JPH08104861A - One-pack solventless reactive type urethane-based adhesive composition and floor structure using the same - Google Patents

Abstract

PURPOSE: To obtain the subject adhesive, containing a chlorinated phosphoric ester-based plasticizer in a specific proportion in a urethane prepolymer, good in operating efficiency of coating works even when an additive is highly filled, excellent in adhesive force and useful for bonding a floor covering material to an underfloor ground material. CONSTITUTION: This composition contains (A) 100 pts.wt. urethane prepolymer and (B) 1-100 pts.wt. chlorinated phosphoric ester-based plasticizer [e.g. tris(β- chloropropyl)phosphate or trisdichloropropyl phosphate]. Furthermore, the component (A) is obtained by blending a polyol with a polyisocyanate so as to provide >1 ratio of isocyanate groups (NCO) in the polyisocyanate to hydroxyl groups (OH) in the polyol, e.g. at 1.5<=NCO/OH<=10 ratio and reacting both at 60-100 deg.C for several hr. The resultant composition is used for bonding a floor covering material made of a vinyl chloride-based resin to an underfloor ground material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a one-component solventless reaction-type urethane adhesive composition and a floor structure using the same.

[0002]

2. Description of the Related Art A one-component reactive urethane adhesive is a vinyl chloride resin that reacts with moisture in the air or moisture in a floor base material or floor material to crosslink and cure to give a tough resin cured product. Since it firmly adheres to various plastic materials and inorganic materials such as wood, concrete and slate, it has become widely used in place of the two-component reactive adhesive.

[0003] The one-component reactive urethane adhesive usually contains an inorganic filler for the purpose of cost reduction. However, if the content is increased, the cost reduction effect becomes large but the viscosity becomes high, resulting in workability. Becomes worse. Therefore, the viscosity has been lowered by adding an organic solvent such as toluene or ethyl acetate to several to several tens of percent.

However, since these organic solvents have high volatility and low ignition temperatures, they are conversely eliminated from the viewpoint of work environment and fire prevention, and dioctyl phthalate is substituted for the above organic solvents. , Phthalic acid esters such as butylbenzyl phthalate, aliphatic dibasic acid esters such as dioctyl adipate, phosphoric acid esters such as tributyl phosphate, high boiling point hydrocarbons,
A one-component reactive urethane adhesive whose viscosity has been reduced by a plasticizer such as chlorinated paraffins has been proposed (JP-A-59-1).
13076, JP-A-5-163477).
However, when the above plasticizer is added, the coatability is improved, but the adhesiveness of the core may be adversely affected.

[0005]

DISCLOSURE OF THE INVENTION As a result of intensive research aimed at solving the above-mentioned problems of the prior art, the present invention has revealed that a one-component reactive urethane adhesive is used in addition to a chlorinated phosphate ester-based adhesive which is a retardant for plastic materials. By adding a plasticizer in a specific ratio, the present invention has been completed based on the finding that the workability in the adhesive construction work is improved and the adhesive property is particularly excellent for vinyl chloride resin products. .

[0006]

The present invention according to claim 1 is a one-component solvent-free reaction type which comprises 1 to 100 parts by weight of a chlorinated phosphate ester-based plasticizer with respect to 100 parts by weight of a urethane prepolymer. A urethane adhesive composition is the subject of the invention.

The present invention according to claim 2 is concerned with a floor structure in which a vinyl chloride resin floor material and a floor base material are bonded by the one-component solvent-free reaction-type urethane adhesive according to claim 1. It is what

The urethane prepolymer used in the present invention according to claim 1 means a hydroxyl group (O
The ratio of isocyanate groups (NCO) of the polyisocyanate to H) is greater than 1, for example 1.
It is produced by mixing a polyol and a polyisocyanate at a ratio of 5 ≦ NCO / OH ≦ 10 and reacting at a temperature of 60 to 100 ° C. for several hours. The urethane prepolymer thus obtained usually has an NCO content of 1 to
It is adjusted to 15% by weight.

Examples of the above-mentioned polyols include various polyether-based polyols, polyester-based polyols, polymer polyols and the like which are generally used in the production of urethane compounds.

As the above polyether polyol,
For example, two active hydrogens composed of diols such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol, 1,6-hexanediol, triols such as glycerin and trimethylolpropane, amines such as ethylenediamine and butylenediamine. In the presence of one kind or two or more kinds of low molecular weight active hydrogen compounds having the above, one of alkylene oxides such as propylene oxide, ethylene oxide and tetrahydrofuran is added.
Examples thereof include polymers obtained by ring-opening polymerization of two or more species.

As the above polyester-based polyol,
For example, polybasic acids such as adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, succinic acid, and bisphenol A, ethylene glycol, 1,2-
Polymers obtained by dehydration condensation with polyhydric alcohols such as propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexanediol, neopentyl glycol, and, for example, ε-caprolactone, α-
Polymers of lactones such as methyl-ε-caprolactone,
Further, examples thereof include a condensation product of a hydroxycarboxylic acid such as castor oil, a reaction product of castor oil and ethylene glycol, and the above polyhydric alcohol.

Examples of the above-mentioned polymer polyol include those obtained by graft-polymerizing an ethylenically unsaturated compound such as acrylonitrile, styrene and methyl (meth) acrylate with the above polyether polyol or polyester polyol, 1,2- or 1 , 4-polybutadiene polyol, or hydrogenated products thereof.

As a raw material for producing the urethane prepolymer, the weight average molecular weight of the polyol compound is 100.
It is preferably about 50,000 to 50,000, more preferably about 500 to 5,000. The above polyol compounds may be used alone or in combination of two or more.

Examples of the polyisocyanate include diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate and dicyclohexylmethane diisocyanate, and trimers of the above diisocyanates and triphenylmethane triisocyanate. Examples thereof include isocyanates, and crude MDI which is a mixture of diphenylmethane diisocyanate, triphenylmethane triisocyanate and the like. These polyisocyanates may be used in one kind,
You may use 2 or more types together.

The chlorinated phosphate ester plasticizer used in the present invention according to claim 1 is, for example, tris (β-
Examples thereof include chloropropyl) phosphate, trisdichloropropylphosphate, tri (chloroethyl) phosphate and the like. These chlorinated phosphoric acid esters may be used alone or in combination of two or more.

If the amount of the chlorinated phosphate ester plasticizer added is less than 1 part by weight based on 100 parts by weight of the urethane prepolymer, the dilution effect of the urethane prepolymer will not be exhibited, and if it exceeds 100 parts by weight. Adhesive strength cannot be sufficiently obtained even if the cohesive strength of the cured product of the adhesive is reduced and the adhesion is not reduced.

In the one-component solventless reaction-type urethane adhesive composition of the present invention according to claim 1, in addition to the above-mentioned materials, a filler, a thixotropic agent, and a plasticizer other than a chlorinated phosphoric acid ester-based agent, if necessary. , An adhesiveness-imparting agent, a curing catalyst, a stabilizer and the like may be added within a range not departing from the spirit of the present invention. However, among the above additives, plasticizers other than chlorinated phosphoric acid ester-based plasticizers may deteriorate the adhesiveness, so when added, it is preferable to keep them to the minimum necessary.

The filler, thixotropic agent, plasticizer other than chlorinated phosphoric acid ester-based adhesive, adhesiveness-imparting agent, curing catalyst, stabilizer and the like may be those usually used for one-component reactive urethane-based adhesives. For example, the invention can be used without any particular limitation.

Examples of the filler include calcium carbonate, surface-hydrophobicized calcium carbonate, carbon black, talc, titanium oxide, rubber powder, organic and inorganic balloons. These fillers may be used alone or in combination of two or more.

Examples of the thixotropic agent include colloidal silica, hydrogenated castor oil, organic bentonite and the like. These thixotropic agents may be used alone or in combination of two or more.

Examples of the plasticizer other than the chlorinated phosphoric acid ester-based plasticizers include phthalic acid esters such as dioctyl phthalate (DOP), dibutyl phthalate and dilauryl phthalate, and dibasic aliphatic dibasic compounds such as dioctyl adipate and diisodecyl adipate. Examples thereof include acid esters, phosphoric acid esters such as trioctyl phosphate, propylene glycol adipate polyester, butylene glycol adipate polyester, alkyl epoxystearate, and epoxidized soybean oil. These plasticizers other than the chlorinated phosphate ester type may be used alone or in combination of two or more.

Examples of the adhesiveness-imparting agent include various titanate-based or silane-based coupling agents, reaction products of coupling agents and isocyanate compounds, and the like. These adhesiveness-imparting agents may be used alone or in combination of two or more.

Examples of the curing catalyst include tertiary amines such as triethylamine and N-methylmorpholine bis (2-dimethylaminoethyl) ether, dibutyltin dilaurate, tin octenoate, lead octenoate, lead naphthenate, and the like. Organometallic compounds may be mentioned. These curing catalysts may be used alone or in combination of two or more.

Examples of the above stabilizers include trade name Tinuvin 327, Irganox 1010 (manufactured by Ciba-Geigy), trade name Tomisorp 800 (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) and the like.

The method for producing a one-component solventless reaction-type urethane adhesive according to the first aspect of the present invention is characterized by the reaction substance, and the reaction operation is not particularly limited. During the production of the urethane prepolymer, various additives such as the above-mentioned filler, thixotropic agent, chlorinated phosphate ester type and other plasticizers, adhesiveness imparting agents, curing catalysts and stabilizers may be added in advance. At the time of addition, it is preferable that various additives be dehydrated in advance. The same applies when various additives are added after the synthesis of the urethane prepolymer.

In the floor structure to which the vinyl chloride resin floor material of the present invention is adhered according to claim 2, the vinyl chloride resin floor material is, for example, Woody-1 (manufactured by Asahi Woodtech Co., Ltd.) or Woodline. (Manufactured by Tajima), etc., wood flooring with vinyl chloride resin backing, wood floor with vinyl chloride resin backing, carpet flooring with vinyl chloride resin base material, vinyl chloride resin tile (Commonly known as P tile), long vinyl chloride resin sheet, artificial grass with flocked vinyl chloride resin base material, and the like.

The above vinyl chloride resin floor materials include concrete slabs, asphalt, plywood, particle boards,
Although it is adhered to vinyl chloride resin coated steel sheets, floor joists, etc., it is possible to use vinyl chloride resin flooring or floor underlaying materials by using comb-like irons, roll brushes, sprays, cartridges, etc. when performing the adhering work. Claim 1 in either or both
The one-component solventless reaction-type urethane adhesive of the present invention described above is applied to bond both.

[0028]

[Function] A one-component solventless reaction-type urethane adhesive containing 1 to 100 parts by weight of a chlorinated phosphate ester-based plasticizer with respect to 100 parts by weight of a urethane prepolymer is used as a floor material for vinyl chloride resin floor materials. In the case of adhering to a base material or the like, the viscosity of the adhesive can be reduced without lowering the adhesiveness to these floor materials or the like, so that an adhesive with good workability is provided.

[0029]

【Example】

Preparation of urethane prepolymer containing filler Polypropylene glycol having a molecular weight of 2,000 (Asahi Denka Kogyo KK, trade name: ADEKA POLYETHER P-2000)
After dehydrating a mixture of 400 parts by weight and 100 parts by weight of polyester diol (manufactured by Asahi Denka Kogyo Co., Ltd., product name: Adeka Polyester YG-226, hydroxyl value 65 mg KOH / g), crude MDI (manufactured by Sumitomo Bayer Urethane Co., Ltd., product name: 270 parts by weight of Sumidule 44V-20) was added and reacted at 80 ° C. for 4 hours in a nitrogen stream to obtain a urethane prepolymer having a terminal isocyanate group content of 8%. Then, the above urethane prepolymer 100 obtained
200 parts by weight of calcium carbonate heated and dried at 130 ° C. for 12 hours and 10 parts by weight of colloidal silica are added to parts by weight,
Stir and mix while heating to 50 ° C in a nitrogen stream,
A urethane prepolymer containing a filler of 0 Pa · s (20 ° C.) was produced.

Example 1 Tris (β-chloropropyl) was added to 310 parts by weight of the above-mentioned filler-containing urethane prepolymer.
5 parts by weight of phosphate was stirred and mixed in a nitrogen stream to obtain a one-component solventless reaction-type urethane adhesive composition.

Example 2 A one-component solventless reaction-type urethane adhesive composition was obtained in the same manner as in Example 1 except that the amount of tris (β-chloropropyl) phosphate added was changed to 20 parts by weight. It was

Example 3 A one-component solventless reaction-type urethane adhesive composition was obtained in the same manner as in Example 1 except that the amount of tris (β-chloropropyl) phosphate added was changed to 50 parts by weight. It was

COMPARATIVE EXAMPLE 1 The above-mentioned filler-containing urethane prepolymer was used as a one-component solventless reaction type urethane adhesive.

(Comparative Example 2) A one-component solventless reaction type urethane adhesive composition was obtained in the same manner as in Example 2 except that dioctyl phthalate was added in place of the above tris (β-chloropropyl) phosphate.

(Comparative Example 3) A one-component solventless reaction type urethane adhesive composition was obtained in the same manner as in Example 2 except that tributyl phosphate was added instead of the above tris (β-chloropropyl) phosphate.

The one-component solventless reaction-type urethane adhesive compositions obtained in the respective examples were evaluated under the following conditions, and the results are shown in Table 1.
It was shown to. 1. Viscosity measurement: Based on JIS K 6833 (General test method for adhesives), using a BH type and B8U type viscometer,
The viscosity at 20 ° C. was measured at 10 rpm.

2. Evaluation of Adhesiveness: A 40 mm × 40 mm piece of Woody-1 (manufactured by Asahi Woodtech Co., Ltd.) was prepared as a vinyl chloride resin floor material and used as a floor base material.
A slate plate having a size of mm × 70 mm × 8 mm is selected, and the one-component solventless reaction-type urethane adhesive obtained in each of the above-mentioned examples is applied to a comb-shaped iron (comb-shaped thread height: 3 mm) at 350 g / m 2.
The amount of ² was applied and immediately the above Woody-1 slices were pasted together, and after curing at 20 ° C. and 60% RH for 7 days, an autograph (manufactured by Shimadzu Corporation) was used, and the pulling speed was 50 mm / m.
In-plane tensile strength was measured and the fracture mode was observed.

3. Evaluation of workability: The difficulty level of workability when the one-component solventless reaction-type urethane adhesive obtained in each example was applied using the comb-gote (comb-peak height: 3 mm) shown in the above item, 5: extremely good, 4: good, 3: normal,
It was comprehensively evaluated by the 5-point method of 2: poor, 1: extremely bad.

[0039]

[Table 1]

[0040]

According to the present invention as set forth in claim 1, by containing a chlorinated phosphate ester type plasticizer as described above, additives such as a filler are highly filled without lowering the adhesive strength. Even in such a case, it is possible to provide an excellent one-pack solvent-free reaction-type urethane adhesive composition that has good workability in coating work.

The present invention according to claim 2 uses the one-component solventless reaction-type urethane adhesive composition according to claim 1 as described above. The adhesiveness is good, and the vinyl chloride resin floor material is firmly bonded to the floor base material with rubber elasticity.

Further, even for a floor base material, which is generally a rough surface, fine filling can be corrected by high filling of a filler or the like, and the adhesive work can be performed. Can provide floor structure. Further, the one-component solventless reaction-type urethane adhesive composition according to claim 1 contains a chlorinated phosphoric acid ester-based plasticizer having a large action as a retardant for vinyl chloride-based resin, and therefore has a fire resistance performance. It is possible to provide a floor structure with further improvement.

Claims (2)

[Claims] 1. A one-component solventless reaction-type urethane adhesive composition containing 1 to 100 parts by weight of a chlorinated phosphoric acid ester plasticizer with respect to 100 parts by weight of a urethane prepolymer. 2. A floor structure in which a vinyl chloride resin floor material and a floor base material are adhered to each other with the one-liquid solventless reaction type urethane adhesive according to claim 1.