JPS5845218A - Polyurethane composition - Google Patents

Abstract

PURPOSE:To obtain the titled rapid-setting composition having excellent physical properties suitable for waterproofing coating material, casting material, etc., by compounding a urethane prepolymer, a curing agent such as 3,3'-dichloro-4,4'- diaminodiphenylmethane (MOCA), etc. and a specific aromatic carboxylic acid. CONSTITUTION:The objective composition is prepared by compounding (A) a urethane prepolymer obtained by the reaction of tolylene diisocyanate (TDI) with a polyol with (B) MOCA and/or a precondensate of o-chloroaniline and HCHO, and (C) the compound of formula (R is H, OH or 1-20C alkyl) (e.g. benzoic acid, ethyl benzoate etc.). The amount of the active hydrogen in the component (B) is preferably 0.7-1.5 equivalent per 1 equivalent of the NCO group of TDI in the component (A), and the amount of the component (C) is 1-5wt% of the components (A)+(B).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fast-curing polyurethane composition, and more specifically, it is an excellent polyurethane composition that is mainly used as an FSTMER composition, for example, for flooring materials, waterproof coating materials, casting materials, sealing materials, etc. The present invention relates to a polyurethane composition having excellent physical properties and fast curing properties.

In recent years, demand for polyurethane has been increasing due to its excellent elongation, durability, elasticity, etc.

Conventional polyurethane-based materials generally have tolylene diisocyanate (hereinafter abbreviated as TD)-based urethane prepolymers as the main ingredient, and 8,8'-dichloro-4,4/-diaminodiphenylmethane (hereinafter abbreviated as MOCA), etc. A composition containing a crosslinking agent is used as a curing agent, and these are used by mixing them, but it takes a long period of time of at least 8 to more than 10 days at room temperature to develop sufficient strength. 1To promote the development of strength, 1For example, ■T
The temperature at the time of mixing the D-based prepolymer and M(')CA and/or at the time of the curing reaction between the two is increased. ■Adding a highly reactive TD emonomer to the TDI-based urethane prepolymer. ■4,4' highly reactive with cross-linking agent and 17
-Diaminosif 1-nylmethane (hereinafter abbreviated as DDM)
Methods such as using . Regarding these methods, the method (■) has the disadvantage of using a large amount of thermal energy, and the method (■) uses highly toxic TD and emomers, so safety and hygiene measures are required for the equipment, and the method (■) However, FiD DM has the drawback that its applications are severely limited because it is not sufficiently soluble in commonly used plasticizers for polyurethane, such as polypropylene glycol.

In view of this situation, the present inventors have conducted extensive studies on a new fast-curing polyurethane composition, and have found that it is possible to incorporate a specific crosslinking agent and a specific amount of a benzoic acid compound into the urethane prepolymer. The present invention was completed based on the discovery that this method is extremely effective.

That is, the present invention consists of (8) a main agent containing a urethane prepolymer obtained by the reaction of tolylene diisocyanate and a polyol; and (C) a curing agent containing an initial condensate of 20 alkyl group) is provided.

In the composition of the present invention, a urethane prepolymer obtained by reacting TI)T with a polyol, or a composition containing the same, is used as the main ingredient. For example, the urethane prepolymers include known urethane prepolymers obtained by the reaction of 2,4- and 2,6-) lylene diisocyanates with polyol compounds such as polyether polyols, polyester polyols, or polyol compounds obtained by the ring-opening reaction of tuctone compounds. Urethane prepolymers, in this case polyether polyols and 15
Teke 1 is a polyether polyol obtained by reacting a low molecular weight polyhydric alcohol such as ethylene glycol, 1,4-butanediol, glycerin, or trimethylolpropane with an alkylene oxide such as ethylene oxide or propylene oxide, and Examples of polyester polyols include polyhydric acids such as adipic acid, phthalic acid, isophthalic acid, and succinic acid, or their acid anhydrides, glycerin, 1,4-butanediol, propylene glycol, dipropylene glycol, It is a polyester polyol compound obtained by reaction with a polyol compound such as ethylene glycol. The urethane prepolymer used in the present invention is preferably liquid at the time of use, and if necessary, it may be used as a composition containing ethyl acetate, toluene, xylene, and cellosolve acetate-1'J(7). Ru.

The curing agent used in the composition of the present invention includes a crosslinking agent and
7te MOC! A and/or A contain an initial condensate of sochloroaniline and formaldehyde, and if necessary, at least one of a filler, a plasticizer, a pigment, a catalyst, etc.

As a crosslinking agent in the composition of the present invention, a commercially available product prepared by liquefying an initial condensate of MOCA6 or orthochloroaniline and formaldehyde with a plasticizer is used, such as Ihafukyuamine ML-100 (manufactured by Ihara Chemical Co., Ltd., MOOA 85% by weight, polyethylene glycol diamide). Penzoate 65 heavy i
t% H-like substance>, Iharakyuamine ML-520 (product of Ihara Chemical Co., Ltd., initial condensation product of orthochloroaniline and formaldehyde 50% by weight, polyether polyol-V
A liquid material consisting of 50% by weight of

Specific examples of fillers that may be used as necessary include calcifier, talc, clay, silicic anhydride (white carbon), carbon, bituminous materials, pine resin, and the like. Examples of plasticizers include liquid buffine, liquid coumaron resin, white tar, dioctyl phthalate, dibutyl phthalate, dioctyl adipate, polypropylene 2゛l recall, polyether polyols such as polyethylene glycol, terminal esterified products of polyether polyols, etc. Examples include plasticizers.

Catalysts include stannous oleate, stannous laurate, stannous acetate, lead octylate, zinc octylate, tin octoate, lead naphthenate, zinc naphthenate, manganese naphthenate, cobalt manganate, chloride. Ferric, stannic chloride, stannous chloride, antimony trichloride, triethylamine, N-methylmorpholine, [liethanolamine, triethylenediamine, N,N.

N', N'-tetramethyl-1,8-butanediamine,
Known materials such as 1,4-diaza-bicyclo[2,2,2)octane and acetylacetone are used, and among them, lead octylate and lead naphthenate are preferred.

The curing agent used in the present invention may further contain an antifoaming agent and a stabilizer.

In the polyurethane composition of the present invention, the base agent and curing agent preferably contain active hydrogen in the crosslinking agent in an amount of 0.7 to 1.5 equivalents, more preferably 0.8 equivalents per equivalent of isoneneto group in TDI. It is blended so that the amount is between 1.2 and 1.2 equivalents.

The compounds represented by the formula used in the present invention include:
Examples include benzoic acid, salicylic acid, methylbenzoic acid, ethylbenzoic acid, cumic acid, 1-butylbenzoic acid, nonylbenzoic acid, and the like. In the formula, the alkyl group bonded to the benzene nucleus is more preferably an alkyl group having 2 to 9 carbon atoms.

The content of the compound is preferably 1 to 5 weight percent, more preferably 1.5 to 8.5 weight percent, based on the total weight of the base agent and curing agent.

When the content is less than 1% by weight, the rapid curing properties targeted by the present invention cannot be obtained, and when the content is more than 5% by weight, the curing properties become extremely fast and workability and physical properties deteriorate. Preferably, the compound is incorporated into a curing agent.

The polyurethane composition according to the present invention can be used to obtain the desired elastomer with high efficiency using a two-component mixing and discharging device, and is particularly suitable for use as flooring materials and waterproofing agents.The present invention will be explained below using examples. . In the text, all parts are parts by weight. Example 1 Sumidur 0614 (product of Sumitomo Bayer Urethane Co., Ltd., free isocyanate content 8.7%, T D
100 parts of the reaction product of I and polyether polyol, 60 voids/25°C), and 100 parts of the crosslinking agent and 17 so
OCA 10 parts, liquid coumaron resin (Nippon Steel Chemical Co., Ltd. product,
A curing agent was obtained by mixing 90 parts of 20 boids/20°C) and 92 parts of leg strength Iv, and a composition obtained by uniformly mixing 8 parts of benzoic acid with this was mixed at room temperature (26°C) with a static mixer attached. The mixture was mixed using a liquid mixing and discharging machine, and the mixture was discharged onto a glass plate and cast into a sheet having a thickness of 2 nm. The mixed and discharged mixture turns into a gel after 4 minutes, and after 1 hour, the hardness (
After 51.2 hours, the hardness reached 53. Also, the strength after 2 hours is tensile strength (measured by J Engineering SA6021) 25kli/14,
Elongation rate (measured by JTSA6021) 600%, tear strength (measured by J-Tech 5A6021) 15ky/d
The strength was such that it could be used as a waterproof polyurethane coating material.

Comparative Example 1゜Casting was carried out on a glass plate in the same manner as in Example 1 except that 1 part of benzoic acid and 99 parts of Buccal were used in Example 1, and the hardness of the obtained sheet after 2 hours of dispensing was as follows: was less than &0, tack remained, and the strength was such that the sheet was destroyed even when pressed with fingers.

Example 2〉Polyflex PL-88 (product of Dai-Kogyo Seiyaku Co., Ltd., free isocyanate content 6.5%, composition consisting of a reaction product of TD resin and polyether polyol and some non-reactive organic solvents) as the main agent. Using 100 parts of buff-t-butylbenzoic acid, 6 parts of buff-t-butylbenzoic acid was uniformly added to a curing agent obtained by mixing 84 parts of Ihalacyuamine ML-520 (above), 16 parts of dioctyl phthalate, and 44 parts of charcoal. Using the composition obtained by mixing, these were discharged onto a glass plate using a two-component mixing and dispensing machine equipped with a static mixer.
The obtained sheet had a smooth surface, and the hardness after 2 hours of ejection was 68.
The physical properties after 2 hours measured by the method of
kti/d, elongation 800%1, tear strength 17kg/
a, and reached a strength that could be used as a polyurethane flooring material. After 8 days, the physical properties were 88 in hardness and 7 in tensile strength.
1 #/d, elongation 200%, tear strength 82 kg/ex. This shows good performance as a polyurethane flooring material.

Comparative Example 2 In an experiment conducted in the same manner as in Example 2, except that 16 parts of buff-t-butylbenzoic acid and 85 parts of charcoal were blended, the surface of the obtained sheet was coated with so-called Countless fine wrinkles called shrinkage occurred, and the physical properties after 2 hours were hardness of 72, tensile strength of 28, and 9/14. It had an elongation of 80% and a tear strength of 14/cII, and was inferior in physical properties.

Example 8゜Polyflex FL-87 (Dai-Kogyo Seiyaku Co., Ltd., free in V anate content 6.5%, reaction product of TD process and polyether polyol compound mainly composed of polyethylene glycol) 100 as main agent A composition obtained by uniformly mixing 8 parts of salicylic acid with a curing agent obtained by mixing 1 part and 40 parts of Ihafucuramine ML-520 (above), 20 parts of dioctyl phthalate, 89 parts of charcoal, and 1 part of an antifoaming agent. The product was discharged onto a glass plate at room temperature (20° C.) using a two-component mixing and dispensing machine equipped with a static mixer, and cast into a V-) having a thickness of 2H.

The sheet thus obtained had a smooth surface and was similar to Example 1.
The hardness of the sheet after 2 hours of discharge measured in the same manner as above was 76, the tensile strength was 68 to 97, the elongation was 2.60%, and the tear strength was 21 kq/ax. It had reached a strength sufficient to be used as wood. The strength of the sheet after 7 days was 96 in hardness and 110 kQ/c in tensile strength.
4. Elongation 180%, tension 9t, asa 56kIi/cIR
Te Atsuta.

Example 4 As a main ingredient, 100 parts of Polyflex WP-1 (manufactured by Dai-Kogyo Seiyaku Co., Ltd., free incyanate content 8.0%, reaction product of TD King and a polyether polyol compound mainly composed of polyethylene glycol), and liquid coumaron NL
A hardening agent obtained by mixing 74 parts of Nippon Steel Chemical Co., Ltd. -20 (manufactured by Nippon Steel Chemical Co., Ltd., Liquid Fushiriku Ron Resin), 18 parts of Inola A Yumin ML-100 (above), 7 parts of xylene, and 91 parts of charcoal was added to the curing agent obtained by mixing P- A composition obtained by uniformly mixing 10 parts of nonylbenzoic acid was discharged onto a glass plate at room temperature (20° C.) using a two-component mixing and dispensing machine equipped with a static mixer to a thickness of 2 MI.
It was cast onto a sheet of I.

The sheet thus obtained has a smooth surface.

The gelation time was 4 minutes. Moreover, the hardness of the sheet reached 45 after 2 hours of discharge. In addition, the tension after 7 days was 70 in hardness, 50 kli/al in tensile strength, 460% in elongation, and 22 to 9/3 in tear strength, demonstrating good performance as a fast-curing polyurethane resin coating waterproofing material. It was something that I had.

Procedural amendments □ 5. Showa 5q #-March 2nd 6゜Dear Director of the Board of Directors, 1981 Patent 1 younger brother 14d568 No. 2, 6 cup polyurethane thread composition 3 of the invention, amendment. Relationship with the case of patent applicant Address: 1.115 Kitahama 5-chome, Sue-ku, Osaka City Name:
(209) Sumitomo Chemical Co., Ltd. Densha Representative Takeshi Hijikata 4 Agent Address Sumitomo Chemical Co., Ltd. 5-115 Kitahama, Sakae-ku, Osaka Name Patent Attorney (6146) KiNkatsu EquipmenttMei)su7*- 3404 Contents of amendment in the title of the invention column of the specification In the third line of page 1 of the specification, the phrase "polyurethane-based composition" is amended to read "polyurethane-based composition."

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Claims (1)

[Scope of Claims] (g) A main component containing a urethane prepolymer obtained by the reaction of tolylene diisocyanate and a polyol. (g) A crosslinking agent, including 8,8'-dichloro-4,4-
A curing agent containing an initial condensate of diamidiphenylmethane and/or orthochloroaniline and formaldehyde, and fcl 1 to 5% by weight based on the total weight of the main agent and curing agent (wherein R is hydrogen) , representing a hydroxyl group or an alkyl group having a return number of 1 to 20).