JPH1036481A - One-part moisture-curable urethane composition and adhesive - Google Patents

Abstract

(57) [Problem] To provide an object of the present invention, in addition to adhesive properties, has excellent characteristics in storage stability and suppression of foaming, and is excellent even under conditions of no solvent or low solvent. Coating workability,
One-component moisture-curable urethane compositions exhibiting initial tackiness and adhesives using the same. SOLUTION: (A) An isocyanate compound and (B)
In a one-pack moisture-curable urethane composition comprising, as essential components, a compound having one or more oxazolidine rings in the molecule, a urethane prepolymer (a1) having (A) two or more isocyanate groups at a terminal and a diisocyanate compound A one-component moisture-curable urethane composition comprising (a2) and a polyisocyanate compound (a3) having more than two isocyanate groups in a molecule as essential components.

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 composition and an adhesive which utilize a reaction with a compound which generates an active hydrogen by hydrolyzing an oxazolidine ring with moisture in the air. More specifically, a one-part moisture-curing type adhesive for adhesives that has excellent adhesive properties, storage stability, foam suppression properties, good coating workability even under conditions of no solvent or low solvent, and excellent initial tackiness. The present invention relates to a urethane composition and an adhesive.

[0002]

2. Description of the Related Art A one-part moisture-curable urethane composition does not require weighing and mixing operations, is easy to apply, has good adhesion to a wide variety of materials, and has a flexible adhesive layer. For this reason, in the field of construction site construction, it is attracting attention as an alternative to the currently mainstream two-component mixed epoxy adhesive. Further, compared with epoxy adhesives, there is less problem of fogging, and no solvent or low solvent can be achieved by designing the resin, which is regarded as important in terms of safety and health.

[0003] Examples of the use of an adhesive for construction site construction include:
In many cases, flooring materials are directly attached to the foundation of concrete, plywood, etc., and the types of flooring materials are roughly divided into floor carpets, vinyl chloride tiles, wood flooring, etc. There are two types, long type with curl like vinyl sheet.

[0004] The adhesive to the flooring material only needs to have initial tackiness and shearing resistance to such an extent that the flooring material does not slip. For example, in Japanese Patent Application Laid-Open No. 6-240226,
What blocked the terminal isocyanate group of the urethane prepolymer with a primary alcohol may be mixed into a urethane composition to improve the adhesiveness. In JP-A-6-78506, a polymer binder having a specific particle size is used. Granular heavy calcium carbonate is contained to suppress slippage of floor tiles. In recent years, low-solvent adhesives that are not required to be labeled under the Industrial Safety and Health Act and are non-hazardous even under the Fire Service Act have been marketed.

[0005] The adhesive to the floor material needs to have a strong initial tackiness to suppress the jump of the floor material end portion, and both the conventional synthetic rubber adhesive and the one-component moisture-curable urethane adhesive are solvent-based. Was used, and when water resistance was required, a two-pack type epoxy adhesive was used. However, synthetic rubber adhesives have adhesive properties,
It lacks heat resistance, shear resistance, and the like, and the two-part epoxy adhesive has low curing properties at low temperatures, in addition to the above-mentioned disadvantages, and thus does not completely prevent the floor material from jumping up. Among them, the one-part moisture-curable urethane adhesive has good initial tackiness, shear resistance, and the like, and contains a specific isocyanate compound as described in JP-A-7-268309. As a result, a well-balanced performance such as improved water-resistant adhesiveness is recognized, and the demand is dramatically increasing at present, but a large amount of organic solvent is volatilized to express initial tackiness, There are still health and safety issues.

In one-component moisture-curable urethane adhesives,
In order to ensure coating workability under solvent-free or low-solvent system conditions, it is essential that the resin viscosity is low, and in order to develop strong initial tackiness, fast curing is also required.

Various one-component moisture-curable urethane compositions have been studied, but most of them are cured by reaction of polyisocyanate with moisture (moisture) accompanied by generation of carbon dioxide gas. Usually, a curing accelerator such as a metal catalyst and an amine catalyst is used in combination because of a low curing speed. However, remarkable foaming is caused to cause a decrease in adhesive strength and poor storage stability. Furthermore, many of the isocyanate compounds used in the urethane prepolymer use diphenylmethane diisocyanate (MDI), which reacts quickly with moisture, and it has been difficult to reduce the viscosity. That is, a one-component moisture-curable urethane adhesive having no solvent or a low solvent has excellent characteristics in terms of storage stability, suppression of foaming in addition to adhesive properties, and has initial tackiness and low viscosity (coating work). None of them had all of (gender).

Examples of the use of a moisture dissociation type latent crosslinking agent in order to solve the problems of curability, storage stability and foam suppression are disclosed in JP-A-6-293821 and JP-A-7-33.
One-component moisture-curable urethane compositions using an oxazolidine compound described as a crosslinking agent in JP-A-852 and the like have been proposed.

However, JP-A-6-293821 has a problem in initial tackiness because it does not contain the diisocyanate compound and the polyisocyanate compound of the present invention.

On the other hand, in JP-A-7-33852,
Initial mixing of NCO-terminated urethane prepolymer with a mixture of a reaction product of an organic diisocyanate such as xylylene diisocyanate or hexamethylene diisocyanate and a hydroxyoxazolidine compound, a so-called low molecular weight reactant having a number average molecular weight of less than 1000, It is inferior in sex.

In other words, all of the above publications have excellent storage stability and foam suppressing effect, but do not achieve strong initial tackiness.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide not only adhesive properties but also excellent storage stability and suppression of foaming, and good properties under no solvent or low solvent conditions. An object of the present invention is to provide a one-component moisture-curable urethane composition exhibiting coating workability and initial tackiness, and an adhesive using the same.

[0013]

The present inventors have conducted intensive studies on the above-mentioned problems, and as a result, have found that a diisocyanate and a polyisocyanate mixture having a different reactivity from a compound having an oxazolidine ring, particularly an oxazolidine compound having a number average molecular weight of 1,000 or more, are obtained. By using together, excellent storage stability in addition to the adhesive properties, showing foaming suppression effect, despite the absence of solvent or low solvent system, good coating workability,
The present inventors have found that a good initial tackiness sufficient to suppress the end of the long sheet having the above-mentioned curl can be obtained, and have completed the present invention.

That is, the present invention relates to a one-pack moisture-curable urethane composition comprising (A) an isocyanate compound and (B) a compound having at least one oxazolidine ring in a molecule as an essential component. Contains, as essential components, a urethane prepolymer (a1) having two or more isocyanate groups at its terminals, a diisocyanate compound (a2), and a polyisocyanate compound (a3) having more than two isocyanate groups in the molecule. Preferably, the urethane prepolymer (a1) having two or more isocyanate groups at the end is obtained by a reaction between a polyol compound and a polyisocyanate compound, and preferably, a compound having one or more oxazolidine rings in the molecule (B ) Is 1000 or more, preferably polyisocyanate Adducts in which a compound having two or more active hydrogens and a diisocyanate compound have reacted, a burette in which a diisocyanate compound has reacted with water, an isocyanurate in which a diisocyanate compound has been trimerized, and One or two
A mixture of more than one species, or a modified product thereof,
Preferably, the isocyanate compound (A) having the highest reactivity with active hydrogen H (primary amine and hydroxyl group) generated by hydrolyzing the oxazolidine ring of the compound (B) is the diisocyanate of the compound (a2) Preferably, the ratio of the isocyanate group of the diisocyanate compound (a2) to the active hydrogen H generated by hydrolysis of the compound (B) is -NCO / -H = 0.
1 to 2.0, preferably the ratio of the total of the isocyanate groups of the compound (A) to the active hydrogen H generated by hydrolysis of the compound (B) is -NCO / -H
= 0.4 to 4.0, and to provide an adhesive comprising the one-part moisture-curable urethane composition.

The present invention will be further described below.

[0016]

DETAILED DESCRIPTION OF THE INVENTION The urethane prepolymer (a1) having two or more isocyanate groups at the terminal of the isocyanate compound (A) used in the present invention is a compound having two or more isocyanate groups and is a polyisocyanate compound. And a polyol compound in the form of a urethane prepolymer prepared in a conventional manner in excess of a polyisocyanate compound.

As the polyisocyanate compound, 2,
4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, partially carbodiimidated diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolidine diisocyanate, naphthalene diisocyanate, phenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, One or a mixture of two or more aromatic diisocyanates, such as xylylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and cyclohexane diisocyanate, aliphatic diisocyanate, and alicyclic diisocyanate.

The polyol compounds used in the present invention include polyether polyols, polyester polyols, other polyols, and mixed polyols thereof. For example, a polyol produced using a double metal cyanide complex as a catalyst is also included.

Examples of the polyether polyol include one or more polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, glucose, sorbitol, and sucrose, and the like. Polyols and polyoxytetramethylene polyols obtained by adding one or more of oxide, butylene oxide, styrene oxide and the like are included.

Examples of the polyester polyol include, for example, one or two of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, glycerin, trimethylolpropane, and other low molecular weight polyols.
Or more and one or more of glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid, hydrogenated dimer acid or other low molecular dicarboxylic acid or oligomeric acid Examples include condensation polymers and ring-opening polymers such as propiolactone, caprolactone, and valerolactone.

Other polyols include, for example, polycarbonate polyols, polybutadiene polyols,
Examples include hydrogenated polybutadiene polyol and acrylic polyol. Also, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol,
Low molecular polyols such as hexanediol, cyclohexanedimethanol glycerin, trimethylolpropane, glucose, sorbitol, and sucrose are also included.

The number of terminal isocyanate groups of the urethane prepolymer (a1) is preferably less than 3, more preferably 2. When it is 3 or more, the duration of the initial tackiness of the adhesive tends to be short, and the adherable time of the adherend tends to be short. When it is less than 2, on the contrary, the expression time of the initial adhesiveness tends to be late. .

Examples of the diisocyanate compound (a2) of the isocyanate compound (A) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, phenylene diisocyanate, and hexamethylene diisocyanate. And aromatic diisocyanates such as isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, cyclohexane diisocyanate, aliphatic diisocyanate and alicyclic diisocyanate, or a mixture of two or more thereof.

The polyisocyanate compound (a3) having more than two isocyanate groups in the molecule of the isocyanate compound (A) is preferably an adduct obtained by reacting a compound having two or more active hydrogens with a diisocyanate compound. And a burette in which diisocyanate and water are reacted, an isocyanurate in which diisocyanate is trimerized, and a mixture of one or more of these, or a modified product thereof. For example, adduct bodies are trimethylolpropane, pentaerythritol,
Obtained by reacting a hydroxyl group of a compound having three or more hydroxyl groups in a molecule such as sorbit with a diisocyanate,
Commercial products include Coronate L (TDI adduct),
Coronate HL (an HDI adduct) may be mentioned. A commercially available buret body is Duranate 24A-10.
0 (HDI buret form), and examples of isocyanurate form include Suprasec SP-3340 (TDI nurate form) and Coronate EH (HDI nurate form).

In the above isocyanate compound (A), active hydrogen H (primary amine and hydroxyl group) generated by hydrolyzing the oxazolidine ring of compound (B)
The diisocyanate compound (a2)>
It is preferable that urethane prepolymer (a1) ≧ polyisocyanate compound (a3). When the reactivity of the polyisocyanate compound (a3) is high, the curability is high, and the initial tackiness expression time is fast, but the duration time is short, and the adherable time of the adherend tends to be short,
Not preferred.

As described in US Pat. No. 4,138,545, the compound (B) having an oxazolidine ring in the molecule may be a reaction between a lower alkyl ether of a polycarboxylic acid and oxazolidine, a transesterification of a polyol with oxazolidine. It can be obtained by a reaction, a transesterification reaction in the presence of a carbonate as described in JP-A-5-117252, a reaction between a urethane prepolymer and an oxazolidine compound as described in JP-A-6-293821.

Preferably, the compound (b1) having two or more isocyanate groups and the oxazolidine compound (b2)
And the reaction.

The isocyanate compound (b) of the compound (B)
As 1), a urethane prepolymer and a polyisocyanate compound can be used. Here, (b1)
Average isocyanate (abbreviated as NCO) groups at the terminal
Is preferably less than 2, more preferably 2. When it is 3 or more, the duration of the initial tackiness of the adhesive tends to be short, and the adherable time of the adherend tends to be short. When it is less than 2, on the contrary, the expression time of the initial adhesiveness tends to be late. . The compound (B) preferably has a number average molecular weight of 1,000 to 15,000. If the molecular weight is less than 1,000, the curability is reduced and the desired initial tackiness cannot be obtained. If the molecular weight exceeds 150,000, the viscosity is high and the coating workability is poor.

When N-2-hydroxyalkyloxazolidine is used as (b2), the reaction ratio between urethane prepolymer (b1) and N-2-hydroxyalkyloxazolidine (b2) is NCO / OH = 0.98. ~
1.4 is preferred, and more preferably 1.02 to 1.15.
Is preferred. If NCO / 0H = 0.98, N-2-
Hydroxyalkyl oxazolidine tends to remain unreacted, adversely affecting storage stability. NCO
When / 0H exceeds 1.4, the amount of the prepolymer having one oxazolidine group in the molecule increases, and there is a problem in that the curing speed decreases and the viscosity increases.

N-2- used in the synthesis of compound (B)
Hydroxyalkyl oxazolidine is synthesized by a dehydration reaction of an alkanolamine having a 1,2 amino group and a 2-hydroxyethyl group with an aldehyde or ketone. Alkanolamines include ethanolamine, diethanolamine, isopropanolamine,
Diisopropanolamine, isobutanolamine, diisobutanolamine, hydroxyethylaminomethyl alcohol, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, diethylenetriamine, bis (aminomethyl) cyclohexane, xylylenediamine, dicyclohexyldiamine, isophoronediamine , Isopropylidenebis (aminocyclohexane), methylenebis (aminocyclohexane), polymethylenepolyamine, diaminotoluene,
It is a compound having a secondary amino-2-hydroxyl group in which a primary amino group such as phenylenediamine is substituted with a 2-hydroxyethyl group.

Aldehydes or ketones include butyraldehyde, trimethylacetaldehyde, triethylacetaldehyde, valeroaldehyde, furfural, benzaldehyde, methylethylketone, cyclohexanone, trimethylcyclohexanone, acetophenone, anisaldehyde, hexanal, octanal,
Decanal, citral and the like can be mentioned.

Further, an isocyanate group of compound (a2) and active hydrogen H generated by hydrolysis of compound (B)
Is preferably -NCO / -H = 0.1 to 2.0, more preferably 0.5 to 1.0 in equivalent ratio. If it is less than 0.1, the curability is slow, so that satisfactory initial adhesiveness cannot be obtained. If it exceeds 2.0, foaming due to carbon dioxide gas occurs in the adhesive layer, and the adhesive properties deteriorate.

The ratio of the total of the isocyanate groups of the compound (A) to the active hydrogen H generated by hydrolysis of the compound (B) is -NCO / -H = 0.4-4.
0, more preferably 1.0 to 1.0.
3.0. If it is less than 0.4, the storage stability and the adhesive properties are inferior. If it exceeds 4.0, foaming due to carbon dioxide gas occurs in the adhesive layer, the adhesive properties are reduced, and the curability is slow, and the initial tackiness is sufficient. Can not be obtained.

The composition of the present invention may contain, if necessary, a curing accelerator, a solvent, a small amount of process oil, a plasticizer, a thixotropic agent, an extender pigment, an ultraviolet inhibitor for maintaining and improving weather resistance, and a stabilizer. And various additives can be added, and these mixtures can be uniformly mixed, and can be manufactured by a mixing and kneading apparatus sufficient to ensure preservation.

As the curing accelerator, an acidic substance having an acid dissociation index pKa in an aqueous solution in the range of 1.0 to 4.0 is used. If the pKa is greater than 4.0, the hydrolysis of the oxazolidine ring of the compound (B) does not occur at a practical rate, so that the moisture curing rate is low and foaming occurs in the adhesive layer. The acid dissociation index pKa in an aqueous solution of an acidic substance is 1.
If it is less than 0, the formation of a stable salt with the amino group generated by hydrolysis of the oxazolidine ring occurs, the reaction with the isocyanate group does not proceed, and as a result, the moisture curing rate is low, and the initial tackiness and adhesive properties are low. Is significantly impaired.

Here, the acid dissociation index pKa is an index indicating the acid strength, and the lower the value, the higher the acid strength. Incidentally, the value of the acid dissociation index pKa in the aqueous solution is:
"The Chemical Society of Japan, Basic Handbook of Chemistry, Revised 4th Edition II-316"
To 321 "can be referred to.

Specific examples of such an acidic substance include one or more selected from the group consisting of inorganic acids, organic acids and their anhydrides, esters, and acidic salts. , Sulfuric acid, phosphoric acid, silicic acid, aluminate, perchloric acid, formic acid, propionic acid, caproic acid, oxalic acid, succinic acid, adipic acid, maleic acid, phthalic acid, benzoic acid, salicylic acid, anthranilic acid, octanoic acid, etc., or Examples thereof include anhydrides, esters, and acid salts thereof.

Among these, phosphoric acid, silicic acid, chloroacetic acid, phthalic acid, and the like are preferable because those having an acid dissociation index pKa in an aqueous solution of 2.0 to 3.0 are remarkable in terms of the effect of promoting curing. Examples thereof include salicylic acid and anthranilic acid, and anhydrides, esters, and acidic salts thereof.

Of these acids, acidic phosphate esters and salicylic acid are particularly preferred because the effects of the present invention are particularly remarkable.

The amount of the acidic substance used is arbitrarily adjusted depending on the desired curing time. Usually, the acid equivalent of the acidic substance is 0.005 to 0.005 equivalent to the active hydrogen equivalent of the compound (B).
It is in the range of 0.1. If it is less than 0.005, the curing speed is very slow, and if it exceeds 0.1, sufficient performance regarding the adhesive properties cannot be obtained.

As the solvents, usual urethane solvents such as toluene, xylene, terpene, ethyl acetate, acetone, naphthene and paraffin can be used. As the process oil, an ordinary high-boiling oil obtained in petroleum refining can be used.

Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, dinonyl phthalate, diisodecyl phthalate, ditridecyl phthalate, diundecyl phthalate, phthalic acid, etc., and tri- (2-ethylhexyl) trimellitate and triisooctyl trimellitate. And general compounds of trimellitic acid such as triisodecyl trimellitate can be used. In particular, diundecyl phthalate, diisodecyl phthalate, tri- (2-ethylhexyl) having a relatively large molecular weight and having little adverse effect on adhesive properties can be used. ) Trimellitate is preferred.

The extender includes carbon black, calcium carbonate, talc, clay, silica, titanium oxide and the like.

Examples of the thixotropic agent include surface-treated calcium carbonate, polyvinyl chloride powder, finely divided silica, bentonite, sepiolite and the like. In addition, the urethane resin composition of the present invention may be mixed with a petroleum-based high-boiling aromatics fraction, a petroleum resin and the like.

The one-component moisture-curable urethane composition of the present invention is mainly used as an adhesive for civil engineering and construction, as well as for vehicles and laminations. Useful as an adhesive.

[0046]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the examples. Unless otherwise noted, “parts” and “%” in the examples are on a weight basis.

(Production Example 1 of Urethane Prepolymer) Polypropylene ether diol 89 having an average molecular weight of 3000
6.0 g and 2,4-tolylene diisocyanate
9 g of NCO / OH equivalent ratio of 2.0 was reacted in a flask under a nitrogen atmosphere at 60 ° C. for 48 hours with stirring, and a urethane prepolymer (NCO%: 2.51%) was reacted.
CO-1) was obtained.

(Production Example 2 of Urethane Prepolymer) Polypropylene ether diol 67 having an average molecular weight of 3000
6.3 g and 2,8.5 tolylene diisocyanate 78.5
g of the polyesterdiol (1,4-butanediol, adipic acid type) having an average molecular weight of 2,000, and then reacting with 145.2 g of NCO / OH. The mixture was reacted while stirring in a flask at a ratio of 1.5 under a nitrogen stream at 60 ° C. for 48 hours to obtain a urethane prepolymer (NCO-2) having an NCO% of 2.8%.

(Preparation Example 1 of Urethane Oxazolidine Compound) 920.4 g of urethane prepolymer (NCO-1)
And 2-isopropyl-3 (2-hydroxyethyl) 1,3 oxazolidine in an equivalent ratio of NCO / OH of 1.1 under a nitrogen stream at 60 ° C. for 48 hours while stirring in a flask to give urethane oxazolidine. A compound (number average molecular weight 3700, called OXZ-1) was obtained. As a result of measuring the GPC of this composition, it was confirmed that the content of the remaining 2-isopropyl-3 (2-hydroxyethyl) 1,3 oxazolidine was 1% or less.

(Production Example 2 of Urethane Oxazolidine Compound) 36.7 g of hexamethylene diisocyanate and 63.3 g of 2-isopropyl-3 (2-hydroxyethyl) 1,3 oxazolidine, that is, an equivalent ratio of NCO / OH of 1.
The reaction was conducted while stirring in a flask at 60 ° C. for 48 hours under a nitrogen stream at 1 to obtain a urethane oxazolidine compound (OXZ-2, number average molecular weight 490). As a result of measuring the GPC of this composition, it was confirmed that the content of the remaining 2-isopropyl-3 (2-hydroxyethyl) 1,3 oxazolidine was 1% or less.

Examples 1 to 7 Comparative Examples 1 to 4 [Formulation of Compound] The compositions shown in Tables 1 and 2 were dried in a closed planetary mixer at 150 ° C. for 2 hours to adjust the water content to 0.05% or less. Calcium carbonate (NS-200, manufactured by Nitto Powder Co., Ltd.), 12
Fatty acid-treated calcium carbonate (Hakuenka CCR made of Shiroishi Calcium), which was dried at 0 ° C. for 3 hours to adjust the water content to 0.1% or less, the urethane prepolymer (NCO-2) obtained in the above preparation example, a diisocyanate compound, and a polyisocyanate Isocyanate compounds, oxazolidine compounds (OXZ-1,
-2), ethyl acetate, diundecyl phthalate (hereinafter referred to as D
UP) and a curing accelerator were added in a predetermined amount as shown in Tables 1 and 2, respectively, and uniformly mixed to obtain a one-part moisture-curable urethane compound.

The results were evaluated by the following test methods, and the results are shown in Tables 1, 2, and 3.

[Test Method] (Workability of Coating) Under a condition of temperature and humidity of 20 ° C. × 50%, the compound was put on a slate plate using a comb-like iron (JIS-A-55).
36 standard product), and those with good workability were marked with 、, and those with poor workability were marked with x.

(Storage stability) 500 g of the compound was collected in a 500 cc sealable metal can, stored in a constant temperature bath at 50 ° C. for 7 days, and expressed as a rate of increase in viscosity with respect to the initial viscosity. The viscosity was measured using a No. 6 rotor of a BH-type rotational viscometer, 20
It was measured at 25 ° C. rpm.

(Bubble Inhibiting Property) Under the condition of temperature and humidity of 20 ° C. × 50%, the compound is applied on a slate plate with a comb-like iron (JIS-A-5536 standard product), and then the condition of 70 ° C. × 50%. It was changed below, and those with foaming of the adhesive layer were marked with x, and those without foaming were marked with o.

(Adhesive Properties) <Preparation of Test Specimen> Under a condition of temperature and humidity of 20 ° C. × 50%, the compound was put on a slate plate using a comb (JIS-A-55).
36 standard product), and after standing for 20 minutes, the vinyl chloride sheet was pressed with a hand roll and cured for 72 hours. After that, a sheet made of vinyl chloride is 1 inch wide and 1 inch long.
The test piece was cut to 0 cm to prepare a test piece.

<Peeling Test> Using a tensile testing machine (Tensilon), a 90 ° peel test was carried out at room temperature at a speed of 200 mm / min.

(Initial Adhesion) Under a condition of temperature and humidity of 20 ° C. × 50%, the compound was applied to a slate plate with a comb (JIS-A-5536 standard), and then left for 20 minutes. The sheet made was pressed with a hand roll, and after 60 minutes, a 90 ° peel test was performed at a speed of 200 mm / min at room temperature using a tensile tester (Tensilon).

[Examples 1 to 7] In any of Examples 1 to 7, they had a non-volatile content of 95% or more, and exhibited excellent foam suppression properties, coating workability, storage stability, initial tackiness, and adhesive properties. Was.

[Comparative Example 1] Since there was no diisocyanate compound having a high reactivity with active hydrogen, the initial tackiness was poor.

Comparative Example 2 Since no polyisocyanate compound was used, the adhesive properties were poor.

[Comparative Example 3] Since the reactivity of the polyisocyanate compound with active hydrogen is faster than that of the diisocyanate compound, the initial tackiness is too fast to be applied, and the coating workability is poor.
In addition, since the tackiness holding time is shortened, the time during which the adherend can be stuck is shortened, and a film is already formed on the compound in an open time of 20 minutes, resulting in poor initial tackiness.

Comparative Example 4 Since the urethane oxazolidine compound has a number average molecular weight of less than 1000, the adhesive properties are maintained, but the initial tackiness is poor.

Comparative Example 5 A commercially available adhesive for vinyl flooring (Rubilon 101, manufactured by Toyo Polymer) was used. Although all performances are balanced, there is a problem in safety and health because it contains about 25% of a solvent.

[0065]

[Table 1] [Blending conditions and test results]

Note) 1); MDI: diphenylmethane diisocyanate; 2); TDI adduct: trimethylolpropane and TD
Adduct of I contains 75% non-volatile content of ethyl acetate (Coronate L, manufactured by Nippon Polyurethane Industry) 3); Acidic phosphate (isopropyl acid phosphate) 4) NCO / (H): NCO group and oxazolidine group open It shows the equivalent ratio to the generated active hydrogen (primary amine + hydroxyl group). 5); number average molecular weight of urethane oxazolidine compound,
Rounded to 10th place

[0067]

[Table 2]

Note) 1); MDI: diphenylmethane diisocyanate TDI: 2,4-tolylene diisocyanate 2); HDI type: HDI burette (duranate 2)
4A-100, manufactured by Asahi Kasei Kogyo Co., Ltd.) TDI adduct: adduct of trimethylolpropane and TDI, nonvolatile matter containing 75% of ethyl acetate (Coronate L,
C-MDI: polymethylene polyphenylisocyanate (Millionate MR200, manufactured by Nippon Polyurethane Industry) 3); acid phosphate (isopropyl acid phosphate) 4) NCO / (H): NCO group and oxazolidine group open The equivalent ratio with active hydrogen (primary amine + hydroxyl group) generated by ringing is shown. 5); number average molecular weight of urethane oxazolidine compound,
Rounded to 10th place

[0069]

[Table 3]

Note) 1); MDI: diphenylmethane diisocyanate TDI: 2,4-tolylene diisocyanate 2); HDI type: HDI burette (duranate 2)
4A-100, manufactured by Asahi Kasei Kogyo Co., Ltd.) TDI adduct: adduct of trimethylolpropane and TDI, nonvolatile matter containing 75% of ethyl acetate (Coronate L,
C-MDI: polymethylene polyphenyl isocyanate (Millionate MR200, manufactured by Nippon Polyurethane Industry) 3); acid phosphate (isopropyl acid phosphate) 4) NCO / (H): NCO group and oxazolidine group are open The equivalent ratio with active water (primary amine + hydroxyl group) generated by ringing is shown. 5); number average molecular weight of urethane oxazolidine compound,
Rounded to 10th place

[0071]

Industrial Applicability The present invention has excellent characteristics in terms of storage stability, suppression of foaming in addition to adhesive properties, and good coating workability even under conditions of no solvent or low solvent.
An object of the present invention is to provide a moisture-curable urethane composition and an adhesive exhibiting initial tackiness.

Since the present invention has a low solvent and low odor, it is industrially useful as an adhesive for civil engineering construction, building material production, woodworking, textile-related, vehicle-related, and film lamination. Yes, it is also useful from a health and safety point of view.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C09J 175/04 JFA C09J 175/04 JFA JFD JFD JFF JFF

Claims (8)

[Claims] 1. An isocyanate compound (A), and (B)
In a one-pack moisture-curable urethane composition comprising, as essential components, a compound having one or more oxazolidine rings in the molecule, a urethane prepolymer (a1) having (A) two or more isocyanate groups at a terminal and a diisocyanate compound A one-component moisture-curable urethane composition comprising (a2) and a polyisocyanate compound (a3) having more than two isocyanate groups in a molecule as essential components. 2. The one-part, moisture-curable urethane prepolymer (a1) having two or more isocyanate groups at its terminals, which is obtained by a reaction between a polyol compound and a polyisocyanate compound. Urethane composition. 3. The one-part, moisture-curable urethane composition according to claim 1, wherein the compound (B) having one or more oxazolidine rings in the molecule has a number average molecular weight of 1,000 or more. . 4. An isocyanate compound (A) having the highest reactivity with active hydrogen H (a primary amine and a hydroxyl group) generated by hydrolyzing an oxazolidine ring of the compound (B) is a diisocyanate of the compound (a2) 4. The one-pack moisture-curable urethane composition according to claim 1, which is a compound. 5. The polyisocyanate compound (a3),
Adducts in which a compound having two or more active hydrogens and a diisocyanate compound have reacted, burettes in which a diisocyanate compound has reacted with water, isocyanurates in which the diisocyanate compound has been trimerized, and one or more of these The one-component moisture-curable urethane composition according to any one of claims 1 to 4, which is a mixture of the above-mentioned or a modified product thereof. 6. The ratio between the isocyanate group of the diisocyanate compound (a2) and the active hydrogen H generated by hydrolysis of the compound (B) is -NCO / -H = 0.
The one-part moisture-curable urethane composition according to any one of claims 1 to 5, wherein the composition is 1 to 2.0. 7. The total of isocyanate groups of compound (A) and active hydrogen H generated by hydrolysis of compound (B)
The one-component moisture-curable urethane composition according to any one of claims 1 to 6, wherein the ratio of -NCO / -H is 0.4 to 4.0 in equivalent ratio. 8. An adhesive comprising the one-part moisture-curable urethane composition according to claim 1.