JP2003221569A - One-pack moisture-curable type polyurethane resin-based adhesive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a one-pack moisture-curable type polyurethane resin-based adhesive reducing the dependency on the application condition of exhibition of initial adhesive force and a period in which the bonding is allowed, making the exchange of formulating compositions of the adhesive for winter and summer unnecessary, capable of being used all through the year, and having excellent adhesiveness, and to provide a floor structure using the adhesive. <P>SOLUTION: This one-pack moisture-curable type polyurethane resin-based adhesive contains (A) a polyurethane resin having an active isocyanate group such as a residue of diphenylmethane diisocyanate in the molecule, (B) a polyisocyanate having a low-active isocyanate group such as a residue of hexamethylene diisocyanate in the molecule, and (C) a nonreactive polar organic solvent as essential components. The floor structure uses the adhesive. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD [0001] The present invention is excellent in the development of the initial adhesive strength when used under low temperature and low humidity conditions in winter, and has a long sticking time when used under high temperature and high humidity conditions in summer. ,
The present invention relates to a one-component moisture-curable polyurethane resin-based adhesive having excellent adhesiveness, and particularly to an adhesive and a floor structure suitable for laying a flooring material on a base material at a construction site.

[0002]

2. Description of the Related Art Recently, as an adhesive used when laying a flooring material on a base material, instead of a two-component type epoxy resin adhesive, there is no need for the two-component type and a curing agent. As one example, one-component moisture-curable polyurethane resin-based adhesives, which are less likely to cause rashes, such as epoxy resin-based adhesives using amine compounds, are becoming mainstream.

Most of the one-component moisture-curable polyurethane resin adhesives are "moisture-curable" which are cured by the reaction of the isocyanate group with air or moisture in the substrate, and therefore, the isocyanate group and the air. The reaction with water in the base material and the base material is greatly affected by temperature and humidity. Therefore, under low temperature and low humidity conditions such as winter, a method of adding a large amount of reaction accelerator is performed in order to impart the initial adhesive force development required to suppress the repulsion of the substrate, and high temperature and high temperature such as summer. In order to secure the sticking time required for work under wet conditions, a method of reducing the amount of the reaction accelerator added or not adding it is used.

However, with such a method, the composition for winter construction has a short sticking time in the summer, and conversely, the composition for summer construction has a problem that the initial adhesive force development in winter is slow. It took time and effort to switch between the composition for winter construction and the composition for summer construction. In addition, the adhesiveness to difficult-to-adhere materials such as plastics and vinyl chloride resin may vary depending on the construction environment, and sufficient adhesiveness may not be obtained.

Several proposals have been made to solve such problems. For example, in Japanese Unexamined Patent Publication No. 9-235540, a composition comprising a one-part moisture-curable urethane resin containing 2,4′-diphenylmethane diisocyanate and an amine catalyst is used to obtain an initial adhesive force. A method for reducing the dependency of the expressivity and the stickable time on the construction environment is disclosed. This technique uses 4,4'-diphenylmethane diisocyanate to produce 4,4 '
-It is possible to reduce the dependency of initial adhesive strength and sticking time on the construction environment compared to the case of using diphenylmethane diisocyanate alone, but it is insufficient, and the reaction accelerator in winter and summer is insufficient. The problem of increasing or decreasing the amount, that is, the problem of switching between the formulation for winter construction and the formulation for summer construction has not been solved.

[0006] Further, in Japanese Patent Laid-Open No. 11-263962, adhesiveness is improved by using a one-component moisture-curable urethane resin using Clude MDI, N-methyl-2-pyrrolidone and a tertiary amine catalyst. Although a technique for imparting improved and quick-curing properties has been disclosed, there is a problem in that the balance between the initial adhesive strength expression required for an adhesive for construction site construction and the stickable time is lacking.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to reduce the dependency of initial adhesive strength and sticking time on the construction environment, and to eliminate the need to switch the composition of the adhesive between winter and summer. It is intended to provide a one-component moisture-curable polyurethane resin-based adhesive having excellent adhesiveness, which can be used all year round, and a floor structure.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have made a specific polyurethane resin, a specific polyisocyanate and a non-reactive polar organic solvent an essential component. When a one-component moisture-curable polyurethane resin adhesive was used, it was found that the above problems could be solved, and the present invention was completed.

That is, according to the present invention, a polyurethane resin (A) having an active isocyanate group in the molecule, a polyisocyanate (B) having a low active isocyanate group in the molecule, and a non-reactive polar resin are used. It is intended to provide a one-component moisture-curable polyurethane resin-based adhesive characterized by containing an organic solvent (C) as an essential component. Further, the present invention provides a floor structure characterized in that a floor material is laid on a base material via the above adhesive.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail.
First, an active isocyanate group (hereinafter referred to as active NC) used in the one-component moisture-curable polyurethane resin-based adhesive of the present invention.
The polyurethane resin (A) having an O group (hereinafter referred to as polyurethane resin (A)) will be described.

By "active" of an active NCO group is meant high reactivity with air or water present in the substrate. The polyurethane resin (A) having an active NCO group effectively acts to develop the initial adhesive strength, which is the object of the present invention.

The polyisocyanate having an active isocyanate group in the molecule used in the present invention is 4,4 '.
-Diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate , 3,3'-dichloro-4,4'-biphenylene diisocyanate and the like. These 1 type, or 2 or more types of mixture can be used.

The polyurethane resin (A) is not particularly limited as long as it has an active isocyanate group, but from the viewpoint of developing the initial adhesive strength, diphenylmethane diisocyanate ( It is preferable to have an active isocyanate group which is a residue of MDI). Examples of MDI include an active NCO group in the molecule such as 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, and 2,2′-diphenylmethane diisocyanate. Examples thereof include pure diphenylmethane diisocyanate having two or more, carbodiimidated diphenylmethane polyisocyanate, polymethylene polyphenyl polyisocyanate and the like. These 1 type, or 2 or more types of mixture can be used.

The structure of the above MDI is not particularly limited, but 4,4'-diphenylmethane diisocyanate-
It is preferable to use a combination of a bismuth and 2,4'-diphenylmethane diisocyanate together from the viewpoint of the balance between the initial adhesive strength development and the stickable time. In this case, the ratio of 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate is not particularly limited, but the balance between the initial adhesive strength expression and the stickable time is shown. From the viewpoint of 4,4'-diphenylmethane diisocyanate-
It is preferable that the weight ratio of 2,2'-diphenylmethane diisocyanate is 90/10 to 40/60.

Also, polyisocyanate other than the above MDI
Can be used as long as the object of the present invention is not impaired. Examples of such polyisocyanate include 2,
4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-
Phenylene diisocyanate, 3,3'-dimethyl-
4,4'-biphenylene diisocyanate, 3,3'-
Dimethoxy-4,4'-biphenylene diisocyanate
3,3'-dichloro-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate,
Trisine diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethyl hexamethylene Diisocyanate, 1,3-Cyclohexylene diisocyanate, 1,4-Cyclohexylene diisocyanate
, Xylylene diisocyanate, tetramethyl xylylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, lysine diisocyanate, isophorone diisocyanate,
4,4'-dicyclohexylmethane diisocyanate,
3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate and the like can be mentioned.

Polyurethane resin (A) used in the present invention
Examples of the polyol constituting the above are polyester polyester, polyether polyol and polycarbonate.
Topolol, polyacetal polyol, polyacrylate polyol, polyesteramide polyol, polythioether polyol, polybutadiene topolol
And polyolefin polyols such as hydrogenated polybutadiene polyol and the like. These 1 type, or 2 or more types of mixture can be used. Of these, polyester polyol and polyether polyol are preferable from the viewpoint of coating workability and adhesiveness.

Examples of the polyester polyols include condensation polymers of glycol components and polybasic acids, ring-opening polymers of lactones such as caprolactone and valerolactone, and copolymerization thereof. For example, ethylene glycol
, Propylene glycol, 1,3-propanedioe
1,4-butanediol, 1,5-pentanediol
, 3-methyl-1,5-pentanediol, dimethylol heptane, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol -(Molecular weight 300 to 6,000), dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediole
, 1,4-cyclohexane dimethanol, glycerin, trimethylolethane, sorbitol, pentaerythritol, trimethylolpropane, bisphenol A, hydrogenated bisphenol A, hydroquinone and their alkylene oxides. Glycol components such as adducts and succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,
3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid , Biphenyl dicarboxylic acid, dimer
Acid, hydrogenated dimer acid, 1,2-bis (phenoxy)
Ethane-p, p'-dicarboxylic acids and anhydrides or ester-forming derivatives of these dicarboxylic acids; p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid and ester-forming derivatives of these hydoxycarboxylic acids. Polyester and the like obtained by dehydration condensation reaction with a polybasic acid component such as.

Further, as the above polyether type polyol, ethylene oxide, propylene oxide, in the presence of a compound having two or more active hydrogen groups in the molecule,
Examples thereof include those obtained by addition-polymerizing one or more monomers such as butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran and cyclohexylene by a conventional method. Examples of the compound having two or more active hydrogen groups in the molecule include ethylene glycol-
, Diethylene glycol, triethylene glycol,
Propylene glycol, dipropylene glycol, trimethylene glycol, butylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 3-methyl- 1,5-pentanedio
Le, dimethylol heptane, neopentyl glycol,
Glycerin, trimethylolethane, trimethylolpropane, glucose, sucrose, sorbitol,
Bisphenol A, sucrose, aconit sugar, trimellitic acid, hemimellitic acid, phosphoric acid, ethylenediamine, diethylenetriamine, butylenediamine, triisopropanolamine, pyrogallol, dihydroxybenzoic acid, hydroxyphthalic acid, 1,2 , 3-propanetrithio-
And the like. The polyurethane resin (A) used in the present invention contains the above MDI and polyol in an NCO group / O
It can be obtained by reacting so that the H group equivalent ratio exceeds 1.0.

Polyurethane resin (A) used in the present invention
A chain extender can be further used in the preparation of

Examples of the chain extender include ethylene glycol, diethylene glycol and triethylene glycol.
, Propylene glycol, dipropylene glycol,
Trimethylene glycol, 1,3-butanediol,
1,4-butanediol, butylene glycol, 1,6
-Hexanediol, 3-methyl-1,5-pentanediol, dimethylolheptane, neopentylglycol-
Le, glycerin, trimethylol-ethane, trimethylol-
Le propane, sorbitol, glucose, sucrose
And bisphenol A, ethylenediamine, diethylenetriamine, butylenediamine, triisopropanolamine, 1,2,3-propanetrithiol, and other compounds having at least two active hydrogen atoms.

Next, the polyisocyanate (B) having a low activity isocyanate group in the molecule used in the present invention will be explained. By "low activity" of such low activity isocyanate groups is meant that the reactivity with air or water present in the substrate is relatively low. Therefore, the low-activity isocyanate group gradually reacts with water, and this reaction has the effect of sustaining the effect, and the polyisocyanate (B) having a low-activity isocyanate group in the molecule is used in the present invention. It effectively acts to secure the target long sticking time.

Examples of the polyisocyanate having a low activity isocyanate group in the molecule used in the present invention include, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and 3 , 3'-Dimethyl-4,4 '
-Biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 1,5
-Naphthalene diisocyanate, tolidine diisocyanate, 1,5-tetrahydronaphthalene diisocyanate
, Tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethyl hexamethylene diisocyanate,
1,3-cyclohexylene diisocyanate, 1,4-
Cyclohexylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate
Hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, lysine diisocyanate
, Isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 3,3′-dimethyl-4,4′-dicyclohexylmethane diisocyanate and the like.

The polyisocyanate (B) having a low activity isocyanate group in the molecule [hereinafter referred to as polyisocyanate (B)] is not particularly limited as long as it has a low activity isocyanate group. However, from the viewpoint of ensuring the sticking time, it is preferable that the low-activity isocyanate group is a residue of hexamethylene diisocyanate. In this case, the structure of the polyisocyanate (B) is not particularly limited, but from the viewpoint of ensuring the sticking time, the burette type polyisocyanate represented by the general formula [1] and the general formula [2] ] Isocyanurate type polyisocyanate represented by the formula [2] and bifunctional prepolymer type polyisocyanate represented by the general formula [3] are preferable. These polyisocyanates may be used alone or in combination of two or more.

[0024]

[Chemical 4]

[0025]

[Chemical 5]

[0026]

[Chemical 6]

In the general formulas [1], [2] and [3], R represents an alkylene group having 6 to 40 carbon atoms, and R'is 2 to 300 carbon atoms. It represents an alkylene group.

Commercially available products of polyisocyanate (B) include, for example, Duranet 24A-100 (buret type), Duranet TPA-100, Duranet.
THA-100 (above isocyanurate type), Duranet D-101, Duranate D-201 (above difunctional prepolymer type) (above Asahi Kasei Corporation), Coronet EH (isocyanurate type) )
(These are manufactured by Nippon Polyurethane Industry Co., Ltd.), Sumijour N3200 (buret type), and Sumijour N3500 (isocyanurate type) (all manufactured by Sumitomo Bayer Urethane Co., Ltd.).

The amount of the polyisocyanate (B) used in the present invention is not particularly limited, but from the viewpoint of the balance between the initial adhesive strength expression and the stickable time,
The weight ratio of the active NCO group of the polyurethane resin (A) to the low active NCO group of the polyisocyanate (B) is
Preferably NCO group of (A) / NCO group of (B) = 90
/ 10 to 50/50, more preferably 75/25 to 50
/ 50.

Non-reactive polar organic solvent (C) which is a constituent of the one-part moisture-curable polyurethane resin adhesive of the present invention
There is no particular limitation as long as it does not react with the active NCO group, but a nitrogen-containing solvent is preferable from the viewpoint of adhesiveness. "Non-reactive" of non-reactive polar organic solvent,
Means that it will not react with the active NCO groups under the conditions used as an adhesive. The conditions for use as an adhesive include, for example, a temperature of about 0 ° C to 50 ° C and a relative humidity of about 10 ° C.
% To 95%. Examples of the nitrogen-containing solvent include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide,
1,3-dimethyl-2-imidazolidine and the like can be mentioned. One kind or a mixture of two kinds thereof can be used, but N-methyl-2-pyrrolidone is preferable from the viewpoint of adhesiveness. It is particularly preferred to use such N-methyl-2-pyrrolidone alone.

The amount of the non-reactive polar organic solvent (C) used in the present invention is not particularly limited, but from the viewpoint of adhesiveness, the polyurethane resin (A) and the polyisocyanate (B) are used. It is preferably 0.5 to 10.0 parts by weight, and more preferably 0.5 to 5.0 parts by weight, based on 100 parts by weight of the total resin content.

The one-component moisture-curable polyurethane resin-based adhesive of the present invention may further contain a tertiary amine type reaction accelerator (D) having a morpholine skeleton in the molecule, from the viewpoint of developing the initial adhesive strength. preferable.

Examples of the tertiary amine type reaction accelerator (D) include bis (morpholinoethyl) ether, bis (2,6-dimethylmorpholinoethyl) ether, and bis (3,5-dimethylmorpholino). Ethyl) ether and the like.

The amount of the tertiary amine type reaction accelerator (D) used in the present invention is not particularly limited, but from the viewpoint of the balance between the initial adhesive strength development and the stickable time,
The total amount of the resin components of the polyurethane resin (A) and the polyisocyanate (B) is 100 parts by weight, preferably 0.
5 to 5.0 parts by weight, more preferably 1.0 to 3.
0 parts by weight.

The one-component moisture-curable polyurethane resin adhesive of the present invention may contain, for example, a diluent, a filler, and
A thixotropy-imparting agent, a tackifier, other additives and the like can be added within a range that does not impair the object of the present invention.

Examples of the diluent include acetone,
Examples thereof include solvents such as methyl ethyl ketone, ethyl acetate, toluene, xylene, alicyclic hydrocarbon type and aromatic hydrocarbon type.

Examples of the filler include calcium carbonate, kaolin, clay, talc, titanium oxide, organic balun, inorganic balun, bentonite, carbon black and the like.

Examples of the thixotropy-imparting agent include, for example,
Fatty acids, fatty acid metal salts, fatty acid esters, paraffin,
The fillers surface-treated with a resin acid, a surfactant, polyacrylic acid or the like, polyvinyl chloride powder, hydrogenated castor oil, fine powder silica, organic bentonite, sepiolite and the like can be mentioned.

Examples of the tackifier include rosin resin type, terpene resin type, phenol resin type and the like.

Further, other additives include, for example, metal-based reaction accelerators, water-removing agents such as 4-paratoluenesulfonyl isocyanate, adsorbents such as quick lime, slaked lime, zeolite, and molecular sieves. Examples thereof include adhesion promoters such as silane coupling agents.

The one-component moisture-curable polyurethane resin-based adhesive of the present invention has a low dependence of initial adhesive strength and sticking time on the construction environment, and the composition of the adhesive cannot be switched between winter and summer. Since it is necessary, it can be used all year round.
Specifically, regardless of the construction environment, the initial adhesive force is developed within 60 minutes after application, and the stickable time after the initial adhesive force is exhibited is 20 minutes or more.

Applications of the one-part moisture-curable polyurethane resin adhesive of the present invention include construction sites, building factories, plywood,
Woodworking, civil engineering, bookbinding, laminating, vehicles, shoes and footwear, packaging and the like can be mentioned, and it is particularly preferably used as an adhesive for laying a floor material on a base material at a construction site.

The floor structure of the present invention comprises a floor material, an adhesive, and a base material. At the construction site, the floor material is bonded to the base material via the one-component moisture-curable polyurethane resin adhesive. The present invention relates to a floor structure of a building formed by laying.

In the floor structure of the present invention, since the base material and the floor material are bonded via the one-component moisture-curable polyurethane resin adhesive as the above-mentioned adhesive, excellent initial performance is achieved regardless of winter and summer. It has a feature that adhesive strength is exhibited and a long sticking time is maintained. Therefore, the flooring material is firmly fixed to the base material regardless of the construction environment, so that the flooring structure is excellent in mechanical strength and the like.

As the floor material, for example, PVC floor sheet,
A PVC floor tile etc. are mentioned. The base material may be, for example, concrete, mortar, or PVC floor sheet.
And PVC floor tiles.

The method for adhering the floor material and the base material is not particularly limited, and a known adhering method can be used. As such an adhesion method, for example, JIS A55
There is a method of using a comb-like iron as defined in 36-1996.

[0047]

EXAMPLES The present invention will be described below with reference to Examples and Comparative Examples.
More specifically, the scope of the present invention is not limited to these examples. The following parts are parts by weight unless otherwise specified.

Synthesis Example 1 Synthesis of Polyurethane Resin In a clean flask, 900.00 g of polypropylene etherdiol having a number average molecular weight of 2000 and 3-methyl-
Polyester diol obtained from 1,5-pentanediol and adipic acid (having a number average molecular weight of 2000) 1
00.00 g was charged, and 4,4'-diphenylmethane diisocyanate 375.
39 g (corresponding to NCO group / OH group = 3.00 equivalent ratio) was charged, and the resin temperature was adjusted to 7 while stirring under a nitrogen atmosphere.
After reacting at 0 to 90 ° C. for 10 hours, the NCO group was 6.11.
A weight% polyurethane resin [hereinafter referred to as polyurethane resin 1] was obtained.

<Synthesis Example 2> Synthesis of polyurethane resin In a clean flask, 900.00 g of polypropylene ether diol having a number average molecular weight of 2000 and 3-methyl-
Polyester diol obtained from 1,5-pentanediol and adipic acid (having a number average molecular weight of 2000) 1
00.00 g was charged, and 4,4'-diphenylmethane diisocyanate and 2,2, while stirring under a nitrogen atmosphere.
375.39 g of a mixture of 4'-diphenylmethane diisocyanate in a weight ratio of 50/50 (NCO group / OH
(Group = 3.00 equivalent ratio), and further, while stirring under a nitrogen atmosphere, the resin temperature is 70 to 90 ° C.
Then, the reaction was carried out for 10 hours to obtain a polyurethane resin having an NCO group of 6.11% by weight [hereinafter referred to as polyurethane resin 2].

<< Examples 1 to 10 >> and << Comparative Examples 1 to 5 >> NS # 200 [surface-untreated heavy calcium carbonate, manufactured by Nitto Koka Kogyo Co., Ltd.] 4 in a closed planetary mixer
00.00 g, white luster CCR [surface-treated light calcium carbonate, manufactured by Shiraishi Industry Co., Ltd.] 100.00 g, and dioctyl phthalate (DOP) 250.00 g were charged, and the temperature of the mixture was 110 to 130. The water content of the mixture was adjusted to 0.05% by weight or less by setting the temperature to be 0 ° C. and dehydrating under a reduced pressure of about 8 kPa. Then, the mixture was cooled to 50 ° C. or lower, 10.00 g of 4-paratoluenesulfonyl isocyanate was added, and mixed until uniform. Further, as shown in Tables 1 to 6, a predetermined amount of polyurethane resin, polyisocyanate, N-methyl-2-pyrrolidone and a tertiary amine type reaction accelerator were charged, and after mixing these until uniform, about 8 kPa After defoaming under reduced pressure, the one-component moisture-curable polyurethane resin adhesive of the present invention was obtained. The charging, mixing and taking out were carried out in a nitrogen atmosphere in order to prevent the entry of moisture. The evaluation results of the one-component moisture-curable polyurethane resin-based adhesive are shown in Table 1, Table 2, Table 3, Table 4, Table 5 and Table 6.

The types of polyisocyanate (B) shown in Tables 1 to 6 are the burette type of Duranate 24A-100 and the isocyanurate type of Duranate TPA-100. D-101
Is a bifunctional prepolymer type.

The evaluation method and evaluation criteria of the one-component moisture-curable polyurethane resin adhesive of the present invention will be described below. [Initial adhesive strength development] Base material (length 20 cm x width 10 c
m, thickness 5 mm), the one-component moisture-curable polyurethane resin-based adhesive obtained in the above Examples and Comparative Examples is applied with a comb eye. Floor material (length 12.5 cm x 10 minutes after application)
Width 25 mm, thickness 3 mm) Adhesive area 10 cm long
It is clamped with a linear pressure of about 50 N / 25 mm × 2 reciprocations so as to have a width of 25 mm, and immediately a shear creep of a load of about 200 g is measured (weight is the length direction of the floor material). The initial adhesive force development time (unit: minutes) was defined as the time at which the deviation length after 50 seconds from the shear creep measurement was 50 mm or less, and the initial adhesive force development was evaluated.

[Available time] Base material (length 20 cm x
The one-component moisture-curable polyurethane resin-based adhesive obtained in the above Examples and Comparative Examples is applied to a width of 10 cm and a thickness of 5 mm with a comb-like iron. Every 10 minutes after application, floor material (length 12.
5 cm x width 25 mm, thickness 3 mm) with an adhesion area of length 1
Approximately 50 N / 25 mm x 2 to be 0 cm x width 25 mm
The floor material is peeled off after 30 seconds of compression with reciprocating linear pressure. The time during which the rate of transfer of the adhesive to the floor material was kept at 50% was defined as the stickable time. The term "transfer rate" as used herein means a rate at which the adhesive adheres to the floor material. In addition, the "attachable time" is the ratio of the adhesive that adheres to the flooring material to 50% of the total adhesive area.
This is the time that is held.

[Adhesive Strength] Using the one-component moisture-curable polyurethane resin adhesive obtained in the above Examples and Comparative Examples, J
The adhesive strength was measured and evaluated according to ISA5536-1996.

The following materials and tools were used for measuring / evaluating the initial adhesive strength development property, the sticking time, and the adhesive strength. In addition, the evaluation of initial adhesive strength, sticking time, and adhesive strength was carried out in an environmental test chamber, and used materials, tools, and one-component moisture-curable polyurethane resin-based adhesives obtained in Examples and Comparative Examples. Was used after being left for 24 hours. Base material: Slate floor material specified in JIS A 5430: Vinyl floor tile specified in JIS A 5705 Vinyl floor sheet specified in JIS A 5705 Comb iron: SS330 specified in JIS G 3101

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

[Table 3]

[0059]

[Table 4]

[0060]

[Table 5]

[0061]

[Table 6]

[0062]

EFFECTS OF THE INVENTION The one-part moisture-curable polyurethane resin-based adhesive of the present invention has low initial adhesive strength and low dependency on the working environment of the stickable time, and has a composition of the adhesive composition in winter and summer. It does not require switching and can be used all year round and has excellent adhesiveness. For this reason, it is extremely useful for bonding the floor material and the base material, particularly in construction site construction. Further, since the floor structure using the adhesive of the present invention is excellent in durability and the like, it has performance satisfying JIS A 5536-1996.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4J040 EF001 EF261 EF321 GA20                       HC20 JA12 JB04 KA17 KA23                       MA06 MA08 MB09 NA12

Claims (13)

[Claims] 1. A polyurethane resin (A) having an active isocyanate group in the molecule, a polyisocyanate (B) having a low active isocyanate group in the molecule, and a non-reactive polar organic solvent (C). ) And 1 are contained as essential components, a one-pack moisture-curable polyurethane resin adhesive. 2. The one-part moisture-curable polyurethane resin adhesive according to claim 1, wherein the active isocyanate group of the polyurethane resin (A) is a residue of diphenylmethane diisocyanate. 3. The polyisocyanate (B) is selected from the group consisting of a compound represented by the general formula [1], a compound represented by the general formula [2] and a compound represented by the general formula [3]. The one-component moisture-curable polyurethane resin-based adhesive according to any one of claims 1 to 3, which is at least one selected from polyisocyanates. [Chemical 1] [Chemical 2] [Chemical 3] (In the general formula [1], the general formula [2] and the general formula [3], R represents an alkylene group having 6 to 40 carbon atoms, and R ′ represents an alkylene group having 2 to 300 carbon atoms. Represent) 4. The one-component moisture-curable polyurethane resin adhesive according to claim 1, wherein the low-activity isocyanate group of the polyisocyanate (B) is a residue of hexamethylene diisocyanate. 5. The weight ratio of the active isocyanate group of the polyurethane resin (A) to the low active isocyanate group of the polyisocyanate (B) is (A) / (B).
= 90/10 to 50/50, The one-component moisture-curable polyurethane resin adhesive according to any one of claims 1 to 4. 6. As the diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate (a-1) and 2,4′-diphenylmethane diisocyanate (a-2) are used in combination. Any one of claims 1 to 4
Item 1. A one-part moisture-curable polyurethane resin-based adhesive. 7. The ratio of the 4,4′-diphenylmethane diisocyanate (a-1) and the 2,4′-diphenylmethane diisocyanate (a-2) is (a) by weight.
-1) / (a-2) = 90 / 10-40 / 60, The one-component moisture-curable polyurethane resin adhesive according to any one of claims 1 to 6. 8. The one-component moisture-curable polyurethane resin adhesive according to claim 1, wherein the polar organic solvent (C) is a nitrogen-containing solvent (c-1). 9. The nitrogen-containing solvent (c-1) is N-methyl-2-pyrrolidone.
Item 1. A one-part moisture-curable polyurethane resin-based adhesive. 10. The amount of the polar organic solvent (C) used is
0.5 based on 100 parts by weight of the total resin content of the polyurethane resin (A) and the polyisocyanate (B).
-10.0 parts by weight, The one-part moisture-curable polyurethane resin adhesive according to any one of claims 1 to 9. 11. The method according to claim 1, further comprising a tertiary amine type reaction accelerator (D) having a morpholine skeleton in the molecule.
The one-component moisture-curable polyurethane resin-based adhesive according to any one of 1. 12. The amount of the tertiary amine-type reaction accelerator (D) used is not more than 0. 0, based on 100 parts by weight of the total resin content of the polyurethane resin (A) and the polyisocyanate (B). The one-part moisture-curable polyurethane resin adhesive according to any one of claims 1 to 11, which is 5 to 5.0 parts by weight. 13. A floor structure, wherein a floor material is laid on a base material via the adhesive according to any one of claims 1 to 12.