain a one-part moisture-curable urethane resin composition.

Example 2 In place of hydrophilic ketimine (1), hydrophilic ketimine (2)
A one-pack moisture-curable urethane resin composition was obtained in the same manner as in Example 1 except that the above was used.

Example 3 A one-part moisture-curable urethane resin composition was obtained in the same manner as in Example 1, except that the amount of Bilit L was changed to 60 parts by weight.

Example 4 In place of hydrophilic ketimine (1), hydrophilic ketimine (2)
A one-part moisture-curable urethane resin composition was obtained in the same manner as in Example 3 except that the above was used.

Example 5 A one-part moisture-curable urethane resin composition was obtained in the same manner as in Example 3, except that the amount of the hydrophilic ketimine (1) was changed to 30 parts by weight.

Example 6 Instead of hydrophilic ketimine (1), hydrophilic ketimine (2)
A one-pack moisture-curable urethane resin composition was obtained in the same manner as in Example 5, except for using.

Comparative Example 1 A one-part moisture-curable urethane resin composition was obtained in the same manner as in Example 1 except that Bilit L was not blended.

Comparative Example 2 A one-part moisture-curable urethane resin composition was obtained in the same manner as in Comparative Example 1, except that the amount of the hydrophilic ketimine (1) was changed to 30 parts by weight.

Comparative Example 3 A one-part moisture-curable urethane resin composition was obtained in the same manner as in Example 3, except that the hydrophilic ketimine (1) was not added.

Each of the one-pack moisture-curable urethane resin compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 3 was evaluated for long-term storage stability, rapid curability and foamability by the following methods. Tables 1 and 2 show the results. [Long-term storage stability] The one-pack moisture-curable urethane resin composition was filled and sealed in an aluminum pack, allowed to stand at 50 ° C for 2 weeks and at 50 ° C for 4 weeks, and then observed for viscosity. The long-term storage stability was evaluated according to the following criteria. ：: No increase in viscosity was observed. ：: Slight increase in viscosity was observed. Δ: Remarkable thickening is observed. X: Gelation is observed.

[Rapidly curable] A one-component moisture-curable urethane resin composition is applied to a stone so as to have a thickness of 10 mm.
It was stuck on the wall at 5 ° C. Then, 16 hours later, the deviation of the stone material was observed, and the judgment was made according to the following criteria. ：: No deviation of stone material occurs. Also, it cannot be peeled off manually. ：: No deviation of the stone material occurs. However, you can do so if you want to. Δ: No deviation of the stone material occurs. However, it can be easily removed manually. ×: Deviation of stone occurs.

[Expansion] Evaluation of the expansion will be described with reference to FIG. One-moisture moisture-curable urethane resin composition 1 is applied to stone 2 to a thickness of 10 mm.
The evaluation was performed by placing the sample on a concrete flat plate 3 under 5% RH and detecting the aging foaming displacement (mm) using an electric dial gauge 4. The evaluation criteria are as follows. Good: Foaming displacement of less than 0.3 mm. Δ: Foaming displacement of 0.3 to 0.5 mm. ×: Foaming displacement of 0.5 mm or more.

[0059]

[Table 1]

[0060]

[Table 2]

As can be seen from the results of the above Examples and Comparative Examples 1 and 2, an isocyanate-terminated urethane prepolymer having a polyoxyalkylene structural unit in the main chain structure, a hydrophilic ketimine having an oxyalkylene structural unit, The one-component moisture-curable urethane resin composition according to the example in which the zeolite powder is blended, the displacement during curing is less than that in the compositions according to Comparative Examples 1 and 2 in which the zeolite powder is not blended, It can be seen that the generated carbon dioxide gas, which is a foaming gas, is well adsorbed on the zeolite powder. In addition, the storage stability and fast-curing properties of the one-pack moisture-curable urethane resin composition according to the examples are shown in Comparative Example 1.
It is clear that these performances were hardly hindered by the addition of the zeolite powder. Further, it can be seen that the one-pack moisture-curable urethane resin composition according to the example is remarkably superior in terms of quick-curing property as compared with the composition according to Comparative Example 3 in which no hydrophilic ketimine is blended. . Further, the displacement during curing is superior to the composition according to Comparative Example 3.
Accordingly, it can be seen that the one-pack moisture-curable urethane resin composition according to the examples has both long-term storage stability and rapid curability, and that foaming during curing is also well prevented.

[0062]

The reason why the one-pack moisture-curable urethane resin composition according to the present invention satisfies the three requirements of long-term storage stability, rapid curability and suppression of foaming during curing is unclear. The present inventors have found that, due to the similarity in molecular structure between the polyoxyalkylene group of the urethane prepolymer and the oxyalkylene group of the hydrophilic ketimine, the affinity is good, and therefore each component is present in a stable state. Therefore, it is estimated that long-term storage stability can be obtained. Further, since the urethane prepolymer and the hydrophilic ketimine are easily compatible with water, it is presumed that the water is hardly selectively adsorbed on the zeolite powder, thereby obtaining a fast curing property. Furthermore, it is speculated that zeolite powder that does not adsorb a large amount of water can adsorb carbon dioxide gas generated at the time of curing well, and can suppress foaming at the time of curing.

[0063]

As described above, the one-pack moisture-curable urethane resin composition according to the present invention satisfies all of long-term storage stability, rapid curability, and suppression of foaming during curing. This realizes a property that makes it difficult to combine them. Therefore, it can be used stably even when stored for a long period of time, and when used, it has an effect that it cures quickly and hardly foams at the time of curing.

Accordingly, the one-pack moisture-curable urethane resin composition according to the present invention can be effectively used as an adhesive, a sealing agent, a paint, and a coating agent. In particular, when a stone is applied to a wall surface, the movement of the stone due to foaming is small, and the stone can be adhered to the wall cleanly, which is useful as an adhesive for stone.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of an apparatus used for evaluating foaming property of a one-component moisture-curable urethane resin composition during curing.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 1 liquid moisture hardening type urethane resin composition 2 Stone material 3 Concrete plate 4 Electric dial gauge

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Shinichi Sato 5-3-35 Nishibori, Urawa-shi, Saitama F-term (reference) in Konishi Co., Ltd. Urawa Research Laboratories 4J034 DA01 DA03 DB03 DF11 DF16 DF20 DF22 DF27 DG02 DG03 DG04 DG14 HA07 HC03 HC09 HC12 HC17 HC22 HC45 HC46 HC52 HC54 HC64 HC67 HC70 HC71 HC73 JA42 MA04 QB12 RA08 4J040 EE022 EE052 EF131 EF281 EF321 GA13 HA316 HC16 JA12 JB04 KA16 LA05 MA02 MA04 MA05 MA06 MA08 MA10 MB05 NA12 QA03

Claims (5)

[Claims] 1. A urethane prepolymer having a polyoxyalkylene structural unit in a main chain structure and having an isocyanate terminal group, a hydrophilic ketimine having an oxyalkylene structural unit, and a zeolite powder. One-component moisture-curable urethane resin composition. 2. The method according to claim 1, wherein 1 to 8 parts by weight of the hydrophilic ketimine and 10 to 15 parts by weight of the zeolite powder are mixed with 100 parts by weight of the urethane prepolymer.
Liquid moisture-curable urethane resin composition. 3. The urethane prepolymer is obtained by reacting a polyol containing 10% by weight or more of a polyoxypropylene polyol with a polyisocyanate, and the oxyalkylene structural unit of the hydrophilic ketimine has a polyoxyethylene structure. 3. The one-pack moisture-curable urethane resin composition according to claim 1, which is an oxypropylene structural unit. 4. An adhesive for stone materials, comprising the one-component moisture-curable urethane resin composition according to claim 1. 5. A method for adsorbing a hydrophilic ketimine having an oxyalkylene structural unit to a zeolite powder, having a polyoxyalkylene structural unit in a main chain structure,
A method for producing a one-pack moisture-curable urethane resin composition, comprising mixing a urethane prepolymer having an isocyanate terminal group with the hydrophilic ketimine and the zeolite powder.