JPH10265545A - Production of liquid polymer composition for one-pack type adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in adhesive strength and good in workability, curability and preservation-stability by mixing a filler in vacuum with a prepolymer obtained from a hydroxyl group-containing liquid diene-based polymer, a polyalkylene glycol and a polyisocyanate. SOLUTION: The subject composition is produced by mixing a filler (preferably, calcium carbonate, clay, talc) in vacuum with a prepolymer obtained by reacting (A) a hydroxyl group-containing liquid diene-based polymer with (B) a polyalkylene glycol and (C) a polyisocyanate compound (preferably, diphenylmethane diisocyanate compound). It is preferable to blend 70-500 pts.wt. of a filler to 100 pts.wt. of the above prepolymer. The filler is preferably mixed under agitation at 15-80 deg.C and 0-1.5×10 Pa.A pressure for 15 minutes - 3 hours. The reaction of the components A-C can be carried out at 20-120 deg.C for 0.5-50 hours.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a liquid polymer composition for a one-component adhesive, and more particularly, to a prepolymer comprising a hydroxyl group-containing diene polymer, a polyalkylene glycol and a polyisocyanate compound.
Liquid polymer for one-component adhesives with excellent adhesion, good workability without sagging during application, and good curability and storage stability by mixing specific fillers under reduced pressure The present invention relates to a method for producing a composition.

[0002]

2. Description of the Related Art As a conventional polyurethane adhesive, a composition obtained by adding a polyisocyanate compound to a polyol comprising a polyalkylene glycol or a diene polymer having a hydroxyl group is used. These adhesives can be used in two-pack type by a one-shot method in which a polyol and a polyisocyanate compound are mixed, or in a one-pack type in which a polyol and a polyisocyanate compound are prepolymerized and cured by moisture. It has been known.

[0003] Among them, from the viewpoint of workability at a construction site, a one-pack type is suitable as an adhesive and widely used. However, although the conventional one-component polyurethane adhesive has a certain degree of adhesive strength, it cannot be said that it has a sufficient adhesive strength in applications where a high load is applied such as flooring. In addition, there is a problem with sagging, curability, viscosity and the like at the time of coating, and the range of use is also limited.

Therefore, in order to overcome such disadvantages,
Conventionally known methods of adding a short-chain diol compound such as ethylene glycol or 1,4-butanediol and a method of adding a filler during the production of a polyalkylene glycol-based isocyanate prepolymer improve the adhesive strength. It has been proposed as a way to make it work. However, the method of adding the short-chain diol compound has a problem that the viscosity of the prepolymer is extremely increased, and the workability is deteriorated. In addition, as a method of adding the filler to the prepolymer, when a commonly used roll or a planetarium mixer is used, there is a disadvantage that only a composition that gels during mixing or has poor storage stability can be obtained. .

[0005]

SUMMARY OF THE INVENTION Under such circumstances, the present invention provides a one-part liquid having excellent adhesive strength, no sagging during coating, good workability, and good curability and storage stability. It is an object of the present invention to provide a method for producing a liquid polymer composition for a mold adhesive.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a prepolymer comprising a hydroxyl group-containing diene polymer, a polyalkylene glycol and a polyisocyanate compound has been specified. By mixing the filler under reduced pressure, the liquid polymer composition for a one-component adhesive has excellent adhesive strength, good workability without sagging at the time of application, and good curability and storage stability. Was found, and the present invention was completed.

That is, the gist of the present invention is as follows. (1) A liquid polymer composition for a one-component adhesive, wherein a filler is mixed under reduced pressure with a prepolymer obtained by a reaction of a hydroxyl group-containing liquid diene polymer, a polyalkylene glycol, and a polyisocyanate compound. Method of manufacturing a product. (2) The production of the liquid polymer composition for a one-part adhesive according to (1), wherein the filler is at least one compound selected from calcium carbonate, clay, and talc. Method.

(3) The polyisocyanate compound according to (1) or (2), wherein the polyisocyanate compound is any diphenylmethane diisocyanate compound selected from diphenylmethane diisocyanate, liquid-modified diphenylmethane diisocyanate, and polymeric diphenylmethane diisocyanate. A method for producing the composition.

(4) The method for producing a composition according to any of (1) to (3), wherein a dehydrating agent is mixed with the filler. (5) The method for producing a composition according to any one of (1) to (4), wherein the adhesive is an adhesive for flooring or tile application.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The hydroxyl group-containing liquid diene polymer of the present invention is known or can be easily produced by a known method. For example, one or two or more selected from diene monomers having 4 to 22 carbon atoms such as butadiene, isoprene, chloroprene, 1,3-pentadiene, and cyclopentadiene are treated with hydrogen peroxide, 2,2
An azo compound having a hydroxyl group such as 2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] or a peroxide having a hydroxyl group such as cyclohexanone peroxide is subjected to radical polymerization using a polymerization initiator to form a hydroxyl group. A liquid diene-based polymer is obtained.

The amount of the polymerization initiator used is the amount of the diene monomer 1
For example, in the case of using hydrogen peroxide, 1.0 to 50 g is 2,2′-azobis [2-methyl-
When N- (2-hydroxyethyl) propionamide] is used, the preferred range is 5.0 to 100 g, and when cyclohexanone peroxide is used, the preferred range is 5.0 to 100 g. The polymerization may be carried out without solvent, but it is preferable to use a solvent from the viewpoint of easy control of the reaction. As the solvent at this time, ethanol, isopropanol, n-butanol and the like are usually used,
The reaction temperature is preferably 80 to 150 ° C, and the reaction time is preferably 0.5 to 15 hours.

Further, a diene monomer is anionically polymerized using a catalyst such as naphthalenedilithium to produce a living polymer, and further a monoepoxy compound or the like is reacted to obtain a hydroxyl group-containing liquid diene polymer. . The polymerization may be carried out without solvent,
From the same viewpoint as in the case of radical polymerization, it is preferable to use a solvent. At this time, a saturated hydrocarbon such as hexane or cyclohexane is used as the solvent, and the reaction temperature is 50.
To 100 ° C., and the reaction time is preferably 1 to 10 hours. Further, at the time of polymerization, two or more kinds of diene monomers may be used as a mixture, or in the range of 0 to 50 mol% based on the diene monomer, butene, pentene, styrene, α-
2 carbon atoms such as methylstyrene, acrylonitrile, acrylic acid and its ester, methacrylic acid and its ester, vinyl chloride, vinyl acetate and acrylamide
To 22 addition polymerizable monomers may be added.

After the completion of the reaction, the solution is distilled under reduced pressure to remove the solvent, unreacted monomers and the like, thereby obtaining a hydroxyl group-containing liquid diene polymer. The thus obtained hydroxyl group-containing liquid diene polymer has a number average molecular weight of 300 to 1
0000, preferably 500-5000,
The hydroxyl group content is 0.2 to 10 meq / g, preferably 0.4 to 7 meq / g. The hydroxyl group-containing liquid diene polymer is preferably structurally such that the sum of 1,4 structures composed of cis- or trans- is in the range of 50 to 95%.

The hydroxyl group of the hydroxyl group-containing liquid diene polymer may be located at the terminal of the molecular chain or inside the molecular chain, but is preferably located at the terminal of the molecular chain. In addition, two or more kinds of hydroxyl group-containing liquid diene polymers may be used. In addition,
When a hydride of a hydroxyl group-containing liquid diene polymer is used instead of a hydroxyl group-containing liquid diene polymer during prepolymer synthesis, the viscosity of the obtained prepolymer increases extremely, which is disadvantageous in terms of cost. Therefore, they are not suitable as the hydroxyl group-containing liquid diene polymer in the present invention.

The polyalkylene glycol referred to in the present invention is not particularly limited as long as it is used as a general polyalkylene glycol for polyurethane, and may be called polypropylene glycol or the like.
A compound having one or more hydroxyl groups. Specifically, propylene oxide and ethylene oxide polymers and their copolymers are generally used. In addition, glycerin, trimethylolpropane, hexanetriol, monoethanolamine, diethanolamine, triethanolamine, diglycerin, pentaerythritol, ethylenediamine, methylglucoside, tolylenediamine, aromatic diamine, sugars such as sorbitol and sucrose, phosphorus Examples thereof include those obtained by adding propylene oxide at an arbitrary ratio using a polyol compound such as an acid as an initiator, and ethylene oxide adducts thereof. The molecular weight of these polyether polyols is about 200 to 10000, and any one can be used within this range.

In the present invention, at least one or more polyol compounds selected from the above polyalkylene glycols are used. The polyisocyanate compound referred to in the present invention is an organic compound having two or more isocyanate groups in one molecule. Examples of the polyisocyanate compound include ordinary aromatic and aliphatic-aromatic compounds. , Aliphatic and alicyclic ones.

Specifically, for example, 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, a mixture of 4,4'-diphenylmethane diisocyanate and 2,2'-diphenylmethane diisocyanate, tolylene diisocyanate, carbodiimide-modified diphenylmethane Diisocyanate, polymethylene polyphenyl isocyanate, phenylene diisocyanate, naphthalene-1,5-diisocyanate, o
-Toluidine diisocyanate, triphenylmethane triisocyanate, tris (isocyanate phenyl)
Examples thereof include aromatic polyisocyanates such as thiophosphate and isopropylbenzene-2,4-diisocyanate.

Further, an aliphatic-aromatic polyisocyanate having no isocyanate group in which an isocyanate group is directly bonded to an aromatic ring via an aliphatic hydrocarbon, that is, having an isocyanate group directly bonded to an aromatic ring in the molecule. Specific examples of the aliphatic-aromatic polyisocyanate include xylylene diisocyanate and tetramethyl xylylene diisocyanate, which are polyisocyanates that are not used.

Specific examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, dodecane diisocyanate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, Examples thereof include 1,3,6-hexamethylene triisocyanate and trimethylhexamethylene diisocyanate.

Further, specific examples of the alicyclic polyisocyanate include transcyclohexane-1,4-diisocyanate, bicycloheptane triisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate (hydrogenated diphenylmethane diisocyanate), hydrogenated tolylene diisocyanate, hydrogenated Additional xylylene diisocyanate, hydrogenated tetramethyl xylylene diisocyanate, and the like can be given.

Among these polyisocyanate compounds, liquid-modified diphenylmethane diisocyanate such as diphenylmethane diisocyanate and carbodiimide-modified diphenylmethane diisocyanate, and diphenylmethane diisocyanate represented by polymeric diphenylmethane diisocyanate such as polymethylene polyphenyl isocyanate, from the viewpoint of versatility and low toxicity. Compounds are preferred.

The prepolymer according to the present invention is obtained by reacting a hydroxyl group-containing liquid diene polymer with a polyalkylene glycol and a polyisocyanate compound at 0 to 150 ° C., preferably 20 to 120 ° C. for 0.1 to 100 hours. It is preferably obtained by reacting for 0.5 to 50 hours.
At this time, the molar ratio (NCO / OH) of the isocyanate group (NCO) of the polyisocyanate compound to the hydroxyl group (OH) of the mixture of the hydroxyl group-containing liquid diene polymer and the polyalkylene glycol is 1.7 to 25. In obtaining this prepolymer, a short-chain polyol compound described below may be added before the reaction. When a compound having a hydroxyl group that reacts with an isocyanate group is compounded, the molar ratio of the isocyanate group to the hydroxyl group (OH) of all the compound having a hydroxyl group (NCO /
OH) must be finally added to be 1.7 to 25.

The filler according to the present invention is mixed for cost reduction and improvement of the physical properties of the adhesive layer. Zinc, aluminum, copper, nickel, glass spheres, glass flakes, glass fiber, channel black, Furnace black, acetylene black, carbon black such as thermal black, carbon fiber, graphite, asbestos, kaolin clay, waxite clay, talc, kasumilite, cryolite, wollastonite, diatomaceous earth, slate powder, whiting, feldspar powder , Mica, gypsum, quartz powder, fine silicic acid, atavulgite, sericite, volcanic ash, vermiculite, silica, alumina, zinc oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, molybdenum dioxide, aluminum hydroxide, magnesium hydroxide , Heavy calcium carbonate Precipitated calcium carbonate surface-treated, magnesium carbonate, barium sulfate, calcium silicate, zeolite, potassium titanate, boron nitride, boron nitrite, inorganic filler such as molybdenum disulfide as a specific example.

Among them, from the viewpoints of versatility, low cost and handling, calcium carbonate such as heavy calcium carbonate and precipitated calcium carbonate, clay such as kaolin clay and lauric clay, and talc are preferable. At least one or more selected fillers can be used. These fillers are added to the prepolymer and mixed, but before adding the filler to the prepolymer, heat treatment with an oven or a low-boiling solvent that can azeotrope with water is added, and azeotropic distillation with water is performed. It is preferable to remove water by a method such as removal.

The amount of these fillers is not particularly limited, but is usually 50 to 1 based on 100 parts by weight of a prepolymer composed of a hydroxyl group-containing liquid diene polymer, a polyalkylene glycol and a polyisocyanate compound.
000 parts by weight, preferably 70 to 500 parts by weight. As the dehydrating agent in the present invention, generally used inorganic dehydrating agents and organic dehydrating agents are used for improving the storage stability of the obtained prepolymer. Specifically, examples of the inorganic dehydrating agent include zeolites such as natural zeolites and synthetic zeolites, anhydrous or hemihydrate gypsum, silica gel, calcium oxide, calcium chloride, and the like.
Examples of the organic dehydrating agent include a monoisocyanate compound and an orthoformate compound. The amount of these dehydrating agents is 0.01 to 10 parts by weight per 100 parts by weight of the prepolymer composed of the hydroxyl group-containing liquid diene polymer, polyalkylene glycol and polyisocyanate compound.
Parts by weight, preferably 0.1 to 5 parts by weight. It is not preferable to add a large amount of these dehydrating agents, because viscosity increase and poor curing occur.

In order to further improve the mechanical properties of the liquid diene polymer composition obtained in the present invention, a short-chain polyol compound may be used. It may be added before the containing liquid diene polymer is reacted with the polyalkylene glycol and the polyisocyanate compound. In the present invention, a compound having two or more hydroxyl groups in one molecule and having a molecular weight range of 50 to 500 is referred to as a short-chain polyol compound. In use, a primary polyol, a secondary polyol, or a tertiary polyol is used. May be used alone, or two or more of them may be used in combination.

Specifically, 1,2-propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-pentanediol, 2,3 -Pentanediol, 2,5-hexanediol, 2,4-hexanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, glycerin, N, N-bis-2-
At least one of hydroxypropylaniline, N, N'-bishydroxyisopropyl-2-methylpiperazine, and a propylene oxide adduct of bisphenol A;
Low molecular weight short-chain polyols containing hydroxyl groups bonded to two secondary carbons.

Further specific examples include ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,4-propylene glycol not containing a hydroxyl group bonded to a secondary carbon.
Butanediol, 1,5-pentanediol, 1,6-
Hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol and the like can be mentioned.

In the present invention, from the viewpoint of accelerating the reaction,
A curing catalyst can be added to the prepolymer. Specific examples of the curing catalyst include triethylenediamine, tetramethylguanidine, N, N, N'N'-tetramethylhexane-1,6-diamine, N, N, N ', N ", N"
Tertiary amines such as -pentamethyldiethylenetriamine, bis (2-dimethylaminoethyl) ether, 1,2-dimethylimidazole, N-methyl-N '-(2-dimethylamino) ethylpiperazine, and diazabicycloundecene; In addition to carboxylic acid salts of tertiary amines, stannas octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin carboxylate, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin marcaptide, dioctyltin thiocarboxylate And organometallic compounds such as phenylmercury propionate and lead octenoate.

The addition amount of these catalysts is 0.001 to 2 parts by weight based on 100 parts by weight of a prepolymer composed of a hydroxyl group-containing liquid diene polymer, a polyalkylene glycol and a polyisocyanate compound. When the amount of the catalyst exceeds 2 parts by weight, not only the effect of promoting the curing during use is not recognized, but also the risk of occurrence of a local abnormal reaction such as gelation of the prepolymer increases, and the obtained prepolymer Is also not preferred because the storage stability of the product also deteriorates significantly.

In the present invention, a plasticizer can be used from the viewpoint of reducing the viscosity and cost of the obtained prepolymer. Specific examples of the plasticizer include dialkyl phthalates such as dioctyl phthalate, process oils such as paraffin, naphthene and aroma, olefin oligomers, alkyl benzene, alkyl naphthalene, alkyl diphenyl ethane, alkyl diphenyl, silicone oil, and liquid paraffin. , 1-decene oligomer, paraffin-based oligomer and the like.

The compounding amount of these plasticizers is usually the amount of the prepolymer 10 comprising a hydroxyl group-containing liquid diene polymer, a polyalkylene glycol and a polyisocyanate compound.
0 to 150 parts by weight, preferably 0 to 50 parts by weight, based on 0 parts by weight. If the amount of the plasticizer exceeds 100 parts by weight, the adhesive strength is undesirably reduced.

In the present invention, if desired, other additives may be added as long as the object of the present invention is not impaired. That is, from the viewpoint of adjusting the viscosity of the liquid diene polymer composition, n-hexane, cyclohexane, toluene, hydrocarbon solvents such as xylene, methyl ethyl ketone, ketone solvents such as cyclohexanone, ester solvents such as butyl acetate, An ether solvent such as tetrahydrofuran may be blended. These various solvents are usually used in an amount of 0 to 50 parts by weight, preferably 0 to 20 parts by weight, based on 100 parts by weight of a prepolymer composed of a hydroxyl group-containing liquid diene polymer, polyalkylene glycol and polyisocyanate. .

Further, from the viewpoint of adjusting the adhesive strength and the adhesive strength of the liquid diene polymer composition, alkyl phenol resin, terpene resin, terpene phenol resin, xylene formaldehyde resin, rosin, hydrogenated rosin, cumarone resin, aliphatic, Alicyclic and aromatic petroleum resins may be blended. Further, from the viewpoint of improving heat resistance and weather resistance, an antioxidant such as an antioxidant, an ultraviolet absorber, and a hindered amine light stabilizer may be added.

In the present invention, a liquid diene polymer composition is prepared by blending the above components in the above ratios. Specifically, a filler, which is preferably dried so that the water content of the filler is 1% by weight or less, is added to the prepolymer, and a mixing device such as a mixer or a kneader capable of mixing under reduced pressure, and kneading. Using a device, usually 0-1
The mixture is stirred and mixed at a temperature of 00C, preferably 15 to 80C, usually for 5 minutes to 5 hours, preferably for 15 minutes to 3 hours.
And it is necessary to reduce the pressure at that time,
Preferably, it is 0 to 5 × 10 ⁴ Pa · A (A = absolute pressure, hereinafter used), more preferably 0 to 1.5 × 10 10 Pa · A.
⁴ Pa · A.

The addition of a dehydrating agent, a plasticizer, a curing catalyst, an antioxidant and the like may be performed after or simultaneously with the addition of the filler. Thus, a liquid diene polymer composition for an adhesive is prepared. This composition can be used as an adhesive between wood flooring boards and concrete used for interiors of apartments and houses, an adhesive between metal columns and floors of OA floors, an adhesive between PVC sheet and floor, and a carpet. Adhesives for flooring materials such as adhesives to the floor surface, or for various adhesives such as sticking to the base of tiles such as kitchens, washrooms, bathrooms, etc. A good adhesive layer is formed.

[0037]

Next, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. First, the following example,
A production example of a hydroxyl group-containing liquid diene copolymer used in a comparative example is shown.

[Production Example 1] Hydroxy-terminated liquid polyisop
Preparation of Rene In a 1-liter stainless steel pressure-resistant reaction vessel, add isoprene
200 g, 40 g of 20% hydrogen peroxide solution and iso
100g propanol, temperature 120 ℃, maximum pressure
The reaction is carried out under the conditions of force 1 MPa · G and reaction time 2 hours.
Was. After the completion of the reaction, the reaction mixture is put into a separatory port, and
After adding 0 g of water and shaking, and left standing for 3 hours, the oil layer was separated.
I took it. Solvents, monomers and low boiling components are removed from this oil layer by 2
Distillation was performed under the conditions of mmHg, 100 ° C. and 2 hours.
Liquid polyisoprene having hydroxyl groups at the ends (yield 66 weight
%). It has a number average molecular weight of 2190, hydroxyl
The group content is 0.97 meq / g, and the viscosity is 64 poise / 3.
At 0 ° C., the bromine number was 219 g / 100 g. 1 at this time
The average number of hydroxyl groups per molecule is 2.12. Also, ¹
The results of the structural analysis by H-NMR were as follows:
58%, cis-1,4 structure 30%, 1,2-vinyl structure
8% and 3,4-vinyl structure 4%.

[Production Example 2] Preparation of hydride of hydroxyl group-terminated liquid polyisoprene 100 g of liquid polyisoprene having a hydroxyl group at a molecular chain terminal obtained by the production method described in Production Example 1 and ruthenium having a ruthenium content of 5% by weight 5 g of a carbon catalyst and 100 g of cyclohexane as a solvent were charged into a 1-liter stainless steel pressure-resistant reaction vessel, and a hydrogenation reaction was performed at 150 ° C. for 6 hours under a hydrogen pressure of 5 MPa · G. After the completion of the reaction, the catalyst was separated and removed from the reaction solution through a 0.45 μm membrane filter.
The solvent was distilled off at 2 ° C. for 2 hours. As a result, a hydride of liquid polyisoprene having a hydroxyl group at a molecular chain terminal was obtained. It had a number average molecular weight of 2,280, a hydroxyl group content of 0.96 meq / g, and a viscosity of 685 poise / 3.
The temperature was 0 ° C. and the bromine value was 2 g / 100 g. At this time, the average number of hydroxyl groups per molecule is 2.19. Also, ¹ H−
Structural analysis by NMR was performed, and the trans-1,4 structure, cis-1,4 structure, 1,2-vinyl structure, 3,4-
No vinyl structure was observed. This is considered to be due to the disappearance of the intramolecular double bond by the hydrogenation reaction.

[Preparation Example 3] Preparation of hydroxyl-terminated liquid polyisoprene A 1-liter stainless steel pressure-resistant reaction vessel was charged with 200 g of isoprene, 100 g of a 30% hydrogen peroxide solution and 300 g of isopropanol, at a temperature of 115 ° C and a maximum pressure of 7 kg. The reaction was performed under the conditions of / cm ² · G and a reaction time of 2.5 hours. After the completion of the reaction, the reaction mixture was put into a separating funnel, 600 g of water was added, the mixture was shaken, and the mixture was allowed to stand for 3 hours. Solvents, monomers and low boiling components were distilled off from the oil layer under the conditions of 2 mmHg, 100 ° C. and 2 hours.
Liquid polyisoprene having a hydroxyl group at a molecular chain terminal (yield: 71% by weight) was obtained. Its number average molecular weight is 135
0, the hydroxyl group content was 1.58 meq / g, and the viscosity was 42 poise / 30 ° C. At this time, the average number of hydroxyl groups per molecule is 2.13. The results of structural analysis by ¹ H-NMR show that the trans-1,4 structure is 56% and the cis-
1,4 structure 32%, 1,2-vinyl structure 7%, 3,4-
The vinyl structure was 5%.

Production Example 4 Preparation of Hydroxyl-Containing Liquid Isoprene-Butadiene Copolymer A 1-liter stainless steel pressure-resistant reactor was charged with 90 g of isoprene, 110 g of butadiene, 40 g of a 20% strength hydrogen peroxide solution and 100 g of isopropanol. The reaction was performed under the conditions of a temperature of 120 ° C., a maximum pressure of 14 kg / cm ² · G, and a reaction time of 2 hours. After completion of the reaction, the reaction mixture was placed in a separating funnel, and 600 g of water was added thereto.
After standing for an hour, the oil layer was separated. The solvent, monomer and low boiling point component were distilled off from this oil layer under the conditions of 2 mmHg, 100 ° C. and 2 hours to obtain a hydroxyl group-containing liquid isoprene-butadiene copolymer (yield 62% by weight). It had a number average molecular weight of 2,230 and a hydroxyl group content of 0.91 meq /
g, viscosity: 43 poise / 30 ° C., bromine number: 218 g / 10
It was 0 g. At this time, the average number of hydroxyl groups per molecule is 2.03. Further, as a result of structural analysis by ¹ H-NMR, the isoprene content was 44% and the butadiene content was 56%. On the other hand, the ratio of the 1,4-structure was 86%.

Example 1 Of the ingredients listed in Table 1, the other components except calcium carbonate were reacted at 80 ° C. for 5 hours to obtain a prepolymer. Then, calcium carbonate was mixed with the prepolymer at 50 ° C. for 30 minutes using a kneader under a pressure of 5 × 10 ³ Pa · A to obtain a liquid diene polymer composition.

The evaluation results of the obtained prepolymer and liquid diene polymer composition are shown in Table 1. [Comparative Example 1] All the ingredients shown in Table 1 were added simultaneously, mixed at atmospheric pressure and reacted as a prepolymer to obtain a liquid diene polymer composition.

The evaluation results of the obtained prepolymer and liquid diene polymer composition are shown in Table 1. Comparative Example 2 A liquid diene polymer composition was obtained in the same manner as in Example 1 except that calcium carbonate was mixed at atmospheric pressure among the ingredients shown in Table 1.

Table 1 shows the evaluation results of the obtained prepolymer and liquid diene polymer composition.

[0046]

[Table 1]

Notes 1) to 6) described in Table 1 are as follows. The unit of the numerical value of each compounding agent described in Example 1 and Comparative Examples 1 and 2 in Table 1 is part by weight. ... 1): Hydroxy group-containing liquid polybutadiene (manufactured by Idemitsu Atchem Co., Ltd., trade name: Poly bd R-45H)
T), hydroxyl group content = 0.85 meq / g, number average molecular weight = 2560, viscosity = 48 poise / 30 ° C. 2): polypropylene glycol (manufactured by Asahi Denka Co., Ltd., trade name: Adeka polyether P-2000) , Hydroxyl group content = 1.00 meq / g, number average molecular weight = 200
0 ... 3): 4,4'-diphenylmethane diisocyanate (manufactured by Mitsubishi Chemical Dow Co., Ltd., trade name: Isonate 125M), NCO content = 33.5 wt% ... 4): Heavy calcium carbonate (Nitto Powdered) Manufactured by Kogyo Co., Ltd., trade name: NS-80) ··· 5): The state after one month at room temperature is visually checked, ○ indicates no change, X indicates hardening or gelation ··· 6): B type Measured by viscometer [Examples 2 to 11] Among the ingredients listed in Table 2, other components except calcium carbonate were reacted at 80 ° C for 5 hours to obtain a prepolymer. Also, in this prepolymer,
Calcium carbonate was mixed at 50 ° C. for 30 minutes using a kneader under a pressure of 5 × 10 ³ Pa · A to obtain a liquid diene polymer composition.

Table 2 shows the evaluation results of the obtained liquid diene polymer composition.

[0049]

[Table 2]

Notes 1) to 14) described in Table 2 are as follows. Examples 2 to 11 in Table 2 were used.
The unit of the numerical value of each component constituting the liquid diene polymer composition described in (1) is part by weight. ... 1): Hydroxy group-containing liquid polybutadiene (manufactured by Idemitsu Atchem Co., Ltd., trade name: Poly bd R-45H)
T), hydroxyl group content = 0.85 meq / g, number average molecular weight = 2560, viscosity = 48 poise / 30 ° C. 2): hydroxyl group-containing liquid polybutadiene (manufactured by Idemitsu Atchem Co., Ltd., trade name: Poly bd R-15H)
T), hydroxyl group content = 1.85 meq / g, number average molecular weight = 1250, viscosity = 14 poise / 30 ° C. 3): polypropylene glycol (manufactured by Asahi Denka Co., Ltd., trade name: Adeka polyether P-2000) , Hydroxyl group content = 1.00 meq / g, number average molecular weight = 200
0 ... 4): 4,4'-diphenylmethane diisocyanate (manufactured by Mitsubishi Chemical Dow Co., Ltd., trade name: Isonate 125M), NCO content = 33.5 wt% ... 5): Carbodiimide-modified diphenylmethane diisocyanate, liquid-modified diphenylmethane Diisocyanate (Nippon Polyurethane Industry Co., Ltd.), isocyanate content = 29.0% 6): Heavy calcium carbonate (Nitto Powder Chemical Co., Ltd., trade name: NS-80) 7): Kaolin Clay (manufactured by Tsuchiya Kaolin Industries, Ltd.) 8): Monofunctional isocyanate (manufactured by Sumitomo Bayer Urethane Industries, Ltd.) 9): Dioctyl phthalate (manufactured by Shin Nippon Rika Co., Ltd.) 10): Jls In conformity with -K6854, the adherend uses natural rubber / cotton pan cloth .. 11): B-type viscosity 12): Applied to a 45 ° concrete plate and checked for sagging. 13): Visually checked the condition one month after room temperature. ○: No change. X: Hardened or Gelation ········· 14): Applied to a concrete plate and confirmed the degree of hardening of the composition after a lapse of room temperature overnight [Comparative Examples 3 to 7] Among the compounding agents shown in Table 3, calcium carbonate was used. The other components were reacted at 80 ° C. for 5 hours,
A prepolymer was obtained. In addition, calcium carbonate was mixed with the prepolymer at 50 ° C. for 80 minutes using a kneader under a pressure of 5 × 10 ³ Pa · A to obtain a liquid diene polymer composition.

Table 3 shows the evaluation results of the obtained liquid diene polymer composition.

[0052]

[Table 3]

Notes 1) to 10) described in Table 3 are as follows. In addition, the unit of the numerical value of each component constituting the liquid diene polymer composition described in Comparative Examples 3 to 7 in Table 3 is part by weight. ... 1): Hydroxy group-containing liquid polybutadiene (manufactured by Idemitsu Atchem Co., Ltd., trade name: Poly bd R-45H)
T), hydroxyl group content = 0.85 meq / g, number average molecular weight = 2560, viscosity = 48 poise / 30 ° C. 2): polypropylene glycol (manufactured by Asahi Denka Co., Ltd., trade name: Adeka polyether P-2000) , Hydroxyl group content = 1.00 meq / g, number average molecular weight = 200
0 ... 3): 4,4'-diphenylmethane diisocyanate (manufactured by Mitsubishi Chemical Dow Co., Ltd., trade name: Isonate 125M), NCO content = 33.5 wt% ... 4): Heavy calcium carbonate (Nitto Powdered) 5): Monofunctional isocyanate (manufactured by Sumitomo Bayer Urethane Industries, Ltd.) 6): Based on Jls-K6854, and the adherend is natural rubber / 7): Measured with a B-type viscometer. 8): Applied to a 45 ° concrete plate to check for sagging. 9): One month after room temperature. Visually check the state, ○: no change, X: hardening or gelling ······· 10): Apply to a concrete plate and check the degree of hardening of the composition after overnight at room temperature

[0054]

The liquid polymer composition for a one-component adhesive of the present invention is obtained by mixing a specific filler with a prepolymer comprising a hydroxyl group-containing diene polymer, a polyalkylene glycol and a polyisocyanate compound under reduced pressure. The composition is characterized by having excellent adhesive strength, no sagging during application, good workability, and good curability and storage stability.

Claims (5)

[Claims] 1. A liquid polymer for a one-component adhesive, wherein a filler is mixed under reduced pressure with a prepolymer obtained by the reaction of a hydroxyl group-containing liquid diene polymer, a polyalkylene glycol, and a polyisocyanate compound. A method for producing a united composition. 2. A filler comprising calcium carbonate, clay,
The method for producing a one-part adhesive liquid polymer composition according to claim 1, wherein the compound is at least one compound selected from the group consisting of talc and talc. 3. The composition according to claim 1, wherein the polyisocyanate compound is any one of diphenylmethane diisocyanate compounds selected from diphenylmethane diisocyanate, liquid modified diphenylmethane diisocyanate, and polymeric diphenylmethane diisocyanate. Manufacturing method. 4. The method for producing a composition according to claim 1, wherein a dehydrating agent is mixed together with the filler. 5. The method for producing a composition according to claim 1, wherein the adhesive is an adhesive for flooring or tile application.