JPH07268309A - Adhesive for floor covering material - Google Patents

Abstract

PURPOSE:To obtain the subject adhesive of one-pack moisture curing type suitable for bonding a PVC decorative sheet, a P tile, etc., to a floor, having excellent workability, sanitation and permanence of water resistance, etc., comprising a specific polyurethane-based prepolymer and an inorganic filler. CONSTITUTION:This adhesive comprises (A) a polyurethane-based prepolymer obtained by blending a polyurethane-based prepolymer containing NCO at the end with an isocyanate-based compound containing two or more NCOs in the molecule and (B) an inorganic filler such clay. The amount of the component A used is preferably 20-80 pts.wt. and that of the component B used is preferably 10-60 pts.wt. based on 100 pts.wt. of the whole adhesive by weight ratio of solid content.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive for floor material construction, in which a soft polyvinyl chloride (hereinafter referred to as PVC) decorative sheet, P tile, wood board, artificial grass, etc. are adhered to the floor. Regarding

[0002]

PRIOR ART Soft PVC decorative sheets, P tiles,
When installing wood boards, artificial grass, etc., vinyl acetate type (water type, solvent type, etc.), SBR latex type (water type, etc.) A system adhesive is used. 2 recently
A one-component moisture-curable polyurethane adhesive is used as an alternative to liquid-type epoxy adhesives in terms of streamlining work (labor in the compounding process, etc.), hygiene, and versatility of adherends. Have begun.

[0003]

However, the conventionally used one-component moisture-curable type polyurethane adhesives are good in workability and adhesiveness but poor in durability, especially in water resistance. It had drawbacks.

It is an object of the present invention to provide a one-part moisture-curing type adhesive for flooring which has excellent durability such as water resistance.

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of the above-mentioned circumstances and found that a polyurethane prepolymer (a) having an NCO group at the terminal and an amount of NCO groups exceeding 2 in the molecule. It was found that the durability, especially the water resistance, can be improved by using the isocyanate compound (b) having the above, and the present invention has been completed.

That is, the present invention relates to a flooring adhesive containing a polyurethane prepolymer (A) and an inorganic filler (B) as essential components, and a polyurethane prepolymer (a) having an NCO group at the terminal. And 2 in the molecule
The present invention relates to an adhesive for flooring, which comprises an isocyanate compound (b) having an NCO group in an amount exceeding three.

The polyurethane prepolymer (a) having an NCO group at the end of the present invention means a polyoxyalkylene resin or a polyester resin having a hydroxyl group at one end (one end or both ends), alone or in combination. A resin having a urethane bond in the molecule and having an isocyanate group at one or both ends, which is obtained by reacting a chain extender and a polyisocyanate accordingly.

The polyoxyalkylene resin having a hydroxyl group at the terminal refers to a resin obtained by ring-opening polymerization of an alkylene oxide such as tetrahydrofuran, which is obtained by ring-opening polymerization of an active hydrogen-containing compound with alkylene oxide.

Examples of the active hydrogen-containing compound include polyhydric alcohols, low molecular weight amines, phenols, etc. These can be used alone or in admixture of two or more.

Alkylene oxide has 2 to 4 carbon atoms.
Of alkylene oxide, such as ethylene oxide, propylene oxide and butylene oxide. These may be used alone or in combination of two or more. When two or more kinds are mixed, they are bonded to the active hydrogen-containing compound by a block bond or a random bond.

The polyester resin having a hydroxyl group at the terminal is generally a polyester polyol obtained by reacting diole and dicarboxylic acid. Diol components used in this case include ethylene glycol, 1,
3-propanediol, 1,4-butanediol, 1,5
-Pentanediol, neopentylglycol, 3-methylpentanediol, 3,3-dimethylolheptane, 1,6-hexanediol, 1,8-octanediol-
Aliphatic diols such as 1,1,10-decanediol, 1,12-dodecandiol, 1,20-eicosandiol
Or an aromatic diol such as an ethylene oxide adduct of bisphenol A and a propylene oxide adduct of bisphenol A.

Examples of the dicarboxylic acid component include isophthalic acid, terephthalic acid, dimethyl isophthalate, terephthalic acid diethylsuccinic acid, adipic acid, azelaic acid,
Sebacic acid, 1,6-hexanedicarboxylic acid, 1,10-
Decanedicarboxylic acid, 1,20-eicosanedicarboxylic acid, succinic anhydride, adipic anhydride, azelaic anhydride, 1,10-decanedicarboxylic anhydride, sebacic acid diethyl ester, 1,12-dodecanedicarboxylic acid Examples thereof include those obtained by polycondensing diethyl ester, 1,20-eicosane dicarboxylic acid dimethyl ester and the like.

It is also possible to use a lactone type polyester polyol represented by ring-opening polymerization of ε-caprolactam, or a polycarbonate diol using a cyclic diol.

Polyurethane prepolymer of the present invention
The polyisocyanate used in the production of (a) is 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, Aromatic polyisocyanates such as 2,4-diphenylmethane diisocyanate, xylylene diisocyanate, polymeric diphenylmethane diisocyanate, carbodiimidated diphenylmethane diisocyanate, and 1,5-naphthylene diisocyanate , Ethylene diisocyanate, ethylidene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, 2,2,
Aliphatic polyisocyanates such as 4-trimethylhexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate and hydrogenated tolylene diisocyanate
And the like. Among these, as the isocyanate used in the present invention, from the viewpoint of reactivity with moisture,
Aromatic polyisocyanates are preferred, especially diphenylmethane diisocyanate or tolylene diisocyanate.
It is preferable to use

The chain extender used in this case is ethylene glycol, 1,3-propanediol,
1,4-butanediol, 1,5-pentanediol, neopentyl glycol, trimethylolpropane, 3-
Examples thereof include methylpentanediol, 3,3-dimethylolheptane, and 1,6-hexanediol.

The isocyanate compound (b) having an amount of NCO groups exceeding 2 in the molecule used in the present invention means a compound having an average value of 2 or more NCO groups in the molecule.

As the isocyanate compound (b),
For example, ethylenediamine, neopentanediamine, 4,
Amino group component of a compound having two or more amino groups in the molecule such as 4′-diaminophenylmethane and dipropylenetriamine, and three or more hydroxyl groups in the molecule such as trimethylolpropane, pentaerythritol and sorbit It refers to a compound having more than two functions, such as an adduct body obtained by reacting a hydroxyl component of the compound with an isocyanate, an isocyanurate body obtained by reacting a polyisocyanate, or a buret body. Among these adducts, the functional group to be reacted with the isocyanate used in the present invention is preferably an adduct obtained by a reaction with a hydroxyl group from the viewpoint of controllability during the reaction.

As the isocyanate used at this time, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate, hexamethylene diisocyanate, etc. Alicyclic polyisocyanates such as isophorone diisocyanate, and isocyanuric acid.

As the isocyanate compound (b),
As commercially available products, Coronet L (TDI adduct body), Coronet HL (HDI adduct body), Sprasec SP-
3340 (TDI Nuret body), Coronet EH (HD
I Nure body (manufactured by Nippon Polyurethane Industry Co., Ltd.), Takenet D-165N90CX (HDI burette body) (Takeda Pharmaceutical Co., Ltd.) and the like.

The molecular weight of the isocyanate compound (b) is not particularly limited, but is 50 in terms of weight average molecular weight.
It is preferably 00 or less. If the molecular weight of the isocyanate compound (b) exceeds 5,000, the durability-imparting effect is small, which is not preferable.

The amount of the isocyanate-based compound (b) used is not particularly limited, but it is not limited to the polyurethane-based prepolymer.
It is preferably 5 to 30 parts by weight based on 100 parts by weight of the solid content of (a). If the amount of the isocyanate compound (b) used is 5 parts by weight or less, the durability-imparting effect is small, and if it is 30 parts by weight or more, there is a drawback that the substrate adhesion is impaired, which is not preferable.

Polyurethane prepolymer of the present invention
(A) is a mixture of the polyurethane prepolymer (a) and the isocyanate compound (b). From the viewpoint of workability, the molecular weight of the polyurethane prepolymer (A) is preferably 250,000 or less in terms of weight average molecular weight.

The amount of the polyurethane prepolymer (A) used is not particularly limited, but it is preferably 20 to 80 parts by weight based on 100 parts by weight of the total amount of the adhesive in a solid content weight ratio.

If the amount is 20 parts by weight or less, the adhesion to the substrate cannot be imparted, and if the amount is 80 parts by weight or more, there is a disadvantage that good workability cannot be obtained, which is not preferable. Not preferable. Examples of the inorganic filler (B) used in the present invention include calcium carbonate, talc, clay, silicic acid anhydride, carbon, and metal powder, and it is preferable to use clay from the viewpoint of stability.

The amount of the inorganic filler (B) to be used is not particularly limited, but it is preferable to use 10 to 60 parts by weight based on 100 parts by weight of the total amount of the adhesive in a weight ratio. 10
When the amount is less than 60 parts by weight or more than 60 parts by weight, there is a drawback that the working performance as an adhesive for flooring agents cannot be secured, which is not preferable.

The adhesive of the present invention is obtained by reacting the above hydroxyl group-terminated polyoxyalkylene resin or polyester resin, alone or in combination, with an isocyanate to obtain a polyurethane prepolymer having an isocyanate group at the end ( Polyurethane prepolymer obtained by blending a) and an isocyanate compound (b) having an isocyanate group in an amount exceeding two.
(A) is a resin component and is compounded with an inorganic filler (B).

The polyurethane prepolymer (a) is produced, for example, as follows. That is, a method in which a polyoxyalkylene resin or a polyester resin is used alone or in combination and dissolved in a suitable solvent, and a polyisocyanate is added thereto for reaction, a polyoxyalkylene resin or a polyester resin is used alone or in combination, and a solvent is used. It is prepared by a method of reacting with a polyisocyanate in the absence of a solvent and dissolving it in a solvent.

In this case, it is possible to use a suitable chain extender in any method. As a chain extender,
Specifically, the same as those listed above can be used.

Examples of the solvent include acetone, methyl ethyl ketone, toluene, xylene, ethyl acetate and the like, and these solvents may be used alone or in combination.

The adhesive of the present invention is usually used in the form of a compound of the above-mentioned one-component moisture-curable urethane type prepolymer (A) and an inorganic filler (B). In addition to the above-mentioned components (A) and (B), if necessary, colorants, storage stabilizers such as monofunctional isocyanates, aerosils, thixotropy imparting agents such as various polymers, silane coupling, etc. Adhesion imparting agents such as agents, catalysts for adjusting the reaction rate, plasticizers, and other additives can be used.

Further, an organic solvent such as an aliphatic or aromatic hydrocarbon-based, ester-based, ketone-based or chlorine-based solvent which is used for a general urethane adhesive may be used. The adhesive of the present invention has particularly excellent permeability to a floor made of an inorganic material,
It has good adhesion to soft PVC decorative sheets, P tiles, wooden boards, artificial turf, etc., and its adhesion does not drop significantly even after immersion test in water.

[0032]

EXAMPLES Next, examples and comparative examples of the present invention will be shown. Hereinafter, unless otherwise specified, parts indicate weight ratios, and% indicates% by weight.

<Synthesis 1 of Polyurethane Prepolymer (a) 1> In a 2 L 4-necked flask, 500 parts of polypropylene diol having a molecular weight of 2000 and polyester diol (1,4-butanediol-adipic acid type) having a molecular weight of 2000 are used. ) 500 parts was charged and dehydrated, then a reflux circuit was set, 52 parts neopentyl glycol and 263 parts ethyl acetate were added and uniformly dissolved. Dibutyltin dilaurate
(50 ppm) and 209 parts of tolylene diisocyanate were added in portions at 40 ° C., and the reaction was allowed to proceed at 75 ° C. until the NCO% became constant. Then add 277 ethyl acetate.
A resin containing 70.0% of the active ingredient at the NCO terminal (hereinafter referred to as resin 1) was obtained.

<Synthesis 2 of Polyurethane Prepolymer (a)> A 2 L 4-neck flask was charged with 1000 parts of polypropylene diol having a molecular weight of 2000 and dehydrated, and then a reflux circuit was set and 52 neopentyl glycol was added. Department,
Add 263 parts of ethyl acetate and dissolve uniformly. Dibutyltin dilaurate (50 ppm) was added, and 209 parts of tolylene diisocyanate was added portionwise at 40 ° C to carry out the reaction at 75 ° C until the NCO% became constant. After that, 277 parts of ethyl acetate was added and the active ingredient was 70.0% at the NCO end.
Resin (hereinafter, this resin is referred to as Resin 2) was obtained.

<Synthesis 3 of Polyurethane Prepolymer (a)> 1000 parts of polyester diol having a molecular weight of 2000 (1,4-butanediol-adipic acid system) was charged in a 2 L 4-necked flask and dehydrated. A reflux circuit is set, and 52 parts of neopentyl glycol and 263 parts of ethyl acetate are added and uniformly dissolved. Dibutyltin dilaurate (50 ppm) was added, and 209 parts of tolylene diisocyanate was added in portions at 40 ° C to carry out the reaction at 75 ° C until the NCO% became constant. Then add ethyl acetate to 27
7 parts by weight of NCO was added to obtain a resin containing 70.0% of active ingredient (hereinafter, this resin is referred to as resin 3).

Examples 1 to 4 and Comparative Examples 1 to 3 As an isocyanate compound (b) having an NCO group in an amount exceeding 2 in a molecule, a coroneate L (TDI adduct, manufactured by Nippon Polyurethane Industry Co., Ltd.) ), And Sprasec SP-3340 (TDI nuret body, manufactured by Nippon Polyurethane Industry Co., Ltd.). Resin 1, resin 2 and resin 3 are combined as a polyurethane prepolymer (a) to form a resin component, and a solvent, an inorganic filler (NN kaolin clay, manufactured by Tsuchiya Kaolin Industry Co., Ltd.) and Aerosil (AEROSIL200). , Nippon Aerosil Co., Ltd.) and organic solvents (ethyl acetate, toluene)
Was compounded into a one-component moisture-curable urethane adhesive. The mixing ratios are as shown in Tables 1 and 2.

The adhesives of Examples 1 to 4 and Comparative Examples 1 to 3 were used to form a comb-like iron (JIS-A-55) on a plate.
36 standard product) and left for 20 minutes under the condition of 23 ° C. × 65% RH, and then the PVC sheet was pressed with a hand roll.

The obtained processed product was tested as follows and evaluated as an adhesive. <Test Method and Evaluation Criteria> Peel strength: After compression, after curing for a predetermined time under conditions of 23 ° C. and 65% RH, a PVC sheet is 1 inch (width) × 10 c.
A test piece is cut into a size of m (length).

However, the peeling test was carried out using Tensilon 23
Measurement is performed at an angle of 180 degrees in an atmosphere of ℃ × 65% RH. Adhesion under normal conditions; measured after 72 hours of curing time. Water-resistant adhesive strength: Measured after 24 hours of aging and immersion in water at 23 ° C. for 48 hours.

The results of these tests are shown in Examples 1 to 1.
4 is shown in Table 1 and Comparative Examples 1 to 3 are shown in Table 2.

[0041]

[Table 1] In the table, the unit of peel strength is Kg / inch, and the * mark indicates that the material of the plate is destroyed.

The viscosity is BH type rotational viscometer rotor No. 6
The value at 20 rotations when used and the thixotropy coefficient shall be the value at 2 rotations divided by the value at 20 rotations (measurement temperature is 2
5 ° C).

[0043]

[Table 2] In the table, the unit of adhesive strength is Kg / inch, and the * mark indicates that the material of the slate plate is destroyed. Viscosity is the value at 20 revolutions when using BH type rotational viscometer rotor No.6, and thixo coefficient is the value obtained by dividing the value at 2 revolutions by the value at 20 revolutions (measurement temperature is 25 ° C). .

[0044]

EFFECT OF THE INVENTION The adhesive of the present invention is applied to the inorganic floor with soft PV.
Excellent water resistance can be imparted to a urethane-based one-component moisture-curable adhesive used when constructing C decorative sheets, P tiles, wooden boards, artificial grass, and the like.

Therefore, it is useful for floor material construction in applications where water resistance is required.

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[Procedure amendment]

[Submission date] April 27, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0024

[Correction method] Change

[Correction content]

If the amount is 20 parts by weight or less, the adhesion to the substrate cannot be imparted, and if the amount is 80 parts by weight or more, there is a disadvantage that good workability cannot be obtained, which is not preferable. The inorganic filler (B) used in the present invention is calcium carbonate,
Examples thereof include talc, clay, silicic acid anhydride, carbon, and metal powder, and it is preferable to use clay from the viewpoint of stability.

Claims (7)

[Claims] 1. A flooring adhesive comprising a polyurethane-based prepolymer (A) and an inorganic filler (B) as essential components, comprising a polyurethane-based prepolymer (A).
Is a polyurethane prepolymer having an NCO group at the end
An adhesive for flooring, which comprises (a) and an isocyanate compound (b) having an NCO group in an amount exceeding 2 in a molecule. 2. An isocyanate compound (b) is an isocyanate or polyisocyanate together with NCO in the molecule.
The adhesive according to claim 1, which is a reaction product of a compound having two or more groups that react with a group or a reaction product of a polyisocyanate and water. 3. The adhesive according to claim 1 or 2, wherein the isocyanate compound (b) has a weight average molecular weight of 5,000 or less. 4. The amount of the isocyanate compound (b) used is 1% by weight of the solid content of the polyurethane prepolymer (a).
It is 5-30 weight part with respect to 00 weight part, The adhesive agent of any one of Claims 1-3 characterized by the above-mentioned. 5. A polyurethane-based prepolymer (A) in a solid content weight ratio of 20 relative to 100 parts by weight of the total amount of the adhesive.
~ 80 parts by weight is used, characterized in that
The adhesive according to any one of 4 above. 6. The adhesive according to any one of claims 1 to 5, wherein the inorganic filler (B) is clay. 7. The inorganic filler (B) is used in a weight ratio of 10 to 60 parts by weight based on 100 parts by weight of the total amount of the adhesive, and the filler is used. Adhesive according to item.