JPH11263906A - Urethane prepolymer composition - Google Patents

Abstract

(57) [Summary] [PROBLEMS] A cured product having excellent flame retardancy and weather resistance,
For example, to provide a urethane prepolymer composition that can be suitably used as an adhesive for ballast. SOLUTION: (A) a polyol compound and (B) a polyisocyanate compound are NCO / OH = 1.1-1.
A urethane prepolymer having an isocyanate group at a terminal obtained by reacting at a ratio of 0.0, wherein the polyol compound (A) is (A-1) a flame-retardant polyol and, if necessary, (A-2) With respect to 100 parts by weight of a urethane prepolymer comprising another polyol, (C)
At least one non-reactive phosphate ester flame retardant
A urethane prepolymer composition containing 100 parts by weight.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a urethane prepolymer composition, and more particularly, to a urethane prepolymer having excellent flame retardancy, which comprises a flame retardant polyol as a polyol component and further contains a phosphate ester flame retardant. It relates to a prepolymer composition.

[0002]

2. Description of the Related Art Ballasts (pebbles and gravel) laid under railway tracks are:
In order to prevent scattering due to wind pressure or other external force caused by passing through the train, it is fixed and held with an appropriate adhesive. Conventionally, an emulsion adhesive or an epoxy adhesive has been used for such ballast fixing. Emulsion adhesives have the advantage that they can be easily applied and the cost is low because they are one component, but due to drying and curing by water volatilization, the time required for curing is extremely long and is easily affected by the weather, Low in nature. On the other hand, epoxy adhesives
Although the curability is better than that of the emulsion adhesive, the cured coating film is hard and the amine is used as a curing agent, which causes toxic problems such as rash. May be connected.

[0003] Including the above-mentioned problems of the conventional adhesive, the problems of the adhesive in the ballast fixing application include (1) low toxicity in consideration of leakage under crosslinking, and (2) renovation and repair. That the ballast layer is fixed only so that it can be carried out smoothly; (3) that it has a quick-hardening property that is not affected by the weather at the time of construction and that quickly solidifies without flowing out even in case of sudden rain; (4) Flame-retardant with respect to the sparks when polishing the track and the heating burner used to adjust the length (5)
It is required that it be cured within 3 to 4 hours and be able to cope with train passing because of night work, and (6) it must have weather resistance to withstand deterioration by wind, rain and sunlight after the work.

In order to solve such problems, for example, Japanese Patent Application Laid-Open No. Hei 6-322706 proposes a ballast consolidation method in which a one-part moisture-curable urethane elastomer is sprayed. Japanese Patent Application Laid-Open No. 166146/1992 discloses that water containing a terminal isocyanate group-containing prepolymer obtained by reacting an organic polyisocyanate compound with a polyether polyol containing at least an ethylene oxide portion and a melamine modified product of the polyether polyol is used in combination. Curable adhesives have been proposed, and by using such a urethane elastomer, the above-mentioned problems (1), (2), (3) and (5) can be improved to some extent. Further, these publications describe the use of a flame-retardant polyol as a polyol component or the use of a flame retardant in combination, but this alone is not sufficient for the above-mentioned problems (4) and (6). The effects of improving the flammability and weather resistance were still insufficient.

[0005]

The present inventors have conducted various studies in view of the present situation, and as a result, have found that a terminal isocyanate group-containing compound obtained by using a phosphorus-based or halogen-based flame-retardant polyol as a polyol component. The urethane prepolymer composition comprising a urethane prepolymer and a phosphate ester-based flame retardant not only cures quickly by using water as a curing agent, but also has excellent flame retardancy and weather resistance. I learned.

[0006] The present invention has been made based on the above-mentioned findings, and has a terminal compound obtained by reacting (A) a polyol compound and (B) a polyisocyanate compound at a ratio of NCO / OH of 1.1 to 10.0. A urethane prepolymer having an isocyanate group, wherein the (A) polyol compound is based on 100 parts by weight of a urethane prepolymer comprising (A-1) a flame-retardant polyol and, if necessary, (A-2) another polyol. And (C) a urethane prepolymer composition comprising at least 1 to 100 parts by weight of a non-reactive phosphate ester flame retardant.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the urethane prepolymer composition of the present invention will be described in detail.

The flame-retardant polyol (A-1) used in the present invention is preferably a phosphorus-containing or halogen-containing polyol. The phosphorus content is 1% by weight.
Above, especially 5% by weight or more, halogen content of 10% by weight
As described above, those containing 30% by weight are particularly preferable, and polyols represented by the following formulas (I) to (III) are particularly preferable.

[0009]

Embedded image

In the above formula, the alkyl group represented by R ₁ or R ₂ includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, tert-amyl, hexyl, heptyl Octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, isononyl, tertiary nonyl, decyl, isodecyl, dodecyl, tridecyl, isotridecyl, tetradecyl,
Hexadecyl, octadecyl, eicosyl, docosyl,
Linear or branched alkyl groups such as tetracosyl and triacontyl are exemplified. As the aryl group, for example,
Groups such as phenyl and naphthyl; and examples of the arylalkyl group include groups such as benzyl, α-methylbenzyl and α, α-dimethylbenzyl. Examples of the alkylaryl group include those exemplified above. And an aryl group substituted with 1 to 5 alkyl groups. Examples of the alkylene group represented by A _{1 to} A ₇ include groups such as methylene, ethylene, propylene, and butylene. Examples of the halogen atom represented by X include chlorine and bromine.

Accordingly, specific examples of the flame-retardant polyol (A-1) used in the present invention include, for example, diisopropyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate, diisobutyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate,
Dioctyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate, dioctadecyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate, diethyl-N, N-bis (2-hydroxyethyl)
Aminomethylphosphonate, diethyl-N, N-bis [2- (2-hydroxyethoxy) ethyl] aminomethylphosphonate, diethyl-N, N-bis [Ω- (2-
(Hydroxy) polyethoxyethyl] aminomethylphosphonate, diethyl-N, N-bis (2-hydroxypropyl) aminomethylphosphonate, tris (2-hydroxyethyl) phosphate, tris (2-hydroxypropyl) phosphate, tris [2- ( 2-hydroxyethoxy) ethyl] phosphate, tris [Ω- (2-
Hydroxyethoxy) polyethoxyethyl] phosphate, tris (2-hydroxypropyl) phosphate,
Tetrakis (2-hydroxyethyl) pyrophosphate, tetrakis (2-hydroxypropyl) pyrophosphate, tetrakis [2- (2-hydroxyethoxy)
Ethyl] pyrophosphate, tetrakis [Ω- (2-hydroxyethoxy) polyethoxyethyl] pyrophosphate, poly (2-hydroxyethyl) polyphosphate, poly (2-hydroxypropyl) polyphosphate, poly [2- (2-hydroxy Ethoxy) ethyl] polyphosphate, poly [Ω- (2-hydroxyethoxy) polyethoxyethyl] polyphosphate, 2,2 ′
-Bis (3,5-dibromophenyl-4-ethanol)
Propane, 2,2'-bis (3,5-dichlorophenyl-4-ethanol) propane, 4,4'-bis [2-
(2-hydroxyethyl) ethoxy] octachlorobiphenyl and the like.

Other polyols of the component (A-2) used in the present invention include, for example, ethylene glycol,
Diethylene glycol, triethylene glycol, 1,
2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, hexamethylene glycol, hydrogenated bisphenol A, bis (hydroxyethoxyphenyl) propane, etc. Low molecular weight polyols or polyether polyols thereof such as ethylene oxide and / or propylene oxide adducts, polyethylene glycol, polypropylene glycol, polyethylene / propylene glycol, polytetramethylene glycol; and the above low molecular weight polyols and / or polyether polyols Acid, glutaric acid,
Polyester polyol which is a condensate with polybasic acid such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, endmethylenetetrahydrophthalic acid, hexahydrophthalic acid or carbonic acid; Polybutadiene polyols obtained by hydroxylating 1,2-polybutadiene, 1,4-polybutadiene, polyisoprene and the like; polycarbonate polyols and the like.

In the present invention, the component (A-2) is optional. However, it is preferable to use the component (A-1) because it can impart flexibility and improve curability. The usage ratio (weight ratio) of the component (A-2) is usually appropriately determined depending on the purpose within the range of (A-1) / (A-2) = 10/1 to 1/10. 5 /
It is preferable to use in the range of 1/5.

Examples of the polyisocyanate compound (B) used in the present invention include aliphatic, alicyclic and aromatic polyisocyanates. Specific examples include trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene. Diisocyanate, 2,4,4-
Trimethylhexamethylene diisocyanate, 2,2
4-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,
4-diphenylmethane diisocyanate, phenylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate ester, 4,4'-diphenyl diisocyanate, 4,4'-diphenyl ether diisocyanate, 1,4- Cyclohexylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, and the like.

The urethane prepolymer used in the present invention comprises the above component (A) [component (A-1) and, if necessary, component (A-2)] and the above component (B) in NCO / O
It can be easily obtained by reacting in a conventional manner at a ratio of H = 1.1 to 10.0. Here, among the components (A), (A-1) and (A-2) Can be reacted with the component (B) at once,
Those previously reacted with the component (B) can also be mixed, and also in this case, NCO / OH =
The reaction is performed at a ratio of 1.1 to 10.0.

The non-reactive phosphate ester flame retardant of the component (C) used in the present invention is a phosphate ester compound having no group capable of reacting with the polyisocyanate compound of the component (B), For example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, octyl diphenyl phosphate, tetrakisphenyl 1,3-phenylenediphosphate, tris (butoxyethyl) phosphate, tetrakisphenyl 4,4'-isopropylene bisphenylene diphosphate, tetrakisoctyl-4,4'-isopropylene bis (tetrabromophenylene) diphosphate, tris (2-chloroethyl) phosphate, tris (2 Bromoethyl) phosphate, tris (3-chloropropyl) phosphate, tris (1,3-dichloro-propyl) phosphate, tris (2,3-dibromopropyl) phosphate, tris (2,3-dibromo-butyl) phosphate, tris (2
-Bromo-3-chloropropyl) phosphate, tris (dichloroisopropyl) phosphate, bis (chloropropyl) dichloropropylphosphate, bis (chloroethyl) dichloropropylphosphate, bis (2,3-dibromopropyl) .2.3- Dichloropropyl phosphate, phenyl bis (2-chloroethyl) phosphate, octyl bis (3-chloropropyl) phosphate, phenyl bis (3-chloropropyl) phosphate, 2-bromotert-butyl bis (2-
Chloroethyl) phosphate, tris (2,4-dichlorophenyl) phosphate, dichloromethylene-bis (2-chloroethyl) phosphate, tetrakis (2-
Chloroethyl) ethylene diphosphate and the like can be mentioned. In particular, it is preferable to use a halogenated phosphoric acid ester-based flame retardant because it shows more excellent flame retardancy.

The amount of the non-reactive phosphate ester flame retardant (C) used is based on 100 parts by weight of the urethane prepolymer obtained from the components (A) and (B),
At least one non-reactive phosphate ester flame retardant
100 parts by weight, preferably 5 to 50 parts by weight. If the amount of the non-reactive phosphate ester flame retardant (C) is less than 1 part by weight, the effect is not sufficiently exhibited, and if it exceeds 100 parts by weight, physical properties are adversely affected. Absent.

It is preferable that the composition of the present invention is further blended with a ketimine compound (D) because a resin composition having more excellent curability can be provided.

The (D) ketimine compound is obtained from an amine and a keto compound. Examples of the amine that can provide these (D) ketimine compounds include, for example, ethylenediamine, 1.2-propylenediamine,
1,3-propylenediamine, 1,3-butylenediamine, 1,4-butylenediamine, pentylenediamine,
Aliphatic amines such as hexylenediamine, 2,4,4-trimethylhexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, dimethylaminopropylamine and diethylaminopropylamine; mensendiamine; 3-bis (aminomethyl) cyclohexane, 1,4-diaminocyclohexylmethane, bis (4
Alicyclic amines such as -aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, (3-methyl-4-aminocyclohexyl) methane, and isophoronediamine; phenylenediamine, tolylenediamine, xylylenediamine, diaminophenol Aromatic amines such as methane, diaminophenylsulfone, diaminobiphenyl, diaminoisopropylpropylbenzene, diaminodiethylbenzene, diaminostilbene, and triaminebenzene; polyetherpolyamines such as polyoxypropylenediamine and polyoxypropylenetriamine; N-aminoethylpiperazine; , 9-Bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.
5] Heterocyclic-containing amines such as undecane and diaminopyridine.

Examples of the keto compound capable of providing the (D) ketimine compound include methyl ethyl ketone, methyl isobutyl ketone, dimethyl ketone, diethyl ketone, dibutyl ketone, diisobutyl ketone, methyl isopropyl ketone, ethyl butyl ketone, and the like. Methyl octyl ketone, methyl phenyl ketone, methyl cyclohexyl ketone, dioctyl ketone, aryl methyl ketone, methyl cyclohexenyl ketone, methoxymethyl butyl ketone, 1,20-eicosandione, 1,18-octadecanedione, ketone resin, etc. .

The method for producing the (D) ketimine compound from these amines and the keto compound is not particularly limited. For example, a method for producing the ketimine compound by dehydration condensation at 160 ° C. to 220 ° C. for 2 to 10 hours is used. It is mentioned as a suitable method.

The amount of the (D) ketimine compound used is
It is preferably from 0.1 to 20 parts by weight, more preferably from 1 to 10 parts by weight, based on 100 parts by weight of the urethane prepolymer. It is not preferable to use more, because not only is it wasteful, but it may adversely affect various performances.

The urethane prepolymer composition of the present invention may contain an antistatic agent such as a fluorine-based or siloxane-based agent, an inorganic colloid sol such as colloidal silica or colloidal alumina, a surfactant, an antioxidant, and an ultraviolet absorber, depending on the purpose. Add conventional additives such as agents, light stabilizers, coloring agents, waxes, anti-fog agents, preservatives, defoamers, plasticizers, solvents, film-forming aids, dispersants, thickeners, and fragrances. Can also.

The urethane prepolymer composition of the present invention comprises:
In particular, when water is used as a curing agent, it cures quickly, and is particularly suitable as an adhesive for ballasts because of its good flame retardancy and weather resistance, but its use is not limited to this. Without, for example, also suitable as a moisture-curable adhesive such as a rubber chip binder,
Also, by reacting with a two-part curable adhesive used in combination with active hydrogen compounds such as polyamines and polyols or these active hydrogen compounds, various molded products, foams, paints,
It can also be used as a raw material for producing an adhesive or the like.

[0025]

EXAMPLES The present invention will be described in more detail with reference to Production Examples and Examples, but the present invention is not limited by the following Examples.

Production Example 1 (Production of urethane prepolymer) 1500 g (6 mol) of luplanate MI (manufactured by BASF: 4,4-diphenylmethane diisocyanate) and F
B-330 (manufactured by Asahi Denka Kogyo KK: propylene oxide adduct of polyphosphoric acid, hydroxyl value 340, number of functional groups: 4.)
5, phosphorus content 7.5% by weight) 447 g (0.6 mol)
, And reacted at 60 to 70 ° C. for 2 hours, and further reacted at 70 to 80 ° C. for 3 hours to obtain a urethane prepolymer (NUP) having an isocyanate content of 19.3%.
-1) was prepared.

Production Example 2 (Production of urethane prepolymer) 825 g (3.3 mol) of luplanate MI was mixed with 40 to 5
Keep at 0 ° C and add FC-450 (Asahi Denka Kogyo Co., Ltd.)
Manufacture: diethyl-N, N-bis (2-hydroxyethyl)
After dropping 250 parts (1 mol) of aminomethylphosphonate, phosphorus content 12.2% by weight) over 5 hours, the mixture is further reacted at 70 to 80 ° C. for 2 hours to obtain a urethane prepolymer having an isocyanate content of 16.7%. (NUP-2)
Was manufactured.

Production Example 3 (Production of urethane prepolymer) FG-3600 (manufactured by Teijin Chemicals Limited; 2,2'-bis (3,5-dibromophenyl-4-ethanol) propane, bromine content 50% by weight 632 g (1 mol) was previously dissolved in 316 g of Amigard V490 (manufactured by Air Brown Co., Ltd .; diethylethylphosphonate), and 750 g (3 mol) of luplanate MI was added thereto.
The reaction is carried out at 0 to 80 ° C. for 3 hours, and the
A 3.0% urethane prepolymer (NUP-3) was produced.

Production Example 4 (Production of urethane prepolymer) 1841 g (7.36 mol) of luplanenet MI, PR
-3007 (made by Asahi Denka Kogyo KK; propylene glycol-ethylene oxide-propylene oxide adduct) 6
44 g (0.21 mol) and 518 g of FB-330
(0.70 mol) at a time, and under a nitrogen stream, 75 to
Reaction at 85 ° C for 3 hours to give isocyanate content of 1
A 5.6% urethane prepolymer (NUP-4) was produced.

Production Example 5 (Production of urethane prepolymer) 708 g (0.14 mol) of M-950 (manufactured by Asahi Glass Co., Ltd .: melamine-modified polyol) and luplanate MI
311 g (2.5 mol) were charged in a lump, and 80 to 9
Reaction at 0 ° C for 3 hours, 8.5% isocyanate content
Of urethane prepolymer (HUP-1).

Production Example 6 (Production of urethane prepolymer) 3000 g (1 mol) of PR-3007 and 500 g (2 mol) of luplanate MI were charged all at once, and
Reaction at 85 ° C. for 5 hours yields an isocyanate content of 2.4
% Urethane prepolymer (UP-1).

Examples 1 to 15 and Comparative Examples 1 to 6 As shown in the following [Table 1], [Table 2] and [Table 3],
The urethane prepolymers obtained in Production Examples 1 to 6 were blended with a flame retardant (in Examples 12 to 14, a ketimine compound was further blended) to prepare a urethane prepolymer composition, and the following tests were performed. The results are shown in the following [Table 1],
The results are shown in [Table 2] and [Table 3].

(Storage Stability Test) The state of the uncured blend left at 40 ° C. for 50 days was visually evaluated according to the following criteria. ：: No separation or precipitation was observed at all. Δ: Some separation or precipitation was observed. ×: Complete separation or precipitation is observed.

(Curability test) An adhesive was sprayed on a ballast having an average square size of 2 cm, and the touch dry time was measured. A: Tack free within 2 hours. ：: Tack-free within 2-3 hours. Δ: tack-free within 3 to 5 hours. ×: Tack-free after 5 hours or more.

(Melting Evaluation Test) The cured product cured with water was cut into a size of 2 cm × 10 cm, and was exposed to a portion 1 cm from the edge by an LPG lighter over an open flame for 10 seconds, and evaluated according to the following evaluation criteria. ◎: No melting is observed ○: Slight melting is observed △: Melting is observed ×: Drops are formed as drops

(Combustion evaluation test) Observation was made simultaneously with (melting evaluation). ◎ ： Does not burn even in flames ○ ： Burns in flames but disappears when the flame is moved away △ ： Burns in flames but disappears after a while away from flames × ： Continues burning away from flames thing

(Weather Resistance Test) The urethane prepolymer composition was applied to a slate plate in a thickness of 1 mm and cured with water. The state after standing for 200 hours in a sunshine weatherometer was observed and evaluated according to the following evaluation criteria. did. ◎: Adhered to the substrate while maintaining flexibility. : Adhesion to the base material, although the flexibility was slightly lost. Δ: The flexibility was lost, and the film was slightly peeled off from the substrate. ×: Hard and brittle, losing adhesiveness, and in some cases, cracking.

(Coating film physical property test) A tensile test was performed in accordance with JIS K 7113, and a tensile strength T _B (kg / cm ² )
And it was determined elongation E _B (%) (Example 8-15 not implemented).

[0039]

[Table 1]

[0040]

[Table 2]

[0041]

[Table 3]

As is clear from the above comparative examples, the cured product of the elastomer obtained by using the non-flame-retardant polyether polyol alone can make the flame close even when a non-reactive phosphate ester-based flame retardant is added. And melts easily. In addition, even in the case of a cured product of an elastomer using a flame-retardant polyol such as a phosphorus-containing or halogen-containing polyol, the effect of improving the flame retardancy is completely insufficient when a non-reactive phosphate ester-based flame retardant is not blended. . Further, when a non-reactive halogen-containing flame retardant is added thereto, the effect of improving the flame retardancy is small, and there is a disadvantage that the weather resistance is further reduced.

On the other hand, as is clear from the above Examples, the composition of the present invention in which a non-reactive phosphate ester flame retardant is used in combination with a urethane prepolymer obtained from a flame retardant polyol and a polyisocyanate compound is used. The flame retardancy is remarkably improved, and the storage stability, weather resistance, and coating film properties are also excellent. In particular, the curability is remarkably improved by using a ketimine compound in combination.

[0044]

As described above, the cured product of the urethane prepolymer composition of the present invention has excellent flame retardancy and weather resistance, and can be suitably used, for example, as an adhesive for ballast.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08G 18/42 C08G 18/42 Z 18/48 18/48 Z

Claims (8)

[Claims] 1. A method according to claim 1, wherein the polyol compound (A) and the polyisocyanate compound (B) are NCO / OH = 1.1-1.
A urethane prepolymer having an isocyanate group at a terminal obtained by reacting at a ratio of 0.0, wherein the polyol compound (A) is (A-1) a flame-retardant polyol and, if necessary, (A-2) With respect to 100 parts by weight of a urethane prepolymer comprising another polyol, (C)
At least one non-reactive phosphate ester flame retardant
A urethane prepolymer composition containing 100 parts by weight. 2. The (A-1) flame-retardant polyol and the (A-2) other polyol are combined with (A-1) /
The urethane prepolymer composition according to claim 1, which is used in a ratio (weight ratio) of (A-2) = 10/1 to 1/10. 3. The urethane prepolymer composition according to claim 1, wherein the (A-2) other polyol is a polyester polyol or a polyether polyol. 4. The urethane prepolymer 10
The urethane prepolymer composition according to any one of claims 1 to 3, wherein the urethane prepolymer composition comprises 0.1 to 20 parts by weight of at least one kind of the ketimine compound (D) with respect to 0 parts by weight. 5. The urethane prepolymer composition according to claim 1, wherein the (A-1) flame-retardant polyol is at least one selected from phosphorus-containing and halogen-containing polyols. 6. The flame-retardant polyol (A-1) is at least one selected from the compounds represented by the following formulas (I) to (III). The urethane prepolymer composition according to any one of the above. Embedded image 7. The method according to claim 1, wherein the composition is cured with water.
7. The urethane prepolymer composition according to any one of items 1 to 6. 8. The urethane prepolymer composition according to claim 1, which is used for fixing a ballast.