JP2006249344A - Two-pack type urethane composition, process for producing the same and process for producing urethane prepolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a two-pack type urethane composition that is excellent in storage stability and is capable of suppressing curing retardation, foaming and the like. <P>SOLUTION: The two-pack type urethane composition comprises a main agent comprising a urethane prepolymer and an organic acid bismuth, and a curing agent comprising an active hydrogen-containing compound. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a two-component urethane composition, a method for producing the same, and a method for producing a urethane prepolymer.

  Conventionally, in a two-pack type urethane composition having a polyisocyanate (urethane prepolymer) as a main component and an active hydrogen-containing compound such as a polyol as a reaction component of a curing agent, lead organic carboxylate is generally widely used as the curing catalyst. It is used. However, there is a concern that lead has an adverse effect on the environment and the human body, and a two-component urethane composition containing no lead is desired.

Therefore, a lead-free two-component urethane composition in which bismuth octylate and calcium octylate are blended instead of organic acid lead has been proposed (see Patent Document 1).
Patent Document 2 describes a two-component polyurethane sealing material composition that is excellent in surface / deep part curability, has good coatability, has excellent non-foaming properties, and does not adversely affect the environment. Has been. This composition contains a main agent containing a urethane prepolymer (A) and a curing agent containing a polyether polyol (B), and bismuth rosin acid as a curing catalyst with respect to 100 parts by weight of the urethane prepolymer (A). It contains 0.6 to 4.7 parts by weight, 0.03 to 1 part by weight of calcium octylate and / or calcium neodecanoate as a curing co-catalyst, and 0.003 to 0.3 parts by weight of organic acid tin.

JP 2001-89549 A JP 2003-165968 A

However, bismuth organic acid used as a curing catalyst in the two-component urethane compositions described in Patent Documents 1 and 2 gradually becomes active due to the influence of moisture contained in the components of the curing agent and humidity in the atmosphere. Loss, delay in curing, foaming, etc. may occur.
Therefore, an object of the present invention is to provide a two-component urethane composition that is excellent in storage stability and can suppress curing delay, foaming, and the like.

As a result of intensive studies, the present inventor has found that deactivation of bismuth of organic acid can be avoided by blending bismuth of organic acid used as a curing catalyst on the main agent side containing a urethane prepolymer. This is because the polyol used as a raw material during the production of the urethane prepolymer is usually dehydrated, the water remaining in the system is consumed by the polyisocyanate compound, and the urethane prepolymer that is usually reactive with water is hermetically sealed. This is probably because it is stored in a high-container container and is not easily affected by moisture in the atmosphere. Moreover, in such a sealed container, the increase in the molecular weight of the urethane prepolymer by bismuth organic acid does not proceed. As a result, it was found that a two-component urethane composition having excellent storage stability and capable of suppressing curing delay, foaming and the like can be obtained.
By the way, the conventional general urethane prepolymer mixes an excess polyisocyanate compound (namely, an excess isocyanate group with respect to a hydroxyl group) with respect to a polyol compound, and is 6 to 72 hours at 50 to 100 ° C. under normal pressure. It is obtained by reacting to some extent. The present inventor has found that when bismuth organic acid is added during the production of the urethane prepolymer, it self-heats to about 60 to 85 ° C. without heating and the reaction is completed in about 30 to 60 minutes. .
The present inventor completed the present invention based on these findings.

  That is, the present invention provides the following (1) to (9).

(1) a main agent containing a urethane prepolymer and bismuth organic acid;
A two-component urethane composition comprising a curing agent containing an active hydrogen-containing compound.

  (2) The two-component urethane material composition according to (1), wherein the bismuth organic acid is bismuth organic carboxylate and / or bismuth resinate.

  (3) The two-component urethane composition according to (2), wherein the organic bismuth carboxylate is at least one selected from the group consisting of bismuth octylate, bismuth 2-ethylhexylate and bismuth neodecanoate.

  (4) The two-component urethane composition according to (2) or (3), wherein the bismuth resinate is bismuth abietic acid.

  (5) The two-component urethane composition according to any one of (1) to (4), wherein the curing agent further contains an organic acid calcium.

  (6) The two-component urethane composition according to (5), wherein the organic acid calcium is organic calcium carboxylate and / or calcium resinate.

  (7) The two-component urethane composition according to (6), wherein the organic calcium carboxylate is at least one selected from the group consisting of calcium octylate, calcium 2-ethylhexylate and calcium neodecanoate.

(8) A method for producing the two-component urethane composition according to any one of (1) to (7) above,
Reacting a polyol compound and an isocyanate group-containing compound in the presence of an organic acid bismuth to produce a main agent containing the urethane prepolymer and the organic acid bismuth;
A method for producing a two-component urethane composition comprising a step of producing a curing agent containing the active hydrogen-containing compound.

  (9) A method for producing a urethane prepolymer, in which a polyol compound and an isocyanate group-containing compound are reacted in the presence of bismuth organic acid to obtain a urethane prepolymer.

The two-component urethane composition of the present invention has excellent storage stability and can suppress curing delay, foaming, and the like.
Further, according to the method for producing a urethane prepolymer of the present invention, it is possible to produce a urethane prepolymer in a short period of time without being time-consuming for heating.

Hereinafter, the present invention will be described in detail.
The two-component urethane composition of the present invention (hereinafter also referred to as “the composition of the present invention”) includes a main agent containing a urethane prepolymer and an organic acid bismuth and a curing agent containing an active hydrogen-containing compound. This is a two-component urethane composition.

First, the main ingredient of the composition of the present invention will be described.
The main agent contains a urethane prepolymer and an organic acid bismuth.
The urethane prepolymer used in the present invention is a urethane prepolymer having an active isocyanate group, that is, an unblocked isocyanate group in the molecule. In addition, as long as the effect of this invention is not impaired, a part of isocyanate group may be blocked. When there is no blocked isocyanate group, there is little difference in physical properties between moisture curing and heat curing.

  Such a urethane prepolymer is not particularly limited, and a urethane prepolymer obtained from a polyol compound and an isocyanate group-containing compound can be used.

  The polyol compound used for the urethane prepolymer is an alcohol obtained by substituting a plurality of hydrogen atoms of a hydrocarbon with a hydroxy group. For example, a product obtained by addition polymerization of at least one alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran to an active hydrogen-containing compound having two or more active hydrogens in the molecule can be given.

Examples of the active hydrogen-containing compound having two or more active hydrogens in the molecule include polyhydric alcohols, amines, alkanolamines, and polyhydric phenols.
Specific examples of the polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, diethylene glycol, glycerin, hexanetriol, trimethylolpropane, and pentaerythritol.
Examples of amines include ethylenediamine and hexamethylenediamine.
Examples of alkanolamines include ethanolamine and propanolamine.
Examples of polyhydric phenols include resorcin, bisphenols, and the like.

Specific examples of the polyol compound include polyether polyols such as polytetramethylene glycol, polyethylene glycol, polypropylene glycol, polyoxypropylene glycol, and polyoxybutylene glycol; polyolefin polyols such as polybutadiene polyol and polyisoprene polyol; adipate Preferable examples include polyester-based polyols such as lactone-based polyols; lactone-based polyols and castor oil.
These may be used alone or in combination of two or more.

  The polyol compound preferably has a number average molecular weight of about 500 to 12000, and more preferably about 2000 to 6000.

As the isocyanate group-containing compound used in the urethane prepolymer, various compounds used in the production of ordinary polyurethane resins can be used. Specifically, for example, TDI such as 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate; MDI such as diphenylmethane-4,4′-diisocyanate; tetramethylxylylene diisocyanate (TMXDI), trimethylhexamethylene Diisocyanate (TMHMDI), 1,5-naphthalene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), triphenylmethane triisocyanate, norbornane skeleton And diisocyanate (NBDI) having a modified form thereof, and modified products thereof.
These may be used alone or in combination of two or more.
Of these, TDI and MDI are preferred because they are inexpensive and easily available.

  The ratio of the number of isocyanate groups of the isocyanate group-containing compound to the number of hydroxy groups of the polyol compound (NCO / OH) is the ratio of mixing the polyol compound and the isocyanate group-containing compound in the production of the urethane prepolymer. It is preferably 0 or more, more preferably 1.5 to 2.0.

The production of the urethane prepolymer used in the present invention is performed, for example, by mixing a polyol compound and an isocyanate group-containing compound at a predetermined quantitative ratio in the same manner as a normal urethane prepolymer, and usually stirring at 60 to 100 ° C. under normal pressure. Can be done.
Moreover, the method of manufacturing a urethane prepolymer by adding organic acid bismuth at the time of manufacture of a urethane prepolymer is mentioned preferably. In addition, the time of manufacture of a urethane prepolymer means the time of starting the reaction with the said polyol compound and an isocyanate group containing compound, or the time of reacting. In particular, since the reaction time is shortened and the amount of heat applied from the outside can be reduced by reaction heat, it is preferable that bismuth organic acid is added at the start of the reaction. Specifically, there is a method for producing a urethane prepolymer in which a polyol compound and an isocyanate group-containing compound are reacted in the presence of bismuth organic acid to obtain a urethane prepolymer (hereinafter, this production method is referred to as “present”. The method for producing the urethane prepolymer of the invention ").

According to the method for producing a urethane prepolymer of the present invention, self-heating occurs at about 60 to 85 ° C. without heating, and the reaction is completed in about 30 to 60 minutes. The time required for heating can be shortened, and the cost required for heating can be reduced. Moreover, since the obtained mixture contains a urethane prepolymer and bismuth organic acid, it can be used as it is as the main component of the composition of the present invention. Furthermore, since the production of the urethane prepolymer is performed in an environment where moisture is blocked using a sufficiently dried polyol compound and isocyanate group-containing compound, the organic acid bismuth does not react with moisture and deactivate. . Therefore, the obtained composition of the present invention is excellent in storage stability, and further can suppress curing delay and foaming caused by the deactivation of bismuth organic acid.
In addition, in the composition of this invention, after manufacturing a urethane prepolymer by the method mentioned above, a predetermined amount of organic acid bismuth can be added and it can also be set as a main ingredient.

Specifically, the method for producing the urethane prepolymer of the present invention is, for example, putting a sufficiently dried polyol compound into a dry reaction vessel, adding a predetermined amount of bismuth octylate, and at room temperature for about 30 minutes. Stir. Next, TDI is added in such an amount that NCO / OH becomes 1.0 or more and stirred at room temperature for about 30 to 60 minutes.
The reaction vessel used for the production of the urethane prepolymer of the present invention is not particularly limited, but a glass or metal sealable container that can protect the reactant and the catalyst from the intrusion of external moisture is preferable.

Specific examples of bismuth organic acid used in the present invention include bismuth organic carboxylate and bismuth resinate (bismuth rosinate).
More specifically, examples of the organic carboxylic acid bismuth include bismuth salts such as octylic acid, 2-ethylhexylic acid, neodecanoic acid, and neododecanoic acid. Among these, bismuth octylate, bismuth 2-ethylhexylate and bismuth neodecanoate are preferable.
Examples of bismuth resin acid include bismuth salts of alicyclic organic acids such as abietic acid, neoabietic acid, d-pimalic acid, iso-d-pimalic acid, podocarpic acid, benzoic acid, cinnamic acid, and p-oxycinnamic acid. Examples thereof include bismuth salts of aromatic organic acids such as acids. Among these, bismuth abietic acid is preferable.
These may be used alone or in combination of two or more.
In order to make the organic acid bismuth liquid, it is usually diluted with an organic acid such as octylic acid, 2-ethylhexylic acid or neodecanoic acid, a plasticizer such as polyol, a solvent such as terpene or toluene. .

  The addition amount of the organic acid bismuth may be appropriately adjusted and is not particularly limited. For example, as will be described later, when the curing agent contains organic acid calcium, the amount of organic acid bismuth added can be reduced. A preferable addition amount of bismuth organic acid is 0.01 to 10 parts by mass with respect to 100 parts by mass of the urethane prepolymer. Within this range, the effects of the present invention can be sufficiently exerted, and the pot life is not shortened because the curing rate is too high. From the point which is excellent by this characteristic, 0.1-5 mass parts is more preferable, and 0.1-3 mass parts is still more preferable.

Next, the curing agent of the composition of the present invention will be described.
The curing agent of the composition of the present invention contains an active hydrogen-containing compound.
As an active hydrogen containing compound, what was illustrated as a raw material of the urethane prepolymer mentioned above can be mentioned, for example, Among these, a polyol compound is preferable. In particular, polypropylene glycol (PPG) is preferably used. In addition to the polyether polyol, a polyester polyol may be used as a reaction component of the curing agent.

In addition to the active hydrogen-containing compound, the curing agent preferably further contains organic acid calcium as a curing promoter. When the curing agent contains organic acid calcium, the curing rate of the composition of the present invention can be increased, the surface / deep part curability is excellent, and the amount of the bismuth organic acid added can be reduced. Moreover, the high modulus of the hardened | cured material which generate | occur | produces by using many organic acid bismuth can be suppressed, and also a pot life can be optimized.
Specific examples of the organic acid calcium include organic calcium carbonate and resin acid calcium (calcium rosinate).
More specifically, examples of calcium organic carboxylate include calcium salts such as octylic acid, 2-ethylhexylic acid, neodecanoic acid, neododecanoic acid and the like. Among these, calcium octylate, calcium 2-ethylhexylate and calcium neodecanoate are preferable.
Examples of calcium resinate include calcium salts of alicyclic organic acids such as abietic acid, neoabietic acid, d-pimalic acid, iso-d-pimalic acid, podocarpic acid, benzoic acid, cinnamic acid, and p-oxycinnamic acid. Examples thereof include calcium salts of aromatic organic acids such as acids. Among these, calcium abietate is preferable.
These may be used alone or in combination of two or more.
The organic acid calcium is usually diluted with an organic acid such as octylic acid, 2-ethylhexylic acid or neodecanoic acid, a plasticizer such as polyol, or a solvent such as terpene or toluene in order to make it liquid. .

  The amount of organic acid calcium added may be appropriately adjusted and is not particularly limited. The preferable amount of organic acid calcium added is 0.01 to 20 parts by mass with respect to 100 parts by mass of the urethane prepolymer. Within this range, the effects of the present invention can be sufficiently exerted, and the pot life is not shortened because the curing rate is too high. From the point which is excellent by this characteristic, 0.1-10 mass parts is more preferable.

  Moreover, it is preferable that the said hardening | curing agent contains organic acid tin further. In the case of containing an organic acid tin, since it is more excellent in surface / deep part curability, it is not delayed in curing, tack is hardly left, excellent in coating property and non-foaming property can be improved.

  Specific examples of the organic acid tin include, for example, tin octylate, dioctyltin dilaurate, dibutyltin dilaurate, acetylacetonatotin, dioctyltin dineodecanoate, etc., among which tin octylate, dioctyltin dilaurate Is preferable because it has stability as a catalyst and is excellent in surface curability.

  The amount of organic acid tin added is not particularly limited as long as it is appropriately adjusted according to the relationship with other components. The preferable addition amount of organic acid tin is 0.0001 to 10 parts by mass with respect to 100 parts by mass of the urethane prepolymer. Within this range, the effects of the present invention can be sufficiently exerted, and the curing time is not so fast that the pot life is not shortened. From the point which is excellent by this characteristic, 0.003-3 mass parts is more preferable.

  The composition of the present invention includes, in addition to the above-mentioned components, a filler, a thixotropy imparting agent, a pigment, a dye, an anti-aging agent, an antioxidant, an antistatic agent, a flame retardant, You may contain additives, such as an adhesion imparting agent and a dispersing agent. These additives can be included in the main agent and / or curing agent as required.

  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, these fatty acids, fatty acid ester treated products, and the like. The blending amount of the filler is preferably 100 to 500 parts by mass with respect to 100 parts by mass of the urethane prepolymer because good physical properties and workability can be obtained.

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.

  Pigments include inorganic pigments and organic pigments. Carbon black, titanium dioxide, zinc oxide, ultramarine, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum and other metal hydrochlorides, sulfuric acid A salt, an oxide, a hydroxide, etc. are mentioned. Examples of organic pigments include azo pigments and copper phthalocyanine pigments.

The production method of the two-component urethane composition of the present invention is the main agent containing the urethane prepolymer and the organic acid bismuth by adding the organic acid bismuth during the production of the urethane prepolymer and producing the urethane prepolymer. And a step of producing a curing agent containing the active hydrogen-containing compound. Specifically, a step of producing a main agent containing the urethane prepolymer and bismuth organic acid by reacting a polyol compound and an isocyanate group-containing compound in the presence of bismuth organic acid, and the active hydrogen-containing compound And a step of producing a curing agent containing
The process which manufactures a main ingredient is performed similarly to the manufacturing method of the urethane prepolymer of this invention mentioned above.
Moreover, the process of manufacturing a hardening | curing agent mixes the said active hydrogen containing compound manufactured by the well-known method, or the commercially available said organic acid calcium as needed, various additives, and fully disperse | distributes it using a stirrer etc. It is a process.

  According to the method for producing the composition of the present invention, in the step of producing the main agent, self-heating occurs without heating to about 60 to 85 ° C., and the reaction is completed in about 30 to 60 minutes. Compared to the case where bismuth organic acid is not added, the time required for production is shortened, and the cost can be reduced. Moreover, since the obtained mixture contains a urethane prepolymer and bismuth organic acid, it can be used as it is as the main component of the composition of the present invention. Furthermore, since the production of a urethane prepolymer is usually performed in an environment where moisture is blocked using a sufficiently dried polyol compound and isocyanate group-containing compound, the organic acid bismuth may react with moisture and deactivate. Absent. Therefore, the obtained composition of the present invention is excellent in storage stability, and further can suppress curing delay and foaming caused by the deactivation of bismuth organic acid.

In a conventional two-component urethane composition using lead organic carboxylate, the lead organic carboxylate is blended on the curing agent side. The reason is that when lead organic carboxylate is blended on the main agent side, curing of the urethane prepolymer proceeds and storage stability is significantly impaired. Further, in the two-pack type urethane composition using bismuth organic acid instead of organic carboxylate described in Patent Document 1 and Patent Document 2, bismuth organic acid is blended on the curing agent side. .
Since the composition of the present invention contains bismuth organic acid on the main agent side, the curing of the urethane prepolymer does not proceed due to the presence of bismuth organic acid, and the organic acid bismuth is deactivated by moisture present in the system. As a result, the storage stability is excellent, and further, curing delay, foaming, and the like caused by deactivation of bismuth organic acid can be suppressed.
Moreover, when bismuth organic acid is added at the time of manufacture of a urethane prepolymer, it does not require the effort of heating, can be manufactured in a shorter time, and cost can be reduced.
In addition, the composition of the present invention can increase the curing rate of the composition of the present invention when the curing agent contains calcium organic acid, has excellent surface / deep curability, and further includes the addition of bismuth organic acid. The amount can be reduced. Moreover, the high modulus of the hardened | cured material by organic acid bismuth can be suppressed, and also a pot life can be optimized.
In addition, the composition of the present invention, when the curing agent contains an organic acid tin, is more excellent in surface / deep part curability, so that it does not cause curing delay, hardly remains tack, has excellent paintability, and is non-foaming. Can also be improved.

  Since the composition of the present invention has excellent properties as described above, it is suitably used for sealing materials, waterproofing materials, adhesives, paints, flooring materials, casting materials, and the like. In particular, it is suitably used as a sealing material because it has a low modulus and has a long pot life.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
<Manufacture of urethane prepolymer (main agent)>
Example 1a
In a dried flask, bifunctional polypropylene glycol (Excenol 1020, number average molecular weight 1000, manufactured by Asahi Glass Co., Ltd., hereinafter referred to as “EXL1020”) 200 g, bifunctional polypropylene glycol (Exenol 2020, number average molecular weight 2000, Asahi Glass Co., Ltd.) Manufactured, hereinafter referred to as “EXL2020”) 200 g, trifunctional polypropylene glycol (Exenol 4030, number average molecular weight 4000, manufactured by Asahi Glass Co., Ltd., hereinafter referred to as “EXL4030”) is added, and the mixture is stirred under vacuum at 110 ° C. for 5 hours. , Dehydrated. Next, 169.5 g of TDI (Cosmonate T80, manufactured by Mitsui Takeda Chemical Co., Ltd.) was added and stirred at room temperature (20 ° C.) for 30 minutes. Thereafter, 16.0 g of a mineral terpene / octylic acid mixed solution (Neostan U660, manufactured by Nitto Kasei Co., Ltd., hereinafter referred to as “U660”) containing 3% by mass of bismuth octylate as the amount of bismuth metal was added, and room temperature (20 As shown in Table 2 below, heat was generated and the temperature reached 77 ° C. 1 minute after the start of stirring, and NCO% was 3.29 after 30 minutes and 3 minutes after 60 minutes. .21. Since the theoretical NCO% of the urethane prepolymer obtained by the above composition is 3.21, it was found that the reaction was almost completed after 60 minutes. The mixture of urethane prepolymer and bismuth octylate 110 minutes after the start of stirring thus obtained was used as the main agent.
Next, a part of the main agent was dispensed into a dry glass bottle, sealed with nitrogen gas, and sealed, and heated to 60 ° C. and held for 3 days, the NCO% was 3.19.
From the results shown in Table 2, it was found that the reaction was almost completed in 30 to 60 minutes after TDI was added and stirring was started.
Further, it is considered that there is no decrease in NCO% during storage and no significant increase in viscosity.

(Examples 2a and 3a)
Each component shown in the following Table 1 was mixed with the composition (g) shown in Table 1, and a urethane prepolymer was produced in the same manner as in Example 1a to obtain a main agent.

Example 4a
To the dried flask, 200 g of EXL1020, 200 g of EXL2020, and 600 g of EXL4030 were added, stirred under vacuum at 110 ° C. for 5 hours, dehydrated, and cooled to 50 ° C. Next, 169.5 g of TDI (Cosmonate T80, manufactured by Mitsui Takeda Chemical Co., Ltd.) was added, stirred for 30 minutes, and further stirred at 80 ° C. for about 27 hours to produce a urethane prepolymer. Here, it was confirmed that the NCO% substantially coincided with the theoretical value of 3.21. Thereafter, 16.0 g of U660 was added, and the mixture was stirred and dispersed uniformly for 30 minutes to obtain a main agent.

(Example 5a)
8000 g of EXL4030 that had been dehydrated by vacuum stirring at 110 ° C. for 5 hours in a dry flask was weighed into a dry 18 L can, sealed with nitrogen gas, sealed, and then cooled to room temperature.
Next, 1000 g of TDI (Cosmonate T80, manufactured by Mitsui Takeda Chemical Co., Ltd.) was added and sealed, and then installed in a gyro mixer (manufactured by COROB) and stirred at a stirring speed of 90 rpm for 5 minutes.
Next, 117.8 g of U660 (bismuth octylate) was added and stirred for 5 minutes at a stirring speed of 90 rpm.
Then, it left still at room temperature for 10 hours. The NCO% at that time was 2.53, and the viscosity was measured using an E-type viscometer, and it was 15.29 Pa · s (20 ° C.). A mixture of the urethane prepolymer and bismuth octylate thus obtained was used as a main agent.
Next, a part of the main agent was dispensed into a dry glass bottle, sealed with nitrogen gas, sealed, and allowed to stand at 60 ° C. for 3 days. The NCO% at that time was 2.51, and the viscosity was measured with an E-type viscometer and found to be 16.04 Pa · s (20 ° C.). From this result, it was found that the obtained urethane prepolymer was excellent in storage stability.
In addition, the said gyro mixer is a mixer stirred by the biaxial rotation of top and bottom rotation and autorotation rotation.

(Comparative Example 1a)
A urethane prepolymer was produced in the same manner as in Example 4a, except that bismuth octylate (U660) was not added, and used as the main agent.

(Comparative Example 2a)
To the dried flask, 8000 g of EXL4030 was added and dehydrated by vacuum stirring at 110 ° C. for 5 hours. Next, 1000 g of TDI (Cosmonate T80, manufactured by Mitsui Takeda Chemical Co., Ltd.) was added and stirred for 30 minutes, then heated to 80 ° C. and stirred for about 24 hours. The urethane prepolymer thus obtained was used as the main agent.
As shown in Table 3 below, the NCO% 30 minutes after the start of stirring was 5.35, and the temperature was raised to 80 ° C. and 21 hours later, the NCO% was 2.58. The mixture was further stirred, and the NCO% after 24 hours was 2.55. The theoretical NCO% of the urethane prepolymer obtained by the above composition is 2.54.
Next, a part of the main agent was dispensed into a dry glass bottle, sealed with nitrogen gas, and then sealed and heated to 60 ° C. and held for 3 days, the NCO% was 2.53. .

The components shown in Table 1 are as follows.
-Bismuth neodecanoate: prototype, manufactured by Nippon Chemical Industry Co., Ltd.
-Bismuth abietate: Pucat B-3, manufactured by Nippon Chemical Industry Co., Ltd.

  As is clear from the results shown in Tables 2 and 3 above, Comparative Example 2a requires about 24 hours from the start of stirring after adding TDI to the end of the reaction. In 1a, the reaction was almost completed 30 to 60 minutes after the addition of TDI. Therefore, when the urethane prepolymer was produced in the presence of bismuth octylate, the reaction rate was remarkably improved as compared with the case where bismuth octylate was not added.

<Preparation of two-component urethane composition>
(Examples 1-5 and Comparative Examples 1-2)
(initial)
Curing agents obtained by mixing the main ingredients of Examples 1a to 5a and Comparative Examples 1a to 2a shown in Table 1 above and the components shown in Table 4 below with the composition (g) shown in Table 4 The mixture was sufficiently mixed using a stirrer to obtain a sealing material composition (initial).

(After storage)
The main agents of Examples 1a to 5a and Comparative Examples 1a to 2a shown in Table 1 above and the curing agent obtained by mixing with the composition (g) shown in Table 4 are each accelerated accelerated at 60 ° C for 3 days. Then, the main agent and the curing agent were sufficiently mixed using a stirrer to obtain a sealing material composition (after storage).
About each obtained sealing material composition after the initial stage and after storage, foamability, internal curability, physical properties and adhesiveness were evaluated by the following methods.
The results are shown in Table 5.

<Foaming test>
Each obtained sealing material composition was left in a constant temperature and humidity chamber at 30 ° C. and 80% RH for 7 days, and then the surface state was observed and evaluated as follows.
“◯” indicates that no foaming was observed on the surface of the sealing material, “△” indicates that foaming of less than 3 mm in diameter was observed on the surface of the sealing material, and foaming of 3 mm or more diameter was observed on the surface of the sealing material. The result was taken as “×”.

<Internal curing test>
Each obtained sealing material composition was placed on an aluminum channel of 30 mm × 15 mm × 100 mm, and the surface smoothed with a spatula was cured for 2 days in an environment of 20 ° C. and 65% RH, and then a cured sealing material was used. The mold was removed from the aluminum channel and the internal curability was evaluated.
What was hardened | cured entirely was set as "(circle)", and the surface or the inside was uncured was set as "x".

<Tensile property test>
According to JIS A1439-2004, each sealing material composition was cured at 23 ° C. and 50% RH for 3 days, and further cured at 50 ° C. for 4 days to prepare an H-type specimen. As an aluminum piece used for this test body, a primer (Primer No. 30, manufactured by Yokohama Rubber Co., Ltd.) was applied in advance to the portion that was in contact with the sealing material, and air-dried for 30 to 60 minutes after application.
The specimen prepared as described above was pulled at a speed of 50 mm / min, 50% modulus (M ₅₀ ) [N / cm ² ], 150% modulus (M ₁₅₀ ) [N / cm ² ], breaking strength (T _B ) [N / cm ² ] and elongation at break (E _B ) [%] were measured.

<Adhesion test>
According to the state of the sealing material attached to the test piece subjected to the tensile test, the state of failure is classified into CF (cohesive failure), TCF (thin layer cohesive failure), and AF (interfacial debonding), and the cohesive failure of each specimen. The ratio of the area occupied by the (CF) state (CF%) is shown.

The components shown in Table 4 are as follows. The bismuth octylate is the same as that shown in Table 1 above.
-EXL5030 (trifunctional polypropylene glycol): Exenol 5030, number average molecular weight of about 5000, manufactured by Asahi Glass Co., Ltd.-EXL3020: (bifunctional polypropylene glycol): Exenol 3020, number average molecular weight of about 3000, manufactured by Asahi Glass Co., Ltd.-Surface treatment Precipitated calcium carbonate: MS-700, manufactured by Maruo Calcium Co., Ltd. ・ Heavy calcium carbonate: Ryton A-4, manufactured by Bihoku Powder Chemical Co., Ltd. ・ Octylate Ca / neodecanoate Ca (calcium octylate and calcium neodecanoate) Mixture of: Catcat Ca-5B, manufactured by Nippon Chemical Industry Co., Ltd.

As is clear from the results shown in Table 5 above, the compositions of Comparative Examples 1 and 2 produced foaming and had low curability after storage, whereas the compositions of Examples 1 to 5 were all. There was little foaming and curability was good. Moreover, it was shown that the physical properties after storage compared with the initial stage are well maintained especially at M ₅₀ and M ₁₅₀ for the compositions of Examples 1 to 5. This is considered due to the fact that the catalytic activity is maintained until the main agent and the curing agent are mixed and cured.

Claims (9)

A main agent containing a urethane prepolymer and bismuth organic acid;
A two-component urethane composition comprising a curing agent containing an active hydrogen-containing compound.   The two-component urethane composition according to claim 1, wherein the bismuth organic acid is bismuth organic carboxylate and / or bismuth resinate.   The two-component urethane composition according to claim 2, wherein the organic bismuth carboxylate is at least one selected from the group consisting of bismuth octylate, bismuth 2-ethylhexylate and bismuth neodecanoate.   The two-component urethane composition according to claim 2 or 3, wherein the bismuth resinate is bismuth abietic acid.   The two-component urethane composition according to any one of claims 1 to 4, wherein the curing agent further contains an organic acid calcium.   The two-component urethane composition according to claim 5, wherein the organic acid calcium is organic calcium carboxylate and / or calcium resinate.   The two-component urethane composition according to claim 6, wherein the organic calcium carboxylate is at least one selected from the group consisting of calcium octylate, calcium 2-ethylhexylate and calcium neodecanoate. A method for producing a two-component urethane composition according to any one of claims 1 to 7,
Reacting a polyol compound and an isocyanate group-containing compound in the presence of an organic acid bismuth to produce a main agent containing the urethane prepolymer and the organic acid bismuth;
A method for producing a two-component urethane composition comprising a step of producing a curing agent containing the active hydrogen-containing compound.   A method for producing a urethane prepolymer, wherein a polyol compound and an isocyanate group-containing compound are reacted in the presence of bismuth organic acid to obtain a urethane prepolymer.