JP2005054122A - Polyurethane hardenable composition and retarder composition for polyurethane - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyurethane hardenable composition having excellent hardenability without a lead type catalyst and permitting arbitrary adjustment of the pot life and a retarder composition permitting arbitrary adjustment of the pot life without adverse effects on the performance of a polyurethane hardenable composition. <P>SOLUTION: The polyurethane composition comprises (A) a compound having an isocyanate group, (B) an organic acid bismuth salt and (C) at least one compound selected from sulfonic acid and sulfuric ester type anionic surfactants. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polyurethane curable composition and a reaction retarder (hereinafter referred to as a retarder) composition for polyurethane, and is particularly suitably applied to a polyurethane curable composition and a polyurethane composition excellent in curability and workability. The present invention relates to a retarder composition.

  In general, as a polyurethane-based sealant, a sealant composed of a main agent containing a urethane prepolymer component having an isocyanate group at the terminal and a curing agent containing a polyol component having two or more hydroxyl groups, a catalyst, and other auxiliaries is known. Since both main component and curing agent components can be appropriately selected from various prepolymers and polyols and combined with various physical properties, they are used in a wide range of applications.

  As the curing catalyst, a lead-based catalyst such as lead organic carboxylate has been conventionally used. However, in recent years, the use of lead-based catalysts has been a problem from the viewpoint of environment and safety. Furthermore, lead-based catalysts have problems in workability such as variation in usable time. There has been a demand for the development of a polyurethane composition that exhibits excellent curability and workability without the use of.

  As a polyurethane composition not using a lead-based catalyst, Patent Document 1 contains a terminal isocyanate-containing urethane prepolymer, a polyol as a curing agent, and a mixture of bismuth organic carboxylate and other organic carboxylic acid metal salt as a curing catalyst. A polyurethane composition is disclosed. However, the composition described in Patent Document 1 has a problem of curability because the gel time of polyurethane is large and the curing speed is low.

Patent Document 2 discloses a two-component curable polyurethane composition comprising a main component containing a compound having an isocyanate group, an active hydrogen compound, an organic acid bismuth salt, a fatty acid alkali metal or fatty acid alkaline earth metal salt, and a basic compound. Things are disclosed. However, the polyurethane composition described in Patent Document 2 has a problem that it is difficult to adjust the pot life because the curing rate is rapidly changed according to the temperature and the addition amount while the curing rate is improved. .
JP 2001-89549 A JP 2003-40962 A JP 54-138058 A JP-A-10-324863 JP 2000-328040 A

  The present invention was made in view of the above-described problems of the prior art, and has a high curability without using a lead-based catalyst, and a polyurethane curable composition that can arbitrarily adjust the pot life, And it aims at providing the retarder composition which can adjust a pot life arbitrarily, without impairing the performance of a polyurethane curable composition.

  In order to solve the above problems, the polyurethane curable composition of the present invention comprises (A) a compound having an isocyanate group, (B) an organic acid bismuth salt, and (C) a sulfonic acid type anionic surfactant and a sulfate. It contains at least one compound selected from the group consisting of type anionic surfactants.

  The polyurethane curable composition of the present invention may further contain (D) an organic acid metal salt (excluding an organic acid bismuth salt).

  The polyurethane retarder composition of the present invention comprises at least one compound selected from the group consisting of a sulfonic acid type anionic surfactant and a sulfate ester type anionic surfactant as an essential component. To do.

  The polyurethane curable composition of the present invention has excellent curability without using a lead-based catalyst, and has been difficult to adjust not only in a good environment but also in high temperature, high humidity and the like so far. Even under conditions, the pot life can be arbitrarily adjusted to improve workability. By adding the polyurethane retarder composition of the present invention to the polyurethane curable composition, the curing can be arbitrarily delayed, and the pot life can be freely adjusted.

  Embodiments of the present invention will be described below, but various modifications can be made in addition to the description examples without departing from the technical idea of the present invention.

  The polyurethane curable composition of the present invention comprises (A) a compound having an isocyanate group, (B) an organic acid bismuth salt, and (C) a sulfonic acid type anionic surfactant and a sulfate type anionic surfactant. It contains at least one compound selected from the group.

  The component (A) compound having an isocyanate group used in the present invention can be an isocyanate compound used in an ordinary polyurethane curable composition, and is not particularly limited, but is a urethane prepolymer having an isocyanate group at the terminal. Is preferred. A component (A) may be used independently and may be used together 2 or more types.

  The urethane prepolymer is a reaction product of an isocyanate compound and a polyol, and any urethane prepolymer may be used as long as it can be used in a normal polyurethane curable composition.

  As the isocyanate compound, all known polyisocyanates used for the synthesis of urethane resins and the like can be used. Specifically, paraphenylene diisocyanate, tolylene diisocyanate (TDI), tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI), octadecyl diisocyanate, naphthalene diisocyanate (NDI), 4,4'-diphenylmethane diisocyanate Examples thereof include (MDI), isophorone diisocyanate (IPDI), p-MDI, triphenylmethane triisocyanate, and modified products thereof. Such polyisocyanate compounds may be used alone or in combination of two or more.

  Examples of the polyol used for producing the urethane prepolymer include polyether polyol, polyester polyol, and polymer polyol.

  Examples of the polyether polyol include polyether polyols such as polypropylene polyol (PPG) and polyethylene polyol (PEG).

  The polyester polyol is a condensate of the alcohols exemplified in the polyether polyol with polybasic carboxylic acids such as adipic acid, fumaric acid, maleic acid, and phthalic acid; castor oil, reaction of castor oil and ethylene glycol Examples thereof include a condensate of a hydroxycarboxylic acid such as a product and the polyhydric alcohol; a lactone polymer obtained by ring-opening polymerization of caprolactone, valerolactone, or the like with an appropriate polymerization initiator.

  Examples of the polymer polyol include those shown in Patent Documents 3 to 5. Specifically, the polyether polyol or the polyester polyol may contain ethylenic polymers such as acrylonitrile, styrene, and methyl (meth) acrylate. A polymer obtained by polymerizing a saturated compound can be used.

  These polyols may be used alone or in combination of two or more, but in any case, those having a weight average molecular weight of 400 to 10,000, particularly 1,000 to 5,000 are preferred. When used, well-balanced physical properties can be obtained.

  The urethane prepolymer is preferably obtained by reacting the above-described polyol with an isocyanate such that the NCO / OH ratio is 1.0 to 2.5, particularly 1.5 to 2.0.

  In the present invention, the component (B) organic acid bismuth salt used as a curing catalyst is not particularly limited, but organic bismuth organic carboxylate is preferable. As the organic bismuth carboxylate, bismuth octylate, bismuth neodecanoate, bismuth naphthenate, bismuth rosinate and the like are suitable.

  Although the compounding ratio of a component (B) is not specifically limited, It is 0.5-5.0 mass parts with respect to 100 mass parts of components (A), Especially it is 1.5-3.5 mass parts. This is preferable because it provides good curability while ensuring working time. The said organic acid bismuth salt may be used independently and may be used together 2 or more types.

  In the present invention, by using the component (C), the pot life can be appropriately adjusted depending on the blending amount. The component (C) is at least one compound selected from the group consisting of sulfonic acid type anionic surfactants and sulfate ester type anionic surfactants.

  Examples of the sulfonic acid type anionic surfactant include alkyl sulfonic acid (for example, polyoxyethylene alkyl sulfonic acid), alkyl aryl sulfonic acid (for example, alkyl benzene sulfonic acid, alkyl naphthalene sulfonic acid, etc.), sulfosuccinic acid, sulfosuccinic acid. Acid esters (for example, dialkylsulfosuccinic acid esters), paraffin sulfonic acids, α-olefin sulfonic acids, N-acyl sulfonic acids, and alkaline earth metal salts thereof (for example, calcium salts), alkali metal salts (for example, Sodium, potassium salt, etc.).

  Examples of sulfate ester type anionic surfactants include long-chain alcohol sulfates, alkyl ether sulfates (eg, polyoxyethylene alkyl ether sulfates), alkyl aryl ether sulfates (eg, polyoxyethylene alkylphenyl ether sulfates). Alkyl sulfates (eg, polyoxyalkyl sulfates), alkylaryl sulfates (eg, polyoxyalkylphenyl sulfates), alkylamide sulfates (sulfate esters of fatty acid alkylolamides), sulfated oils, And alkaline earth metal salts thereof (for example, calcium salts), alkali metal salts (for example, sodium salts, potassium salts, etc.), and the like.

  The mixing ratio of the component (C) is not particularly limited and can be appropriately selected as necessary. When an alkaline earth metal salt is used as the component (C), the amount of the component (A) is 100 parts by mass. 0.5 to 11.0 parts by mass is preferable, 1.0 to 5.5 parts by mass is more preferable, and 1.0 to 3.0 parts by mass is particularly preferable. When an alkali metal salt is used as the component (C), the amount is preferably 0.5 to 25.0 parts by mass, particularly preferably 1.0 to 20.0 parts by mass with respect to 100 parts by mass of the component (A). . When a component other than a metal salt is used as the component (C), the amount is preferably 0.1 to 10.0 parts by mass, more preferably 0.1 to 5.5 parts by mass with respect to 100 parts by mass of the component (A). Especially preferably, it is 0.5-2.0 mass parts. The component (C) may be used alone or in combination of two or more. When two or more types are used in combination, the combination is not particularly limited, and two or more types may be selected from sulfonic acid type anionic surfactants or sulfate ester type anionic surfactants. And a sulfate ester type anionic surfactant may be mixed and used.

  The blending method of component (C) is not particularly limited. For example, when the polyurethane curable composition of the present invention is used in a two-pack type, it may be used by being contained in a curing agent component, and may be added as a retarder when mixing the main component and the curing agent component. . Further, calcium carbonate or balloon treated with the component (C) may be added and used.

  In addition to the organic acid bismuth salt, the polyurethane curable composition of the present invention may further contain an organic acid metal salt (D) other than the organic acid bismuth salt as a curing catalyst. The organic acid metal salt other than the organic acid bismuth salt is not particularly limited, but an organic carboxylic acid metal salt is preferable. Examples of organic carboxylic acid metal salts include metal salts such as octylic acid, neodecanoic acid, naphthenic acid, and rosin acid, such as calcium, tin, titanium, zirconium, zinc, iron, and cobalt salts. And organic calcium carboxylates such as calcium neodecanoate are preferred.

  Although the mixture ratio of a component (D) is not specifically limited, 0.03-3.0 mass parts of a component (D) is preferable with respect to 100 mass parts of components (A), More preferably, 1.5-3. 0 parts by mass. These organic acid metal salts may be used alone or in combination of two or more.

  Furthermore, the polyurethane curable composition of the present invention can be used with a plasticizer added, but it is preferable that the polyurethane curable composition does not substantially contain a plasticizer. When a plasticizer is blended, the surface tack after curing is strong due to softening by an external additive, which gives rise to defects such as adhesion of wrinkles and dust. Moreover, when it hardens | cures under low temperature, a plasticizer may become a binder and hardening may become slow. In addition, the surface of a polyurethane sealant is usually applied on a daily basis, but the plasticizer in the sealant leaches out over time, causing discoloration of the painted surface, darkening, and adhesion of dust. What happens is a problem.

  Since the polyurethane curable composition of the present invention can obtain desirable physical properties without containing a plasticizer, the volume shrinkage of the cured product is small, and the transition of the plasticizer such as softening and discoloring the finished paint after curing ( Since the problem due to bleeding does not occur, the paintability can be further improved. Furthermore, if a plasticizer such as a phthalic acid plasticizer is not blended, adverse effects on the environment and the human body can be suppressed. The phrase “substantially containing no plasticizer” means that a compound imparting plasticity generally used as a plasticizer is not added. The volatile components of such compositions are usually 3% by weight or less.

  In addition to the components described above, the polyurethane curable composition of the present invention includes, as necessary, a plasticizer, a filler, a thixotropy imparting agent, a pigment, a dye, an anti-aging agent, an antioxidant, an antistatic agent, and a flame retardant. Ordinarily added additives such as adhesion promoters, dispersants, solvents, tackifiers, and foam inhibitors and auxiliary materials may be blended.

  Fillers can be organic or inorganic in various shapes, fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide. Calcium carbonate, magnesium carbonate, zinc carbonate; carbon black; inorganic balloons such as shirasu balloon, saran balloon, phenol balloon, and organic balloons; or these fatty acids and fatty acid ester treated products. The blending amount of the filler is preferably 150 to 250 parts by mass with respect to 100 parts by mass of the urethane prepolymer because good physical properties and workability can be obtained. These fillers may be added in an appropriate amount within the curing agent component.

  Examples of the antioxidant include butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), diphenylamine, phenylenediamine, and triphenyl phosphite. Examples of the antiaging agent include hindered phenol compounds, benzotriazole compounds, hindered amine compounds, and the like.

  The pigment includes an inorganic pigment and an organic pigment, and examples of the inorganic pigment include titanium dioxide, zinc oxide, ultramarine, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate, and the like. Examples of organic pigments include azo pigments and copper phthalocyanine pigments.

  The curable composition of the present invention is preferably used in a two-pack type. In this case, as the polyol used as a curing agent, polyether polyols such as polypropylene polyol (PPG) and polyethylene polyol (PEG), and the above-mentioned The same polyol as used as a raw material for the urethane prepolymer can be used. The weight average molecular weight of such a polyol is preferably from 400 to 12,000, particularly preferably from 3000 to 7000, since balanced physical properties can be obtained. Moreover, the curable composition of this invention can also be used as a one-component type.

  The polyurethane retarder composition of the present invention contains at least one compound selected from the group consisting of the sulfonic acid type anionic surfactant and sulfate ester type anionic surfactant as an essential component. . The polyurethane retarder composition of the present invention can be added arbitrarily according to the environment and needs to adjust the pot life.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, it goes without saying that the present invention should not be construed as being limited to these examples.

(Examples 1 to 10 and Comparative Example 1)
As shown in Table 1, urethane prepolymer (NCO% 3.0) was used as the main agent. Moreover, what mixed PPG (molecular weight 5000), calcium carbonate, and bismuth octylate (Bi25%) (* 1) with the compounding ratio shown in Table 1 was used as a hardening | curing agent.

The compounding amounts of the compounding substances in Table 1 are shown in parts by mass, and (* 1 to * 5) are as follows.
* 1: Product name “Pucat 25”, manufactured by Nippon Chemical Industry Co., Ltd. * 2: Product name “Taika Power BC2070M-A”, manufactured by Teika Co., Ltd. * 3: Product name “Emar 270J”, manufactured by Kao Corporation * 4: Product name “Neoperex GS”, manufactured by Kao Corporation * 5: Product name “Pucat Ca-5B”, manufactured by Nippon Chemical Industry Co., Ltd.

1. Measurement of pot life Under the conditions shown in Table 2, the sulfonic acid type anionic surfactant [Examples 1 to 6: dodecyl] as the main agent and component (C) with respect to the curing agent according to the blending ratio shown in Table 1 Calcium benzenesulfonate (* 2), Examples 9 and 10: Dodecylbenzenesulfonic acid (* 4)] or sulfate ester type anionic surfactant [Examples 7 and 8: Sodium polyoxyethylene lauryl ether sulfate (* 3) )], And as a component (D), a mixture of calcium neodecanoate and calcium octylate (* 5) (Example 6) was added and then mixed for 15 minutes with a dedicated mixer to obtain a curable composition. .

  The time during which the obtained curable composition was sucked with a caulking gun and pushed out was measured every 30 minutes. The measurement conditions and the results are shown together in Table 2 (shown as pot life 1).

  The obtained curable composition was filled in a container having a diameter of 50 mm and a depth of 5 mm, and the time until a thin film was formed on the surface was measured every 5 minutes. The measurement conditions and the results are shown together in Table 2 (shown as pot life 2).

2. Measurement of Hardness Each component was mixed at 20 ° C. according to the blending ratio shown in Table 1, and then cured at 20 ° C. for 1 week and at 50 ° C. for 1 week to obtain a sample. About the obtained sample, based on JIS K6253 type E, hardness was measured using the Asker C-type hardness meter. The results are shown in Table 2.

  As shown in Table 2, the curable compositions of Examples 1 to 10 have sufficient hardness, and the pot life is extended as compared with the curable composition of Comparative Example 1. In particular, the Examples In the curable compositions of 1 to 5, the pot life was extended depending on the amount of calcium dodecylbenzenesulfonate.

The polyurethane curable composition of the present invention has excellent curability without using a lead-based catalyst, and has been difficult to adjust not only in a good environment but also in high temperature, high humidity and the like so far. Even under conditions, the pot life can be arbitrarily adjusted and workability can be improved, so that it is suitably used as a polyurethane sealing material particularly used in the fields of construction, civil engineering, automobile production and the like. By adding to the polyurethane curable composition, the polyurethane retarder composition of the present invention does not impair the performance of the polyurethane curable composition, and not only in a good environment, but also at high temperature, high humidity, etc. Even under conditions that have been difficult to adjust, the curing can be delayed arbitrarily and the pot life can be adjusted freely, so it is used especially in the fields of architecture, civil engineering, and automobile manufacturing. It is suitably used as a retarder composition for polyurethane sealing materials.

Claims (3)

(A) a compound having an isocyanate group,
A polyurethane comprising (B) an organic acid bismuth salt and (C) at least one compound selected from the group consisting of a sulfonic acid type anionic surfactant and a sulfate ester type anionic surfactant. Curable composition.   The polyurethane curable composition according to claim 1, further comprising (D) an organic acid metal salt (excluding an organic acid bismuth salt). A polyurethane retarder composition comprising as an essential component at least one compound selected from the group consisting of a sulfonic acid type anionic surfactant and a sulfate ester type anionic surfactant.