JP2009035665A - One-pot reactive polyurethane resin-based adhesive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a one-pot reactive polyurethane resin-based adhesive composition developing strong initial tackifying power in a short time regardless of use environments, and having high strength and high water-proof heat-proof properties. <P>SOLUTION: This one-pot reactive polyurethane resin-based adhesive composition includes an amine-modified urethane resin (A) and a polyisocyanate compound (B). This one-pot reactive polyurethane resin-based adhesive composition preferably includes a solvent (C). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a one-component reactive polyurethane resin-based adhesive composition, and in particular, a one-component reactive polyurethane that can express a strong initial adhesive force in a short time regardless of the use environment and has high strength and high water and heat resistance. The present invention relates to a resin-based adhesive composition.

  One-component reactive polyurethane resin-based adhesives exhibit adhesiveness by reacting with water in the air or base material, and are hardened compared to conventional two-component reactive urethane resin-based adhesives. It is used in a wide range of fields, including the construction industry, because there is no need to mix agents.

  The one-component reactive polyurethane resin-based adhesive is used in the construction industry, for example, in a construction process for pasting a floor material on a base material, and can be applied in a short time regardless of the construction environment. The thing which can express the initial stage adhesive strength of the level is calculated | required from a viewpoint of workability | operativity. In addition, since the construction is often performed in a range having a wide area at a time, the adhesive is required to have a sufficiently long pasting time. However, the one-component reactive polyurethane resin adhesive has an initial adhesive pressure development time and a pastable time (a time that can be adhered after the adhesive is applied) depending on the amount of moisture contained in the air and the substrate. The conventional one-component reactive polyurethane resin-based adhesives have to be appropriately adjusted in composition according to the usage environment.

  In addition, the one-component reactive polyurethane resin adhesive has a problem that the initial adhesive strength is weak, and the end of the flooring material jumps up at the time of construction of a long flooring material with wrapping. In addition, when laying floor materials such as P tiles and tile carpets on the ground, there is a risk that the floor materials will move and move when the operator moves during construction.

As a one-component moisture-curing urethane adhesive with improved initial adhesive strength, Patent Document 1 blends a urethane prepolymer having two or more isocyanate groups at the terminal and a urethane prepolymer in which the isocyanate groups are inactivated. A one-component moisture-curing urethane adhesive is described. However, the one-component moisture-curing urethane adhesive has a problem in initial adhesive strength at low temperatures.
JP-A-6-240226

  An object of the present invention is to provide a one-component reactive polyurethane resin-based adhesive composition that can develop a strong initial adhesive force in a short time regardless of the use environment, and has high strength and high water and heat resistance.

  In order to solve the above problems, the one-component reactive polyurethane resin-based adhesive composition of the present invention is characterized by containing (A) an amine-modified urethane resin and (B) a polyisocyanate compound.

  The one-component reactive polyurethane resin adhesive composition of the present invention preferably further comprises (C) a solvent.

According to the present invention, it is possible to provide a one-component reactive polyurethane resin-based adhesive composition that can develop a strong initial adhesive force in a short time regardless of the use environment, and has high strength and high water and heat resistance.
Since the one-component reactive polyurethane resin-based adhesive composition of the present invention has a strong adhesive force, when a long PVC sheet with curly flaws is adhered, curling flaws can be suppressed. Since the displacement of the tile can be suppressed when adhering to the base material, it is particularly suitable as an adhesive for laying a polymer-based adhesive floor material such as a long PVC sheet and a PVC tile on the base material.

  Embodiments of the present invention will be described below, but these are exemplarily shown, and it goes without saying that various modifications are possible without departing from the technical idea of the present invention.

  The one-component reactive polyurethane resin-based adhesive composition of the present invention is characterized by containing (A) an amine-modified urethane resin and (B) a polyisocyanate compound.

The (A) amine-modified urethane resin is not particularly limited as long as it is a urethane resin modified with an amine. For example, a polyisocyanate compound and an active hydrogen-containing compound are reacted, and preferably an NCO / OH equivalent ratio of 1. After obtaining a urethane prepolymer of 10 to 10.00, more preferably 1.25 to 5.00, the urethane prepolymer and an amine compound can be obtained by reacting in the presence of a solvent, if necessary. it can. The NCO / active hydrogen equivalent ratio of the amine-modified urethane resin is preferably 1.00 to 2.00, and more preferably 1.00 to 1.20.
The amine-modified urethane resin used in the present invention is preferably dissolved in a solvent in order to prevent solidification. As the solvent for dissolving the amine-modified urethane resin, a solvent may be added after the production, or a solvent added during the production may be used as described above.

The active hydrogen-containing compound is not particularly limited as long as it is a compound containing an active hydrogen group, but monool or polyol is preferable, polyether polyol or polyester polyol is more preferable, and polyether polyol is more preferable. .
More specifically, for example, as the polyether polyol, one or two kinds of diols such as ethylene glycol, propylene glycol and butylene glycol, triols such as glycerin and trimethylolpropane, and amines such as ammonia and ethylenediamine are used. Examples include polyether polyols such as random or block copolymers obtained by ring-opening polymerization of propylene oxide and / or ethylene oxide in the presence of the above.
Examples of polyester polyols include polyester polyols such as copolymers obtained by polycondensation of adipic acid, sebacic acid, terephthalic acid, etc. in the presence of ethylene glycol, propylene glycol, 1,4 butanediol, neopentyl glycol, etc. In addition, low molecular active hydrogen compounds having two or more active hydrogen groups such as bisphenol A and ramester of castor oil can be mentioned.
As the active hydrogen-containing compound, those having a molecular weight of 100 to 20000 and 1 to 4 OH groups in one molecule can be preferably used.

  Examples of the polyisocyanate compound include aromatic polyisocyanates such as diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), naphthalene diisocyanate, and aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI) and lysine methyl ester diisocyanate. Cycloaliphatic polyisocyanates such as isocyanates, hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, norbornane diisocyanate, and hydrogenated tolylene diisocyanate can be mentioned. Among these, MDI is preferably used from the viewpoint of toxicity and price.

As the amine compound, primary and secondary amines can be used, and primary amines are preferred. Moreover, although both monoamine and polyamine can be used, polyamine is preferable and diamine is more preferable.
Examples of the polyamine include aliphatic diamines such as ethylenediamine, 1,3-diaminopropane, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, and neopentanediamine; 4,4′-diaminocyclohexylmethane, Cycloaliphatic diamines such as isophoronediamine, bisaminomethylcyclohexane, 2,5- or 2,6-diaminomethylbicyclo [2,2,1] heptane, diaminocyclohexane; diaminodiphenylmethane, diaminodiphenyl ether, xylylenediamine, phenylenediamine Aromatic diamines such as 3,5-diethyl-2,4- or 2,6-diaminotoluene; 1,3,5-tris (aminomethyl) benzene, 1,3,5-tris (aminomethyl) cyclohexane Aromatic or alicyclic triamines such as sun; obtained by converting the hydroxyl group of polyoxyalkylene glycols obtained by addition polymerization of propylene oxide and / or ethylene oxide to water, ethylene glycol, propylene glycol, etc. to amino groups Polyoxyalkylene diamines such as polyoxyalkylene triamines obtained by converting the hydroxyl groups of polyoxyalkylene triols obtained by addition polymerization of propylene oxide and / or ethylene oxide to glycerin, trimethylolpropane, etc. to amino groups, etc. Can be mentioned.
Examples of the monoamine include aliphatic primary amines such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, and hexylamine; aliphatics such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, and dibutylamine. Secondary amines; aliphatic unsaturated amines such as allylamine and diallylamine; cycloaliphatic amines such as cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine; aniline, diphenylamine, methylaniline, ethylaniline, toluidine, xylidine, benzylamine And aromatic amines such as naphthylamine.

  In the production of the amine-modified urethane resin, a low molecular compound having two or more active hydrogen groups in the molecule (for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 1,6- Diols such as hexanediol and bisphenol A; polyhydric alcohols such as glycerin, trimethylolpropane, glucose, sorbitol, and shoelace; amines such as ethylenediamine and butylenediamine) may be used.

The (B) polyisocyanate compound is not particularly limited as long as it has two or more isocyanate groups. For example, diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and dicyclohexylmethane diisocyanate. Dimers (carbodiimide-modified) and trimers of these diisocyanates; triisocyanates such as triphenylmethane triisocyanate; crude MDI (also called polymeric MDI) which is a mixture of diphenylmethane diisocyanate, triphenylmethane triisocyanate, etc. (Liquid polyisocyanate compound such as (methylene diisocyanate) or the reaction between polyisocyanate compound and polyol) Urethane prepolymers include having two or more active isocyanate group obtained by, and more preferably crude MDI in terms of viscosity and price. As the urethane prepolymer, the urethane prepolymer described in the description of the amine-modified urethane resin is preferably used.
These polyisocyanate compounds may be used alone or in combination of two or more, but it is preferable to use a liquid polyisocyanate compound and a urethane prepolymer in combination.

Although there is no restriction | limiting in the mixture ratio of the said (B) polyisocyanate compound in the 1 liquid reactive polyurethane resin-type adhesive composition of this invention, (A) 5 weight part-300 weight part with respect to 100 weight part of amine modified urethane resin. Parts are preferred, and 10 to 100 parts by weight are preferred.
In particular, when the urethane prepolymer described above is used as the (B) polyisocyanate compound, the amount is preferably 20 to 300 parts by weight with respect to 100 parts by weight of the (A) amine-modified urethane resin. Moreover, when using the liquid isocyanate compound mentioned above as (B) polyisocyanate compound, 5 to 150 weight part is preferable with respect to 100 weight part of (A) amine modified urethane resin.

In addition to the said component, it is preferable that the 1 liquid reactive polyurethane resin-type adhesive composition of this invention mix | blends (C) solvent as needed. The solvent is preferably an organic solvent containing no active hydrogen, for example, hydrocarbons such as toluene, xylene and cyclohexane; halogenated hydrocarbons such as 1,1,1-trichloroethane and carbon tetrachloride; methyl ethyl ketone, methyl acetone and the like Ketones; esters such as ethyl acetate and ethyl propionate.
These are used alone or in admixture of two or more, and contribute as a viscosity modifier.
Although there is no restriction | limiting in the compounding ratio of the said (C) solvent in the 1 liquid reactive polyurethane resin-type adhesive composition of this invention, 10-80 weight% is with respect to 1 liquid reactive polyurethane resin-type adhesive composition. preferable.

  In the one-component reactive polyurethane resin adhesive composition of the present invention, it is preferable to further blend (D) calcium carbonate in order to improve workability. The calcium carbonate may be either heavy or light, and surface-treated calcium carbonate may be used. In particular, from the viewpoint of economy and ease of handling, it is preferable to mix heavy calcium carbonate, and heavy calcium carbonate whose water content is adjusted to 0.1% or less is more preferable. The said calcium carbonate may be used independently and may mix 2 or more types. When two or more calcium carbonates are blended, ones having different particle sizes can be blended.

  In addition to the above-described components, the one-component reactive polyurethane resin adhesive composition of the present invention includes a curing catalyst, an adhesion-imparting agent, a physical property modifier, a filler, a plasticizer, a thixotropic agent, Various additives such as a dehydrating agent (storage stability improving agent), a tackifier, an anti-sagging agent, an ultraviolet absorber, an antioxidant, a flame retardant, a colorant, and a radical polymerization initiator may be blended.

  The present invention will be described more specifically with reference to the following examples. However, it is needless to say that these examples are shown by way of illustration and should not be construed in a limited manner.

(Synthesis Example 1)
In a stirrer equipped with a thermometer, 605.3 parts by weight of polypropylene glycol having a molecular weight of 2000 (trade name: Diol-2000, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) was dehydrated, and then 4,4-diphenylmethane diisocyanate (MDI). 94.7 parts by weight were added and reacted at 70 to 90 ° C. for 3 hours under a nitrogen stream to obtain urethane prepolymer A having an NCO / OH equivalent ratio of 1.25.

  In a stirrer equipped with a thermometer, 494.5 parts by weight of the obtained urethane prepolymer A and 500 parts by weight of acetone were added and uniformly dispersed, and ethylene oxide diamine having a molecular weight of 148 (manufactured by Huntsman USA, trade name: (Jeffamine EDR-148) 5.5 parts was added dropwise to obtain an amine-modified urethane resin A1 having a solid content of 50% and an NCO / active hydrogen equivalent ratio of 1.00.

(Synthesis Example 2)
A urethane prepolymer A was obtained in the same manner as in Synthesis Example 1.
In a stirrer equipped with a thermometer, 492.2 parts by weight of urethane prepolymer A and 500 parts by weight of acetone are added and uniformly dispersed, and 7.8 parts by weight of butylamine having a molecular weight of 73 is added dropwise to a solid content of 50%. An amine-modified urethane resin A2 having an NCO / active hydrogen equivalent ratio of 1.00 was obtained.

(Synthesis Example 3)
In a stirrer equipped with a thermometer, 589.3 parts by weight of polypropylene glycol having a molecular weight of 2000 (trade name: Diol-2000, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) was dehydrated, and then 4,4-diphenylmethane diisocyanate (MDI). 110.7 parts by weight were added and reacted at 70 to 90 ° C. for 3 hours under a nitrogen stream to obtain a polyisocyanate compound B1 having an NCO / OH equivalent ratio of 1.50.

(Synthesis Example 4)
A urethane prepolymer A was obtained in the same manner as in Synthesis Example 1.
In a stirrer equipped with a thermometer, 496.5 parts of urethane prepolymer A and 500 parts of acetone are added and uniformly dispersed, 3.5 parts of ethyl alcohol is added dropwise, and the solid content is 50%, NCO / active hydrogen. A terminal monoalcohol-modified urethane resin having an equivalent ratio of 1.00 was obtained.

Example 1
Amine-modified urethane resin A1 obtained in Synthesis Example 1, polyisocyanate compound B1 obtained in Synthesis Example 3, polyisocyanate compound B2 (trade name: Cosmonate M-300, manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.), solvent (acetone) And the dry calcium carbonate (Shiraishi calcium Co., Ltd. make, brand name White SB) was mix | blended in the ratio shown in Table 1, and the adhesive agent was prepared.

  In Table 1, the blending amount of each material is parts by weight, the amine-modified urethane resin A1 is the amine-modified urethane resin A1 obtained in Synthesis Example 1, and the amine-modified urethane resin A2 is the amine-modified urethane resin A2 obtained in Synthesis Example 2. Polyisocyanate compound B1 is polyisocyanate compound B1 obtained in Synthesis Example 3, and polyisocyanate compound B2 is Cosmonate M-300 (Mitsui Chemical Polyurethane Co., Ltd., special polymeric MDI).

The following test was done with respect to the obtained adhesive. The results are shown in Table 2.
(1) PVC sheet curl suppressing property A long PVC sheet of 25 mm x 300 mm and a thickness of 2.0 mm is wound around a 9.0 cm paper can and allowed to stand for 24 hours, and curl is applied. An adhesive was applied to the flexible board with a comb iron defined in JIS A5366, waited for 20 minutes after application, a vinyl chloride sheet was affixed, and pressed twice with a linear pressure of 40 N / 25 mm to prepare a test specimen. After preparing the test body, the lifting of the end portion of the PVC sheet was visually determined. The measurement was performed at 5 ° C and 23 ° C. The evaluation criteria are as follows.
◎: No lifting, ○: Almost no lifting, Δ: Slight lifting is observed, but there is no problem in strength and appearance, x: Lifting is observed, and there is a problem in strength and appearance.

(2) PVC tile slippage suppression (strong adhesion)
Apply the adhesive to the flexible board with a comb iron specified in JIS A5536, wait 20 minutes after applying, paste 40mm x 40mm, 2.0mm thickness PVC homogenia style, and press twice with 40N / 25mm linear pressure A test specimen was prepared. Immediately after the creation, the vinyl chloride tiles were shifted by hand to evaluate the resistance. The measurement was performed at 5 ° C and 23 ° C. The evaluation criteria are as follows.
A: No shift at all, O: Strong resistance is felt but slightly shifted, Δ: Resistance is felt, shifted, ×: Easy shift by hand

(3) Initial adhesive strength measurement Cut the flexible board and PVC homogenia style into 5cm squares, apply adhesive on the flexible board side with a comb-shaped iron, leave it for 20 minutes, and then paste the PVC homogenia style after 5 minutes. The strength was measured by subjecting it to a plane tensile test at a pulling speed of 50 mm / min.

(4) Adhesive strength Adhesive strength was measured according to JIS A5536. That is, an adhesive was applied to the flexible board with a comb iron as defined in JIS A5536, waited for 20 minutes after application, a polyvinyl chloride sheet was attached, and a test specimen was prepared by pressing twice with a linear pressure of 40 N / 25 mm.
The normal strength was obtained by performing a 90-degree floating roller tensile test after the specimen was cured for 48 hours, and the heat-resistant strength was obtained by curing the specimen for 48 hours and then standing at 80 ° C. for 168 hours to float 90 degrees. The roller tensile test was conducted, and the water immersion strength was obtained by curing the specimen for 48 hours and then immersing it in water for 168 hours and then performing a 90-degree floating roller tensile test. The evaluation criteria are as follows.
A: 1.5 N / 25 mm or more, B: 1.0 N / 25 mm or more and less than 1.5 N / 25 mm, X: 1.0 N / 25 mm or less.

(5) Coating property Based on JIS A5536, the soldering property of the jointing iron when applying the obtained adhesive using a standard jointing iron was evaluated under the condition of 23 ° C. The evaluation criteria are as follows.
A: There is no sense of resistance and the handling of the comb-shaped iron is very light.
○: There is little resistance and the judgment of the comb-shaped iron is light.
Δ: There is a slight sense of resistance, and the judgment of the comb-shaped iron is felt somewhat heavy.
X: Strong sense of resistance and heavy handling of the comb-shaped iron.

(Examples 2 to 13)
An adhesive was prepared in the same manner as in Example 1 except that the formulation was changed as shown in Table 1, and each measurement was performed. The results are shown in Table 2.

(Comparative Examples 1-5)
An adhesive was prepared in the same manner as in Example 1 except that the formulation was changed as shown in Table 3, and each measurement was performed. The results are shown in Table 4.

  In Table 3, the blending amount of each material is parts by weight, the terminal monoalcohol-modified urethane resin is the terminal monoalcohol-modified urethane resin obtained in Synthesis Example 4, and the phenolic resin is a trade name: Tamanol 521 (Arakawa Chemical Industries, Ltd. ), Terpene resin is trade name: YS Resin TO85 (manufactured by Yasuhara Chemical Co., Ltd.), styrene resin is trade name: FTR6100 (manufactured by Mitsui Chemicals), and polyisocyanate compound B1 is polyisocyanate obtained in Synthesis Example 3. Compound B1 and polyisocyanate compound B2 are Cosmonate M-300 (Mitsui Chemical Polyurethane Co., Ltd., special polymeric MDI).

(Comparative Example 6)
The test was conducted in the same manner as in Example 1 using a vinyl acetate resin solvent adhesive for flooring (trade name: No. 190, vinyl acetate resin adhesive manufactured by Cemedine Co., Ltd.) as an adhesive. The results are shown in Table 4.

(Comparative Example 7)
The test was conducted in the same manner as in Example 1 by using a rubber solvent adhesive for floors (trade name: G500, NBR rubber adhesive manufactured by Cemedine Co., Ltd.) as an adhesive. The results are shown in Table 4.

Claims (2)

A one-component reactive polyurethane resin-based adhesive composition comprising (A) an amine-modified urethane resin and (B) a polyisocyanate compound.   The one-component reactive polyurethane resin adhesive composition according to claim 1, further comprising (C) a solvent.